WO2015133857A1 - Method for coating metal using silsesquioxane composite polymer - Google Patents
Method for coating metal using silsesquioxane composite polymer Download PDFInfo
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- WO2015133857A1 WO2015133857A1 PCT/KR2015/002174 KR2015002174W WO2015133857A1 WO 2015133857 A1 WO2015133857 A1 WO 2015133857A1 KR 2015002174 W KR2015002174 W KR 2015002174W WO 2015133857 A1 WO2015133857 A1 WO 2015133857A1
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- methyl
- pomma
- phenyl
- glyp
- eche
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- 0 *C(*)(C1(*)*)*(*)(*2)OC(*)(*)C(*)(*)O[Si]12*=C Chemical compound *C(*)(C1(*)*)*(*)(*2)OC(*)(*)C(*)(*)O[Si]12*=C 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to a metal coating method using a silsesquioxane composite polymer, and more particularly, to a silsesquioxane composite including a linear silsesquioxane chain and a cage silsesquioxane having a specific structure in one polymer.
- a metal coating method using a silsesquioxane composite polymer excellent in adhesion.
- metals or plated metals are easily rusted by moisture and oxygen in the air when exposed to air. This corrosion decreases the gloss of the metal and thus is aesthetically unfavorable and can seriously affect the quality of the product.
- conventional methods such as painting, plating, oxide film, cathodic protection, and alloys have been attempted.
- the corrosion resistance (rustproof) sustainability may be deteriorated in some cases. Since it is necessary and expensive, there is still a need for research on a method of excellent anti-rust sustainability while being practically easily applied to metal using a coating solution.
- Korean Patent Laid-Open Publication No. 10-2011-0054009 discloses a method of rustproofing a zinc or zinc alloy surface using a blackening chemical treatment solution containing phosphate ions, iron ions, manganese ions, and nitrate ions on a metal surface.
- a blackening chemical treatment solution containing phosphate ions, iron ions, manganese ions, and nitrate ions on a metal surface.
- the present invention not only facilitates the coating process by coating using a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, moisture shielding properties, antifouling properties.
- An object of the present invention is to provide a metal coating method which is excellent in glossiness, surface strength, and thermal stability and at the same time excellent in adhesion.
- an object of the present invention is to provide a metal coating composition capable of imparting antirust properties, scratch resistance, water repellent properties, water shielding properties, antifouling properties, glossiness, surface strength, and thermal stability to metals.
- the present invention provides a metal coating method comprising coating and curing a metal coating composition comprising a silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 on a metal surface:
- Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
- Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
- R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups;
- Cyclohexyl epoxy group (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ⁇ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ⁇ C 40 heteroaryl group; An aralkyl group of C 3 ⁇ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen,
- a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
- b are each independently an integer of 1 to 500
- e are each independently 1 or 2, preferably 1,
- n is independently an integer of 1-20, Preferably it is 3-10.
- the present invention provides a metal coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 9.
- the present invention is characterized in that the metal coating composition comprising a silsesquioxane composite polymer represented by any one of the above formulas (1) to (9) is coated on the surface to include a cured cured product to provide.
- the present invention also provides an article comprising the silsesquioxane composite polymer coating metal.
- the metal coating method according to the present invention not only facilitates the coating process by coating with a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, water shielding property, antifouling property, glossiness, surface of the formed coating layer.
- Excellent strength, thermal stability, and adhesiveness make it useful for automobiles, kitchen utensils, metal pipes (including water pipes), metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc. In addition, it can be efficiently used in the field of semiconductor and display where metal wiring is used.
- the metal coating method of the present invention provides a metal coating method comprising coating and curing a metal coating composition comprising a silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 on a metal surface:
- Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
- Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
- R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
- a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
- b are each independently an integer of 1 to 500
- e are each independently 1 or 2, preferably 1,
- n is independently an integer of 1-20, Preferably it is 3-10.
- the metal coating method of the present invention and the metal coating composition used therein have a repeating unit of [A] a and [D] d, and have a specific structure having a repeating unit of [B] b or [E] e.
- the formation of a single coating layer through the solution process provides excellent anti-rust sustainability, scratch resistance, water repellency, water shielding properties, antifouling properties, glossiness, surface strength, And thermal stability.
- the metal to be coated is not particularly limited as long as it is composed of a metal.
- all metals such as iron, copper, aluminum, and stainless may be applied, and both metal and plating may be applied.
- steel, steel, structures, pipes (water pipes, sewer pipes, gas pipes, etc.), accessories, etc., if they are made of metal, can all be included in the coating, and can be applied to metal wiring (electronics such as semiconductors, displays, etc.).
- R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
- a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic.
- the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
- the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5
- the pH of the reaction solution of the second step is preferably 2 to 4
- the pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
- the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
- step 1 Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled;
- the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added.
- a second step of stirring A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
- the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9,
- the pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4.
- the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
- the terminal may further include a repeating unit of [E] e.
- a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
- the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba.
- the amine based catalyst may be tetramethylammonium hydroxide (TMAH)
- the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ).
- the content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted.
- the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation.
- the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
- the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art.
- organic solvent commonly used in the art.
- solvents such as nit
- the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Organosilanes comprising R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 can be used
- the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer
- the organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
- organosilane compound examples include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane,
- n of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of the above formulas may be substituted with an integer of 1 to 20, preferably 3 to 10, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
- R is as defined above.
- n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
- R is as defined above.
- the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below.
- ECHE Epoxycyclohexyl
- GlyP means Glycidoxypropyl
- POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use.
- n is 1-8 each independently.
- the silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
- the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
- the silsesquioxane composite polymer of Chemical Formula 3 may be a polymer described in Table 5 or 6 below.
- the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
- the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
- the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
- the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
- the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
- the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
- the silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
- the weight average molecular weight of the silsesquioxane composite polymer according to the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.
- the metal coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more kinds of composite polymers, and is preferably represented by any one of Formulas 3 to 9. It is preferable to use a silsesquioxane composite polymer.
- the physical properties of the coating can be further improved by including the repeating unit [B] b or [E] e.
- the metal coating composition may be coated alone as a solventless type when the silsesquioxane composite polymer is in a liquid state, and may include an organic solvent in the case of a solid phase.
- the coating composition may further include an initiator or a curing agent.
- the coating composition is characterized in that it comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art that is compatible with the composite polymer, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
- additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
- the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
- organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol,
- polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto.
- the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
- an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group
- various curing using heat or light is possible.
- the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
- various initiators may be used, and the initiator may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
- a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride.
- sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations).
- Iodonium such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopent
- the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
- phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
- the hardener is preferably included in 0.1-20 parts by weight based on 100 parts by weight of the composition.
- triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutyl
- the present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
- additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
- Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength.
- Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
- Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aral
- polyester hydroxy polydimethylsiloxane Polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc
- the method of coating the metal coating composition on the metal surface is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping,
- the curing temperature in the case of thermosetting is 80 to 120.
- the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, even more preferably 1 to 100 um. Within the above range, not only can the surface hardness of 7H or more be stably secured, but also excellent physical properties of the substrate surface properties. In particular, when the coating layer is laminated to a thickness of 10um or more, the surface hardness can be represented stably 9H.
- the present invention is a silsesquioxane composite polymer coating metal, characterized in that it comprises a cured hardened by coating a metal coating composition comprising a silsesquioxane composite polymer represented by any one of the above formulas (1) to (9)
- a metal coating composition comprising a silsesquioxane composite polymer represented by any one of the above formulas (1) to (9)
- the silsesquioxane composite polymer coating metal may be prepared by the metal coating method.
- the silsesquioxane composite polymer coating metal according to the present invention has excellent adhesion between the silsesquioxane composite polymer coating layer and the metal, and the formed silsesquioxane composite polymer coating layer has excellent rust resistance, scratch resistance, It imparts water repellent properties, moisture shielding properties, antifouling properties, glossiness, surface strength, and thermal stability.
- Articles containing the silsesquioxane composite polymer coating metal of the present invention is a product containing the silsesquioxane composite polymer coating metal can be usefully used in various fields, in particular, automobiles, kitchen appliances, metal pipes (including water pipes) ), As well as metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc., as well as can be efficiently used in the field of semiconductors and displays where metal wiring is used.
- ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
- GPTMS is Glycidoxypropytrimethoxysilane
- MAPTMS is (methacryloyloxy) propyltrimethoxysilane
- PTMS is Phenyltrimethoxysilane
- MTMS is Methyltrimethoxysilane
- ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane
- MAPTMDS stands for Di (methacryloyloxy) propy
- PTMDS stands for Di (phenyl) tetramethoxy disiloxane
- MTMDS stands for Di
- a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
- KOH Potassium hydroxide
- TMAH tetramethylammonium hydroxide
- Example 1-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
- the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
- Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
- Example 1-c 30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare a coating composition of 100 g. Thereafter, 3 parts by weight of chloro acetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV 3500 were added to 100 parts of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
- Example 1-c 50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
- Example 1-c alone constitute a coating composition without a separate composition.
- Example 1 In order to prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
- Example 1-b 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
- silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Example 2.
- Example 1 In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
- Example 1-c To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and the mixture was adjusted to a temperature of 4 for 30 minutes. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
- Example 3-a After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- Example 3-b After the reaction mixture was obtained in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
- the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was 17,000 in terms of styrene
- n value was 4-6
- the results of formula (3) are as follows.
- silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
- a continuous hydrolysis and condensation were carried out stepwise to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent to that described in Example 1.
- a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
- KOH Potassium hydroxide
- TMAH tetramethylammonium hydroxide
- Example 4-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
- the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
- XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
- Example 6-b 0.35 wt% HCl aqueous solution was added dropwise very slowly to the mixed solution of Example 4-b, the pH was adjusted to have acidity, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, it could be confirmed that the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made.
- the terminal was converted into a cage structure using a trifunctional monomer.
- 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
- the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 4 results are as follows.
- silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
- Example 1 The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
- Example 4-b To the mixture of Example 4-b during the reaction, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture.
- Example 5-a After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
- the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.
- silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Example 5.
- Example 1 To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.
- Example 4-c To the mixture obtained in Example 4-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to be acidic, and stirred at a temperature of 4 for 30 minutes. It was. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
- Example 6-a After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- Example 6-b the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
- the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was obtained in the styrene conversion value of 21,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are as follows.
- silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Example 6.
- Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Example 1.
- a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
- KOH Potassium hydroxide
- TMAH tetramethylammonium hydroxide
- Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
- the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
- Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
- the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
- XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.
- Example 7-a catalyst To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours.
- the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
- Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
- the terminal was converted into a cage structure using a trifunctional monomer.
- 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state.
- the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was a styrene conversion value of 24,000
- the n value of X was 4-6
- the n value of Y was 4-6.
- silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Example 7.
- Example 1 In order to manufacture a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
- Example 7-d 15 parts by weight of 0.36 wt% HCl aqueous solution was added very slowly to the mixed solution of Example 7-d, which was in progress, adjusted to have an acidic pH, and stirred at a temperature of 4 for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted.
- the terminal was converted into a cage structure using a trifunctional monomer.
- 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state.
- the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
- silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 26 below. At this time, the manufacturing method was equally applied to the method used in Example 8.
- Example 1 In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
- Example 7-g To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, the pH was adjusted to have an acidity, and the mixture was stirred at a temperature of 4 for 30 minutes. It was. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
- Example 9-a After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
- Example 9-b After the reaction mixture was obtained in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
- the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction.
- the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
- the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.
- silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
- the coating composition prepared in Examples 1 to 9 was coated on a galvanized steel sheet, stainless steel, and copper wiring, and cured to measure surface properties.
- the pencil hardness method (JIS 5600-5-4) is generally rated at 750 g load, which is 10 mm horizontal at a rate of 0.5 mm per second at a 45-degree angle to the coating surface at a more severe 1 kgf load.
- the coating film was moved to evaluate the scratches. If the scratches are not confirmed more than 3 mm more than 3 times in 5 experiments, select the pencil of the higher hardness, and if the scratches are more than 2 times, select the pencil and the pencil hardness lower than the pencil hardness is the pencil of the coating film.
- the hardness is shown in Table 28 below.
- the metal coating method according to the present invention not only facilitates the coating process by coating with a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, water shielding property, antifouling property, glossiness, surface of the formed coating layer.
- Excellent strength, thermal stability, and adhesiveness make it useful for automobiles, kitchen utensils, metal pipes (including water pipes), metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc. In addition, it can be efficiently used in the field of semiconductor and display where metal wiring is used.
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Abstract
The present invention relates to a method for coating metal using a silsesquioxane composite polymer, and more specifically, by coating the metal surface by means of a silsesquioxane composite polymer comprising, within a single polymer, a linear silsesquioxane chain of a particular structure and cage-type silsesquioxane, the method for coating metal using silsesquioxane composite polymer facilitates the coating process and the formed coating layer has superb characteristics for sustained rust resistance, scratch resistance, water repellency, moisture blocking, soil resistance, glossiness, surface strength, and thermal stability, and additionally has an excellent adhesive property.
Description
본 발명은 실세스퀴옥산 복합 고분자를 이용한 금속코팅방법에 관한 것으로, 보다 상세하게는 하나의 고분자 내에 특정 구조의 선형 실세스퀴옥산 사슬 및 케이지형 실세스퀴옥산을 포함하는 실세스퀴옥산 복합 고분자를 이용하여 금속표면을 코팅함으로써 코팅공정이 용이할 뿐만 아니라 형성된 코팅층의 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성이 우수하며 동시에 접착성이 우수한 실세스퀴옥산 복합 고분자를 이용한 금속코팅방법에 관한 것이다.The present invention relates to a metal coating method using a silsesquioxane composite polymer, and more particularly, to a silsesquioxane composite including a linear silsesquioxane chain and a cage silsesquioxane having a specific structure in one polymer. By coating the metal surface with a polymer, the coating process is not only easy, but also the rust resistance, scratch resistance, water repellent property, water shielding property, antifouling property, glossiness, surface strength, and thermal stability of the formed coating layer It relates to a metal coating method using a silsesquioxane composite polymer excellent in adhesion.
일반적으로 금속 또는 도금된 금속들은 공기 중에 노출 되었을 때 공기 중의 수분 및 산소에 의해 쉽게 녹이 쓰는 현상이 있다. 이러한 부식은 금속의 광택을 줄여 미관상 좋지 못하며, 제품의 품질에 심각하게 영향을 줄 수 있다. 이러한 부식을 지연 또는 방지하고자 종래 도장, 도금, 산화막, 음극화보호, 합금 등의 방법이 시도되고 있으나, 종래 방법들은 경우에 따라 내부식성(방청) 지속능력이 떨어질 수 있으며, 여러 단계의 공정이 필요하고, 비용 또한 고가일 수 있어서 실용적으로 코팅용액을 이용하여 손쉽게 금속에 적용될 수 있으면서도 방청지속능력이 우수한 방법에 대한 연구가 여전히 요청되고 있는 실정이다.Generally, metals or plated metals are easily rusted by moisture and oxygen in the air when exposed to air. This corrosion decreases the gloss of the metal and thus is aesthetically unfavorable and can seriously affect the quality of the product. In order to delay or prevent such corrosion, conventional methods such as painting, plating, oxide film, cathodic protection, and alloys have been attempted. However, in the conventional methods, the corrosion resistance (rustproof) sustainability may be deteriorated in some cases. Since it is necessary and expensive, there is still a need for research on a method of excellent anti-rust sustainability while being practically easily applied to metal using a coating solution.
이러한 용액형 코팅소재로 금속에 방청특성을 부여함에 있어서 물리적으로 금속과의 접착성, 코팅의 평탄성, 기타 발수 또는 수분차폐특성 등이 요청된다. 특히 코팅층이 금속과 강한 접착력을 가지고, 코팅층 형성 공정 시 유동특성이 부여될 수 있도록 코팅조성물을 화학적으로 설계하는 것이 요청된다.In providing the rust-preventing property to the metal with such a solution type coating material, physical adhesion to the metal, flatness of the coating, and other water repellent or moisture shielding properties are required. In particular, it is required to chemically design the coating composition so that the coating layer has a strong adhesion with the metal and can be given flow characteristics in the coating layer forming process.
종래 대한민국특허공개 제10-2011-0054009호에서는 금속 표면에 인산이온, 철이온, 망간이온, 질산이온을 포함하는 흑색화 화성처리액을 이용하여 아연 또는 아연합금 표면을 방청처리하는 방법이 개시되어 있으며, 대한민국특허공개 제10-2014-0013265호에서는 아연도금 강판에 실리케이트 화합물을 도포하여 방청 효과를 구현하고자 하는 시도가 있었지만 방청지속능력에 대한 여전한 부족함이 있으며, 내스크레치성, 방오특성 또는 광택성 등을 동시에 요구하는 수요자의 요구를 만족시키기에는 어려움이 많았다. Korean Patent Laid-Open Publication No. 10-2011-0054009 discloses a method of rustproofing a zinc or zinc alloy surface using a blackening chemical treatment solution containing phosphate ions, iron ions, manganese ions, and nitrate ions on a metal surface. In the Republic of Korea Patent Publication No. 10-2014-0013265, there was an attempt to implement the antirust effect by applying a silicate compound to the galvanized steel sheet, but there is still a lack of the rust resistance persistence, scratch resistance, antifouling properties or gloss There were many difficulties in satisfying the needs of consumers who demanded their backs at the same time.
상기와 같은 문제점을 해결하기 위해, 본 발명은 금속 표면 위에 코팅용액을 이용하여 코팅함으로써 코팅공정이 용이할 뿐만 아니라 형성된 코팅층의 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성이 우수하며 동시에 접착성이 우수한 금속코팅방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention not only facilitates the coating process by coating using a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, moisture shielding properties, antifouling properties, An object of the present invention is to provide a metal coating method which is excellent in glossiness, surface strength, and thermal stability and at the same time excellent in adhesion.
또한 본 발명은 금속에 대하여 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성을 부여할 수 있는 금속코팅조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a metal coating composition capable of imparting antirust properties, scratch resistance, water repellent properties, water shielding properties, antifouling properties, glossiness, surface strength, and thermal stability to metals.
또한 본 발명은 표면에 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성이 우수하며 동시에 접착성이 우수한 코팅층을 가지는 금속을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a metal having a coating layer having excellent antirust property, scratch resistance, water repellent property, water shielding property, antifouling property, glossiness, surface strength, and thermal stability and excellent adhesiveness on the surface. It is done.
또한 본 발명은 상기 코팅층을 가지는 금속을 포함하는 것을 특징으로 하는 물품을 제공하는 것을 목적으로 한다.It is also an object of the present invention to provide an article comprising a metal having the coating layer.
상기 목적을 달성하기 위해 본 발명은 금속 표면 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 금속코팅방법을 제공한다:In order to achieve the above object, the present invention provides a metal coating method comprising coating and curing a metal coating composition comprising a silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 on a metal surface:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,
A는A is
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기;R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups;
사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
또한 본 발명은 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물을 제공한다.In another aspect, the present invention provides a metal coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 9.
또한 본 발명은 표면 위에 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물이 코팅되어 경화된 경화물을 포함하는 것을 특징으로 실세스퀴옥산 복합 고분자 코팅 금속을 제공한다.In another aspect, the present invention is characterized in that the metal coating composition comprising a silsesquioxane composite polymer represented by any one of the above formulas (1) to (9) is coated on the surface to include a cured cured product to provide.
또한 본 발명은 상기 실세스퀴옥산 복합 고분자 코팅 금속을 포함하는 물품을 제공한다.The present invention also provides an article comprising the silsesquioxane composite polymer coating metal.
본 발명에 따른 금속코팅방법은 금속 표면 위에 코팅용액을 이용하여 코팅함으로써 코팅공정이 용이할 뿐만 아니라 형성된 코팅층의 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성이 우수하며 동시에 접착성이 우수하여 자동차, 주방용품, 금속관(상수도관 포함), 금속조형물, 가로등, 교통표지판, 태양전지 외관프레임, 도로분리대, 건축물 등에 유용하게 사용할 수 있을 뿐만 아니라 금속 배선이 사용되는 반도체, 디스플레이 분야에도 효율적으로 사용될 수 있다.The metal coating method according to the present invention not only facilitates the coating process by coating with a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, water shielding property, antifouling property, glossiness, surface of the formed coating layer. Excellent strength, thermal stability, and adhesiveness make it useful for automobiles, kitchen utensils, metal pipes (including water pipes), metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc. In addition, it can be efficiently used in the field of semiconductor and display where metal wiring is used.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 금속코팅방법은 금속 표면 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 금속코팅방법을 제공한다:The metal coating method of the present invention provides a metal coating method comprising coating and curing a metal coating composition comprising a silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 9 on a metal surface:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,
A는A is
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
본 발명의 금속코팅방법과 이에 사용되는 금속코팅조성물은 상기 [A]a와 [D]d의 반복단위를 가지며, 선택적으로 [B]b 또는 [E]e 반복단위를 가지는 특정 구조의 실세스퀴옥산 고분자를 금속의 표면에 코팅하고 경화함으로써, 용액공정을 통한 단일 코팅층의 형성만으로도 금속에 대하여 우수한 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성을 가지게 할 수 있다.The metal coating method of the present invention and the metal coating composition used therein have a repeating unit of [A] a and [D] d, and have a specific structure having a repeating unit of [B] b or [E] e. By coating and curing the quioxane polymer on the surface of the metal, the formation of a single coating layer through the solution process provides excellent anti-rust sustainability, scratch resistance, water repellency, water shielding properties, antifouling properties, glossiness, surface strength, And thermal stability.
본 발명에 있어서 코팅의 대상이 되는 상기 금속은 금속으로 구성된 것이면 특별히 한정되지 않으며, 일예로 철, 구리, 알루미늄, 스테인레스 등 일반금속이 모두 적용될 수 있으며, 도금 및 합금에도 모두 적용될 수 있다. 또한 강판, 강재, 구조물, 관(상수도관, 하수도관, 가스관 등), 악세서리 등 금속으로 이루어진 것이면 코팅대상에 모두 포함될 수 있으며, 금속 배선(반도체, 디스플레이 등의 전자제품)에도 적용될 수 있다.In the present invention, the metal to be coated is not particularly limited as long as it is composed of a metal. For example, all metals such as iron, copper, aluminum, and stainless may be applied, and both metal and plating may be applied. In addition, steel, steel, structures, pipes (water pipes, sewer pipes, gas pipes, etc.), accessories, etc., if they are made of metal, can all be included in the coating, and can be applied to metal wiring (electronics such as semiconductors, displays, etc.).
본 발명의 상기 화학식 1로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 1 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 하기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR2)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 10; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 2 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
[화학식 10][Formula 10]
상기 식에서 R1, R2, R16, D, a 및 d는 화학식 1 내지 9에서 정의한 바와 같다.Wherein R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
본 발명의 상기 화학식 2로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 2 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR3)2 및 [D]d(OR4)2 구조를 화학식 2와 같이 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 제3단계 반응을 거쳐, 단독으로 생성되는 부산물인 cage 구조를 재결정으로 제거하여주는 정제단계를 진행하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [D] d (OR 3 ) 2 and [D] d (OR 4 ) 2 structures into the chemical formula 10 after the first step, as shown in the chemical formula 2. A second step of adding and stirring an excess of the organic silane compound after the adjustment; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And through a third step of the reaction, it can be prepared by proceeding to the purification step to remove the cage structure as a by-product generated by recrystallization.
본 발명의 상기 화학식 3으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 3 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR5)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 5 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
본 발명의 상기 화학식 4로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 4 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도를 조절하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR7)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and adjusting the degree of condensation; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 7 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic acid, and then the organic silane compound A second step of adding and stirring; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
본 발명의 상기 화학식 5로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (5) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR8)2, [D]d(OR9)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 제3단계; 및 제3단계 이후 재결정과 필터과정을 통하여, 단독 cage 생성 구조를 제거하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [B] b structure and the [D] d (OR 8 ) 2 , [D] d (OR 9 ) 2 structure into the chemical formula 10 after the first step. A second step of adding and stirring an excess of the organic silane compound after adjusting to acidity; And a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic. And a fourth step of removing the single cage generation structure through recrystallization and filtering after the third step.
본 발명의 상기 화학식 6으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (6) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR10)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 10 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic, and then the organic silane compound A second step of adding and stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
바람직하기로 상기 화학식 1 내지 6을 제조하는 방법에서 본 발명의 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, Ee을 도입하는 제4단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
본 발명의 상기 화학식 7로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (7) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조 및 [D]d(OR12)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the structure [B] b and the structure [D] d (OR 12 ) 2 to the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; And four steps of condensing and connecting two or more materials obtained through the three steps under basic conditions.
본 발명의 상기 화학식 8로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (8) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조, [D]d(OR14)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계; 상기 4단계 이후 [D]d(OR13)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 및 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the [B] b structure, the [D] d (OR 14 ) 2 structure into the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
본 발명의 상기 화학식 9로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (9) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 화합물을 염기성 조건에서 축합하여 연결하는 4단계; 상기 제4단계 이후 [D]d(OR5)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계; 상기 제6단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제7단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; A second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid in order to introduce the structure [B] b into the chemical formula 10 obtained in step 1, and then adding and stirring an organic silane compound; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more compounds obtained through the three steps in basic conditions; A fifth step of adding an acidic catalyst to a reactor for introducing [D] d (OR 5 ) 2 to adjust the reaction solution to acidic acid after the fourth step, and then adding and stirring an organic silane compound; A sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction; After the sixth step, to introduce the [E] eX 2 structure at the end of the composite polymer to the acidic catalyst in the reactor to convert the reaction solution into an acidic atmosphere and a mixture of the organosilane compound comprising a seventh step of stirring Can be prepared.
바람직하기로 상기 화학식 7 내지 9의 고분자를 제조하는 방법에서 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, 제4단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제5단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제6단계의 반응액의 8 내지 11.5인 것이 바람직하고, Ee를 도입하는 제7단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably, the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9, The pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
또한 필요한 경우 각각의 복합 고분자에 [B]b 구조 및 [D]d(OR)2 구조를 더욱 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 단계; 및 상기 단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 단계를 통하여 복합 고분자 내에 [B]b 반복단위를 더욱 포함할 수 있다.If necessary, in order to further introduce the [B] b structure and the [D] d (OR) 2 structure to each of the composite polymers, an acidic catalyst was added to the reactor to adjust the reaction solution to acidic acid, and then an organic silane compound was added. Stirring; And [B] b repeating units in the composite polymer through the step of performing a condensation reaction by adding a basic catalyst to the reactor and converting the reaction solution to basic after the above step.
또한 필요한 경우 각각의 복합 고분자의 말단에 [E]eX2 구조를 도입하기 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 단계를 포함하여 복합 고분자의 말단에 [E]e의 반복단위를 더욱 포함할 수 있다.In addition, if necessary, in order to introduce an [E] eX 2 structure at the end of each composite polymer, an acidic catalyst was added to the reactor to convert the reaction solution into an acidic atmosphere, and the mixture of the organosilane compounds was stirred. The terminal may further include a repeating unit of [E] e.
상기 실세스퀴옥산 복합 고분자의 제조방법에서는 염기성 촉매로서 바람직하기로는 2종 이상의 염기성 촉매의 혼합촉매를 사용하고, 이를 산성 촉매로 중화 및 산성화하여 재 가수분해를 유도하며, 다시 2종 이상의 염기성 촉매의 혼합촉매를 이용하여 염기성으로 축합을 진행함으로써 하나의 반응기내에서 산도와 염기도를 연속적으로 조절할 수 있다.In the production method of the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
이때, 상기 염기성 촉매는 Li, Na, K, Ca 및 Ba 으로 이루어진 군에서 선택된 금속계 염기성 촉매 및 아민계 염기성 촉매에서 선택되는 2종 이상의 물질을 적절히 조합하여 제조될 수 있다. 바람직하게는 상기 아민계 염기성 촉매가 테트라메틸암모늄 하이드록시드(TMAH)이고, 금속계 염기성 촉매가 포타슘 하이드록시드(KOH) 또는 중탄산나트륨 (NaHCO3)일 수 있다. 상기 혼합촉매에서 각 성분의 함량은 바람직하기로는 아민계 염기성 촉매와 금속계 염기성 촉매의 비율이 10 내지 90: 10 내지 90 중량부의 비율에서 임의로 조절할 수 있다. 상기 범위 내인 경우 가수분해시 관능기와 촉매와의 반응성을 최소화시킬 수 있으며, 이로 인해 Si-OH 또는 Si-알콕시 등의 유기 관능기의 결함이 현저히 감소하여 축합도를 자유로이 조절할 수 있는 장점이 있다. 또한, 상기 산성 촉매로는 당분야에서 통상적으로 사용하는 산성 물질이라면 제한 없이 사용될 수 있으며, 예를 들어, HCl, H2SO4, HNO3, CH3COOH 등의 일반 산성물질을 사용할 수 있고, 또한 latic acid, tartaric acid, maleic acid, citric acid 등의 유기계 산성물질도 적용할 수 있다.In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine based catalyst may be tetramethylammonium hydroxide (TMAH), and the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ). The content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted. Within the above range, the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation. In addition, the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
본 발명의 실세스퀴옥산 복합 고분자의 제조방법에서 상기 유기용매는 당분야에서 통상적으로 사용하는 유기용매라면 제한 없이 사용될 수 있으며, 예를 들어, 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 사용할 수 있다.In the method for preparing the silsesquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art. For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Alcohols such as cellosolves, ketones such as lactate, acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Polar solvents such as methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane and acro Various solvents, such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzyl alcohol, can be used.
또한, 상기 유기 실란계 화합물로는 본 발명의 실세스퀴옥산 복합 고분자인 화학식 1 내지 9의 R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22를 포함하는 유기 실란이 사용될 수 있으며, 바람직하기로 실세스퀴옥산 복합 고분자의 내화학성을 증가시켜 비팽윤성을 향상시키는 효과가 있는 페닐기 또는 아미노기를 포함하는 유기 실란 화합물, 또는 복합 고분자의 경화 밀도를 증가시켜 경화층의 기계적 강도 및 경도를 향상시키는 효과가 있는 에폭시기 또는 (메타)아크릴기를 포함하는 유기 실란 화합물을 사용할 수 있다.In addition, as the organosilane compound, the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Organosilanes comprising R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 can be used Preferably, the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer The organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
상기 유기 실란계 화합물의 구체적인 예로는 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3-(메타아크릴옥시)프로필트리메톡시실란, 3,4-에폭시부틸트리메톡시실란, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 아미노프로필트리에톡시실란, 비닐트리에톡시실란, 비닐트리-t-부톡시실란, 비닐트리이소부톡시실란, 비닐트리이소프로폭시실란, 비닐트리페녹시실란, 페닐트리에톡시실란, 페닐트리메톡시실란, 아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 디메틸테트라메톡시실록산, 디페닐테트라메톡시실록산 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 병용하여 사용할 수도 있다. 최종 제조되는 조성물의 물성을 위하여 2종 이상을 혼합하여 사용하는 것이 보다 바람직하다.Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimeth Methoxysilane, dimethyl tetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, You may use individually by 1 type or in combination of 2 or more types. It is more preferable to mix and use 2 or more types for the physical property of the composition currently manufactured.
본 발명에서 상기 화학식들의 반복단위 [D]d에 도입된[(SiO3/2R)4+2nO] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 11과 같다:In the present invention, n of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of the above formulas may be substituted with an integer of 1 to 20, preferably 3 to 10, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
[화학식 11][Formula 11]
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
본 발명에서, 상기 화학식들의 반복단위 [B]b 또는 [E]e에 도입된[(SiO3/2R)4+2nR] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 12와 같다: In the present invention, n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
[화학식 12][Formula 12]
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
구체적인 예로 본 발명에 따른 실세스퀴옥산 고분자는 하기 표 1 내지 18에 고분자일 수 있다. 하기 표 1 내지 9에서 ECHE는 (Epoxycyclohexyl)ethyl, GlyP는 Glycidoxypropyl, POMMA는 (methacryloyloxy)propyl을 의미하며, 두 개 이상이 기재된 경우 혼합사용을 의미한다. n은 각각 독립적으로 1 내지 8이다.As a specific example, the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below. In Tables 1 to 9, ECHE means (Epoxycyclohexyl) ethyl, GlyP means Glycidoxypropyl, POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use. n is 1-8 each independently.
상기 화학식 1의 실세스퀴옥산 복합고분자는 하기 표 1 또는 2에 기재된 고분자일 수 있다.The silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
표 1
Table 1
No | R1 | R2 | R16 | R19 | Y의 R |
1-1 | OH,메톡시 | H,메틸 | ECHE | ECHE | ECHE |
1-2 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | 페닐 |
1-3 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | 메틸 |
1-4 | OH,메톡시 | H,메틸 | GlyP | GlyP | GlyP |
1-5 | OH,메톡시 | H,메틸 | POMMA | POMMA | POMMA |
1-6 | OH,메톡시 | H,메틸 | ECHE | 페닐 | 페닐 |
1-7 | OH,메톡시 | H,메틸 | ECHE | 메틸 | 메틸 |
1-8 | OH,메톡시 | H,메틸 | ECHE | GlyP | GlyP |
1-9 | OH,메톡시 | H,메틸 | ECHE | POMMA | POMMA |
1-10 | OH,메톡시 | H,메틸 | 페닐 | ECHE | ECHE |
1-11 | OH,메톡시 | H,메틸 | 페닐 | 메틸 | 메틸 |
1-12 | OH,메톡시 | H,메틸 | 페닐 | GlyP | GlyP |
1-13 | OH,메톡시 | H,메틸 | 페닐 | POMMA | POMMA |
1-14 | OH,메톡시 | H,메틸 | 메틸 | ECHE | ECHE |
1-15 | OH,메톡시 | H,메틸 | 메틸 | 페닐 | 페닐 |
1-16 | OH,메톡시 | H,메틸 | 메틸 | GlyP | GlyP |
1-17 | OH,메톡시 | H,메틸 | 메틸 | POMMA | POMMA |
1-18 | OH,메톡시 | H,메틸 | GlyP | ECHE | ECHE |
1-19 | OH,메톡시 | H,메틸 | GlyP | 페닐 | 페닐 |
1-20 | OH,메톡시 | H,메틸 | GlyP | 메틸 | 메틸 |
1-21 | OH,메톡시 | H,메틸 | GlyP | POMMA | POMMA |
1-22 | OH,메톡시 | H,메틸 | POMMA | ECHE | ECHE |
1-23 | OH,메톡시 | H,메틸 | POMMA | 페닐 | 페닐 |
1-24 | OH,메톡시 | H,메틸 | POMMA | 메틸 | 메틸 |
1-25 | OH,메톡시 | H,메틸 | POMMA | GlyP | GlyP |
No | R1 | R2 | R16 | R19 | Y R |
1-1 | OH, methoxy | H, methyl | ECHE | ECHE | ECHE |
1-2 | OH, methoxy | H, methyl | Phenyl | Phenyl | Phenyl |
1-3 | OH, methoxy | H, methyl | methyl | methyl | methyl |
1-4 | OH, methoxy | H, methyl | GlyP | GlyP | GlyP |
1-5 | OH, methoxy | H, methyl | POMMA | POMMA | POMMA |
1-6 | OH, methoxy | H, methyl | ECHE | Phenyl | Phenyl |
1-7 | OH, methoxy | H, methyl | ECHE | methyl | methyl |
1-8 | OH, methoxy | H, methyl | ECHE | GlyP | GlyP |
1-9 | OH, methoxy | H, methyl | ECHE | POMMA | POMMA |
1-10 | OH, methoxy | H, methyl | Phenyl | ECHE | ECHE |
1-11 | OH, methoxy | H, methyl | Phenyl | methyl | methyl |
1-12 | OH, methoxy | H, methyl | Phenyl | GlyP | GlyP |
1-13 | OH, methoxy | H, methyl | Phenyl | POMMA | POMMA |
1-14 | OH, methoxy | H, methyl | methyl | ECHE | ECHE |
1-15 | OH, methoxy | H, methyl | methyl | Phenyl | Phenyl |
1-16 | OH, methoxy | H, methyl | methyl | GlyP | GlyP |
1-17 | OH, methoxy | H, methyl | methyl | POMMA | POMMA |
1-18 | OH, methoxy | H, methyl | GlyP | ECHE | ECHE |
1-19 | OH, methoxy | H, methyl | GlyP | Phenyl | Phenyl |
1-20 | OH, methoxy | H, methyl | GlyP | methyl | methyl |
1-21 | OH, methoxy | H, methyl | GlyP | POMMA | POMMA |
1-22 | OH, methoxy | H, methyl | POMMA | ECHE | ECHE |
1-23 | OH, methoxy | H, methyl | POMMA | Phenyl | Phenyl |
1-24 | OH, methoxy | H, methyl | POMMA | methyl | methyl |
1-25 | OH, methoxy | H, methyl | POMMA | GlyP | GlyP |
표 2
TABLE 2
No | R1 | R2 | R16 | R19 | Y의 R | n |
2-1 | OH,메톡시 | H,메틸 | ECHE | 알킬사이올 | ECHE | 1~8 |
2-2 | OH, CF3 | H,에틸 | 페닐 | 페닐 | 페닐 | 1~8 |
2-3 | OH,메톡시 | H,아세틸틸 | 알킬사이올 | 메틸 | 메틸 | 1~8 |
2-4 | CF3,메톡시 | 비닐,메틸 | GlyP | 도데실 | GlyP | 1~8 |
2-5 | OH,메톡시 | H,메틸 | POMMA | 알킬사이올 | POMMA | 1~8 |
2-6 | OH, C8F13 | H, F | ECHE | 페닐 | 페닐 | 1~8 |
2-7 | OH, CF3 | CF3,메틸 | ECHE | 옥틸 | 메틸 | 1~8 |
2-8 | OH, C8F13 | H,메틸 | F | 알킬사이올 | GlyP | 1~8 |
2-9 | OH,메톡시 | H, CF3 | ECHE | POMMA | POMMA | 1~8 |
2-10 | OH,메톡시 | H,메틸 | 페닐 | 알킬사이올 | ECHE | 1~8 |
2-11 | OH, C8F13 | 아릴,메틸 | 알킬사이올 | 메틸 | 헥실 | 1~8 |
2-12 | OH,알킬사이올 | H,메타크릴 | 페닐 | GlyP | GlyP | 1~8 |
2-13 | OH,메톡시 | H,메틸 | 알킬사이올 | POMMA | POMMA | 1~8 |
2-14 | OH, 아크릴 | H,옥틸 | 메틸 | ECHE | 아미노프로필 | 1~8 |
2-15 | 비닐 ,메톡시 | H,메틸 | 메틸 | 알킬사이올 | 페닐 | 1~8 |
2-16 | 알킬아민 | H,메틸 | 메틸 | GlyP | GlyP | 1~8 |
2-17 | OH,에틸,메틸 | 알킬사이올,메틸 | 메틸 | POMMA | POMMA | 1~8 |
2-18 | 아세톡시,메톡시 | H,메틸 | GlyP | ECHE | 아미노프로필 | 1~8 |
2-19 | 프로폭시,메톡시 | H, CF3 | GlyP | 페닐 | 페닐 | 1~8 |
2-20 | OH, 메톡시 | H,메틸 | 아미노프로필 | 메틸 | 옥틸 | 1~8 |
2-21 | C8F13,메톡시 | C8F13,메틸 | GlyP | POMMA | POMMA | 1~8 |
2-22 | OH,아릴 | H,프로필 | POMMA | 프로필 | ECHE | 1~8 |
2-23 | OH,메톡시 | F,메틸 | POMMA | 페닐 | 페닐 | 1~8 |
2-24 | CF3,메타크릴 | H,메틸 | POMMA | 메틸 | 메틸 | 1~8 |
2-25 | OH,메톡시 | H,에틸 | 아미노프로필 | GlyP | GlyP | 1~8 |
No | R1 | R2 | R16 | R19 | Y R | n |
2-1 | OH, methoxy | H, methyl | ECHE | Alkyl siol | ECHE | 1-8 |
2-2 | OH, CF 3 | H, ethyl | Phenyl | Phenyl | Phenyl | 1-8 |
2-3 | OH, methoxy | H, acetyltyl | Alkyl siol | methyl | methyl | 1-8 |
2-4 | CF 3 , methoxy | Vinyl, methyl | GlyP | Dodecyl | GlyP | 1-8 |
2-5 | OH, methoxy | H, methyl | POMMA | Alkyl siol | POMMA | 1-8 |
2-6 | OH, C 8 F 13 | H, F | ECHE | Phenyl | Phenyl | 1-8 |
2-7 | OH, CF 3 | CF 3 , methyl | ECHE | Octyl | methyl | 1-8 |
2-8 | OH, C 8 F 13 | H, methyl | F | Alkyl siol | GlyP | 1-8 |
2-9 | OH, methoxy | H, CF 3 | ECHE | POMMA | POMMA | 1-8 |
2-10 | OH, methoxy | H, methyl | Phenyl | Alkyl siol | ECHE | 1-8 |
2-11 | OH, C 8 F 13 | Aryl, methyl | Alkyl siol | methyl | Hexyl | 1-8 |
2-12 | OH, alkyl siol | H, methacryl | Phenyl | GlyP | GlyP | 1-8 |
2-13 | OH, methoxy | H, methyl | Alkyl siol | POMMA | POMMA | 1-8 |
2-14 | OH, acrylic | H, octyl | methyl | ECHE | Aminopropyl | 1-8 |
2-15 | Vinyl, methoxy | H, methyl | methyl | Alkyl siol | Phenyl | 1-8 |
2-16 | Alkylamine | H, methyl | methyl | GlyP | GlyP | 1-8 |
2-17 | OH, ethyl, methyl | Alkyl siol, methyl | methyl | POMMA | POMMA | 1-8 |
2-18 | Acetoxy, methoxy | H, methyl | GlyP | ECHE | Aminopropyl | 1-8 |
2-19 | Propoxy, methoxy | H, CF 3 | GlyP | Phenyl | Phenyl | 1-8 |
2-20 | OH, methoxy | H, methyl | Aminopropyl | methyl | Octyl | 1-8 |
2-21 | C 8 F 13 , methoxy | C 8 F 13 , methyl | GlyP | POMMA | POMMA | 1-8 |
2-22 | OH, aryl | H, profile | POMMA | profile | ECHE | 1-8 |
2-23 | OH, methoxy | F, methyl | POMMA | Phenyl | Phenyl | 1-8 |
2-24 | CF 3 , methacryl | H, methyl | POMMA | methyl | methyl | 1-8 |
2-25 | OH, methoxy | H, ethyl | Aminopropyl | GlyP | GlyP | 1-8 |
구체적인 예로 상기 화학식 2의 실세스퀴옥산 복합고분자는 하기 표 3 및 4에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
표 3
TABLE 3
No | R3 | R4 | R16 | R19 | Y의 R |
3-1 | H,메틸 | H,메틸 | ECHE | ECHE | ECHE |
3-2 | H,메틸 | H,메틸 | 페닐 | 페닐 | 페닐 |
3-3 | H,메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
3-4 | H,메틸 | H,메틸 | GlyP | GlyP | GlyP |
3-5 | H,메틸 | H,메틸 | POMMA | POMMA | POMMA |
3-6 | H,메틸 | H,메틸 | ECHE | 페닐 | 페닐 |
3-7 | H,메틸 | H,메틸 | ECHE | 메틸 | 메틸 |
3-8 | H,메틸 | H,메틸 | ECHE | GlyP | GlyP |
3-9 | H,메틸 | H,메틸 | ECHE | POMMA | POMMA |
3-10 | H,메틸 | H,메틸 | 페닐 | ECHE | ECHE |
3-11 | H,메틸 | H,메틸 | 페닐 | 메틸 | 메틸 |
3-12 | H,메틸 | H,메틸 | 페닐 | GlyP | GlyP |
3-13 | H,메틸 | H,메틸 | 페닐 | POMMA | POMMA |
3-14 | H,메틸 | H,메틸 | 메틸 | ECHE | ECHE |
3-15 | H,메틸 | H,메틸 | 메틸 | 페닐 | 페닐 |
3-16 | H,메틸 | H,메틸 | 메틸 | GlyP | GlyP |
3-17 | H,메틸 | H,메틸 | 메틸 | POMMA | POMMA |
3-18 | H,메틸 | H,메틸 | GlyP | ECHE | ECHE |
3-19 | H,메틸 | H,메틸 | GlyP | 페닐 | 페닐 |
3-20 | H,메틸 | H,메틸 | GlyP | 메틸 | 메틸 |
3-21 | H,메틸 | H,메틸 | GlyP | POMMA | POMMA |
3-22 | H,메틸 | H,메틸 | POMMA | ECHE | ECHE |
3-23 | H,메틸 | H,메틸 | POMMA | 페닐 | 페닐 |
3-24 | H,메틸 | H,메틸 | POMMA | 메틸 | 메틸 |
3-25 | H,메틸 | H,메틸 | POMMA | GlyP | GlyP |
No | R3 | R4 | R16 | R19 | Y R |
3-1 | H, methyl | H, methyl | ECHE | ECHE | ECHE |
3-2 | H, methyl | H, methyl | Phenyl | Phenyl | Phenyl |
3-3 | H, methyl | H, methyl | methyl | methyl | methyl |
3-4 | H, methyl | H, methyl | GlyP | GlyP | GlyP |
3-5 | H, methyl | H, methyl | POMMA | POMMA | POMMA |
3-6 | H, methyl | H, methyl | ECHE | Phenyl | Phenyl |
3-7 | H, methyl | H, methyl | ECHE | methyl | methyl |
3-8 | H, methyl | H, methyl | ECHE | GlyP | GlyP |
3-9 | H, methyl | H, methyl | ECHE | POMMA | POMMA |
3-10 | H, methyl | H, methyl | Phenyl | ECHE | ECHE |
3-11 | H, methyl | H, methyl | Phenyl | methyl | methyl |
3-12 | H, methyl | H, methyl | Phenyl | GlyP | GlyP |
3-13 | H, methyl | H, methyl | Phenyl | POMMA | POMMA |
3-14 | H, methyl | H, methyl | methyl | ECHE | ECHE |
3-15 | H, methyl | H, methyl | methyl | Phenyl | Phenyl |
3-16 | H, methyl | H, methyl | methyl | GlyP | GlyP |
3-17 | H, methyl | H, methyl | methyl | POMMA | POMMA |
3-18 | H, methyl | H, methyl | GlyP | ECHE | ECHE |
3-19 | H, methyl | H, methyl | GlyP | Phenyl | Phenyl |
3-20 | H, methyl | H, methyl | GlyP | methyl | methyl |
3-21 | H, methyl | H, methyl | GlyP | POMMA | POMMA |
3-22 | H, methyl | H, methyl | POMMA | ECHE | ECHE |
3-23 | H, methyl | H, methyl | POMMA | Phenyl | Phenyl |
3-24 | H, methyl | H, methyl | POMMA | methyl | methyl |
3-25 | H, methyl | H, methyl | POMMA | GlyP | GlyP |
표 4
Table 4
No | R3 | R4 | R16 | R19 | Y의 R |
4-1 | OH,메톡시 | H,메틸 | ECHE | 알킬사이올 | ECHE |
4-2 | OH, CF3 | H,에틸 | 페닐 | 페닐 | 페닐 |
4-3 | OH,메톡시 | H,아세틸틸 | 알킬사이올 | 메틸 | 메틸 |
4-4 | CF3,메톡시 | 비닐,메틸 | POMMA | 도데실 | GlyP |
4-5 | OH, 아크릴 | H,메틸 | POMMA | 알킬사이올 | 옥틸 |
4-6 | 비닐 ,메톡시 | H, F | ECHE | 페닐 | POMMA |
4-7 | 알킬아민 | CF3,메틸 | ECHE | 옥틸 | 메틸 |
4-8 | OH,에틸,메틸 | H,메틸 | F | 아미노프로필 | GlyP |
4-9 | 아세톡시,메톡시 | H, CF3 | 아미노프로필 | POMMA | 헥실 |
4-10 | 프로폭시,메톡시 | H,메틸 | 페닐 | 알킬사이올 | ECHE |
4-11 | OH, C8F13 | 아릴,메틸 | 알킬사이올 | 메틸 | 헥실 |
4-12 | OH,메톡시 | H,메타크릴 | 페닐 | GlyP | GlyP |
4-13 | CF3,메톡시 | H,메틸 | 옥틸 | POMMA | POMMA |
4-14 | OH, 아크릴 | H,옥틸 | 메틸 | ECHE | 아미노프로필 |
4-15 | 비닐 ,메톡시 | H,메틸 | 옥틸 | 알킬사이올 | 페닐 |
4-16 | 알킬아민 | H,메틸 | 옥틸 | GlyP | GlyP |
4-17 | OH,메톡시 | 알킬사이올,메틸 | 메틸 | POMMA | POMMA |
4-18 | 아세톡시,메톡시 | H,메틸 | GlyP | ECHE | 아미노프로필 |
4-19 | 프로폭시,메톡시 | H, CF3 | GlyP | 아미노프로필 | 페닐 |
4-20 | OH, 메톡시 | H,메틸 | 아미노프로필 | 메틸 | 옥틸 |
4-21 | 프로폭시,메톡시 | C8F13,메틸 | GlyP | POMMA | POMMA |
4-22 | OH, 메톡시 | H,프로필 | POMMA | 프로필 | ECHE |
4-23 | C8F13,메톡시 | F,메틸 | POMMA | 페닐 | 페닐 |
4-24 | OH,아릴 | H,메틸 | GlyP | 메틸 | GlyP |
4-25 | OH,메톡시 | H,에틸 | 아미노프로필 | GlyP | GlyP |
No | R3 | R4 | R16 | R19 | Y R |
4-1 | OH, methoxy | H, methyl | ECHE | Alkyl siol | ECHE |
4-2 | OH, CF 3 | H, ethyl | Phenyl | Phenyl | Phenyl |
4-3 | OH, methoxy | H, acetyltyl | Alkyl siol | methyl | methyl |
4-4 | CF 3 , methoxy | Vinyl, methyl | POMMA | Dodecyl | GlyP |
4-5 | OH, acrylic | H, methyl | POMMA | Alkyl siol | Octyl |
4-6 | Vinyl, methoxy | H, F | ECHE | Phenyl | POMMA |
4-7 | Alkylamine | CF 3 , methyl | ECHE | Octyl | methyl |
4-8 | OH, ethyl, methyl | H, methyl | F | Aminopropyl | GlyP |
4-9 | Acetoxy, methoxy | H, CF 3 | Aminopropyl | POMMA | Hexyl |
4-10 | Propoxy, methoxy | H, methyl | Phenyl | Alkyl siol | ECHE |
4-11 | OH, C 8 F 13 | Aryl, methyl | Alkyl siol | methyl | Hexyl |
4-12 | OH, methoxy | H, methacryl | Phenyl | GlyP | GlyP |
4-13 | CF 3 , methoxy | H, methyl | Octyl | POMMA | POMMA |
4-14 | OH, acrylic | H, octyl | methyl | ECHE | Aminopropyl |
4-15 | Vinyl, methoxy | H, methyl | Octyl | Alkyl siol | Phenyl |
4-16 | Alkylamine | H, methyl | Octyl | GlyP | GlyP |
4-17 | OH, methoxy | Alkyl siol, methyl | methyl | POMMA | POMMA |
4-18 | Acetoxy, methoxy | H, methyl | GlyP | ECHE | Aminopropyl |
4-19 | Propoxy, methoxy | H, CF 3 | GlyP | Aminopropyl | Phenyl |
4-20 | OH, methoxy | H, methyl | Aminopropyl | methyl | Octyl |
4-21 | Propoxy, methoxy | C 8 F 13 , methyl | GlyP | POMMA | POMMA |
4-22 | OH, methoxy | H, profile | POMMA | profile | ECHE |
4-23 | C 8 F 13 , methoxy | F, methyl | POMMA | Phenyl | Phenyl |
4-24 | OH, aryl | H, methyl | GlyP | methyl | GlyP |
4-25 | OH, methoxy | H, ethyl | Aminopropyl | GlyP | GlyP |
구체적인 예로 상기 화학식 3의 실세스퀴옥산 복합고분자는 하기 표 5 또는 6에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 3 may be a polymer described in Table 5 or 6 below.
표 5
Table 5
No | R5 | R16 | R19 | R20 | Y의 R | X의 R |
5-1 | H,메틸 | ECHE | ECHE | ECHE | ECHE | ECHE |
5-2 | H,메틸 | 페닐 | 페닐 | 페닐 | 페닐 | 페닐 |
5-3 | H,메틸 | 메틸 | 메틸 | 메틸 | 메틸 | 메틸 |
5-4 | H,메틸 | GlyP | EGCDX | GlyP | EGCDX | GlyP |
5-5 | H,메틸 | POMMA | POMMA | POMMA | POMMA | POMMA |
5-6 | H,메틸 | ECHE | ECHE | 페닐 | ECHE | 페닐 |
5-7 | H,메틸 | ECHE | ECHE | 메틸 | ECHE | 메틸 |
5-8 | H,메틸 | ECHE | ECHE | GlyP | ECHE | GlyP |
5-9 | H,메틸 | ECHE | ECHE | POMMA | ECHE | POMMA |
5-10 | H,메틸 | ECHE | 페닐 | ECHE | 페닐 | ECHE |
5-11 | H,메틸 | ECHE | 메틸 | ECHE | 메틸 | ECHE |
5-12 | H,메틸 | ECHE | GlyP | ECHE | GlyP | ECHE |
5-13 | H,메틸 | ECHE | POMMA | ECHE | POMMA | ECHE |
5-14 | H,메틸 | 페닐 | 페닐 | ECHE | 페닐 | ECHE |
5-15 | H,메틸 | 페닐 | 페닐 | 메틸 | 페닐 | 메틸 |
5-16 | H,메틸 | 페닐 | 페닐 | EGDCX | 페닐 | EGDCX |
5-17 | H,메틸 | 페닐 | 페닐 | POMMA | 페닐 | POMMA |
5-18 | H,메틸 | 페닐 | ECHE | 페닐 | ECHE | 페닐 |
5-19 | H,메틸 | 페닐 | 메틸 | 페닐 | 메틸 | 페닐 |
5-20 | H,메틸 | 페닐 | GlyP | 페닐 | GlyP | 페닐 |
5-21 | H,메틸 | 페닐 | POMMA | 페닐 | POMMA | 페닐 |
5-22 | H,메틸 | 메틸 | 메틸 | ECHE | 메틸 | ECHE |
5-23 | H,메틸 | 메틸 | 메틸 | 페닐 | 메틸 | 페닐 |
5-25 | H,메틸 | 메틸 | 메틸 | GlyP | 메틸 | GlyP |
5-25 | H,메틸 | 메틸 | 메틸 | POMMA | 메틸 | POMMA |
5-26 | H,메틸 | 메틸 | ECHE | 메틸 | ECHE | 메틸 |
5-27 | H,메틸 | 메틸 | 페닐 | 메틸 | 페닐 | 메틸 |
5-28 | H,메틸 | 메틸 | GlyP | 메틸 | GlyP | 메틸 |
5-29 | H,메틸 | 메틸 | POMMA | 메틸 | POMMA | 메틸 |
5-30 | H,메틸 | GlyP | GlyP | ECHE | GlyP | ECHE |
5-31 | H,메틸 | GlyP | GlyP | 페닐 | GlyP | 페닐 |
5-32 | H,메틸 | GlyP | GlyP | 메틸 | GlyP | 메틸 |
5-33 | H,메틸 | GlyP | GlyP | POMMA | GlyP | POMMA |
5-34 | H,메틸 | GlyP | ECHE | GlyP | ECHE | GlyP |
5-35 | H,메틸 | GlyP | 페닐 | GlyP | 페닐 | GlyP |
5-36 | H,메틸 | GlyP | 메틸 | GlyP | 메틸 | GlyP |
5-37 | H,메틸 | GlyP | POMMA | GlyP | POMMA | GlyP |
5-35 | H,메틸 | POMMA | POMMA | ECHE | POMMA | ECHE |
5-39 | H,메틸 | POMMA | POMMA | 페닐 | POMMA | 페닐 |
5-40 | H,메틸 | POMMA | POMMA | 메틸 | POMMA | 메틸 |
5-41 | H,메틸 | POMMA | POMMA | GlyP | POMMA | GlyP |
5-42 | H,메틸 | POMMA | ECHE | POMMA | ECHE | POMMA |
5-43 | H,메틸 | POMMA | 페닐 | POMMA | 페닐 | POMMA |
5-44 | H,메틸 | POMMA | 메틸 | POMMA | 메틸 | POMMA |
5-45 | H,메틸 | POMMA | GlyP | POMMA | GlyP | POMMA |
No | R5 | R16 | R19 | R20 | Y R | X, R |
5-1 | H, methyl | ECHE | ECHE | ECHE | ECHE | ECHE |
5-2 | H, methyl | Phenyl | Phenyl | Phenyl | Phenyl | Phenyl |
5-3 | H, methyl | methyl | methyl | methyl | methyl | methyl |
5-4 | H, methyl | GlyP | EGCDX | GlyP | EGCDX | GlyP |
5-5 | H, methyl | POMMA | POMMA | POMMA | POMMA | POMMA |
5-6 | H, methyl | ECHE | ECHE | Phenyl | ECHE | Phenyl |
5-7 | H, methyl | ECHE | ECHE | methyl | ECHE | methyl |
5-8 | H, methyl | ECHE | ECHE | GlyP | ECHE | GlyP |
5-9 | H, methyl | ECHE | ECHE | POMMA | ECHE | POMMA |
5-10 | H, methyl | ECHE | Phenyl | ECHE | Phenyl | ECHE |
5-11 | H, methyl | ECHE | methyl | ECHE | methyl | ECHE |
5-12 | H, methyl | ECHE | GlyP | ECHE | GlyP | ECHE |
5-13 | H, methyl | ECHE | POMMA | ECHE | POMMA | ECHE |
5-14 | H, methyl | Phenyl | Phenyl | ECHE | Phenyl | ECHE |
5-15 | H, methyl | Phenyl | Phenyl | methyl | Phenyl | methyl |
5-16 | H, methyl | Phenyl | Phenyl | EGDCX | Phenyl | EGDCX |
5-17 | H, methyl | Phenyl | Phenyl | POMMA | Phenyl | POMMA |
5-18 | H, methyl | Phenyl | ECHE | Phenyl | ECHE | Phenyl |
5-19 | H, methyl | Phenyl | methyl | Phenyl | methyl | Phenyl |
5-20 | H, methyl | Phenyl | GlyP | Phenyl | GlyP | Phenyl |
5-21 | H, methyl | Phenyl | POMMA | Phenyl | POMMA | Phenyl |
5-22 | H, methyl | methyl | methyl | ECHE | methyl | ECHE |
5-23 | H, methyl | methyl | methyl | Phenyl | methyl | Phenyl |
5-25 | H, methyl | methyl | methyl | GlyP | methyl | GlyP |
5-25 | H, methyl | methyl | methyl | POMMA | methyl | POMMA |
5-26 | H, methyl | methyl | ECHE | methyl | ECHE | methyl |
5-27 | H, methyl | methyl | Phenyl | methyl | Phenyl | methyl |
5-28 | H, methyl | methyl | GlyP | methyl | GlyP | methyl |
5-29 | H, methyl | methyl | POMMA | methyl | POMMA | methyl |
5-30 | H, methyl | GlyP | GlyP | ECHE | GlyP | ECHE |
5-31 | H, methyl | GlyP | GlyP | Phenyl | GlyP | Phenyl |
5-32 | H, methyl | GlyP | GlyP | methyl | GlyP | methyl |
5-33 | H, methyl | GlyP | GlyP | POMMA | GlyP | POMMA |
5-34 | H, methyl | GlyP | ECHE | GlyP | ECHE | GlyP |
5-35 | H, methyl | GlyP | Phenyl | GlyP | Phenyl | GlyP |
5-36 | H, methyl | GlyP | methyl | GlyP | methyl | GlyP |
5-37 | H, methyl | GlyP | POMMA | GlyP | POMMA | GlyP |
5-35 | H, methyl | POMMA | POMMA | ECHE | POMMA | ECHE |
5-39 | H, methyl | POMMA | POMMA | Phenyl | POMMA | Phenyl |
5-40 | H, methyl | POMMA | POMMA | methyl | POMMA | methyl |
5-41 | H, methyl | POMMA | POMMA | GlyP | POMMA | GlyP |
5-42 | H, methyl | POMMA | ECHE | POMMA | ECHE | POMMA |
5-43 | H, methyl | POMMA | Phenyl | POMMA | Phenyl | POMMA |
5-44 | H, methyl | POMMA | methyl | POMMA | methyl | POMMA |
5-45 | H, methyl | POMMA | GlyP | POMMA | GlyP | POMMA |
표 6
Table 6
No | R5 | R16 | R19 | R20 | Y의 R | X의 R |
6-1 | H,메틸 | ECHE | ECHE | ECHE | ECHE | ECHE |
6-2 | H,에틸 | 페닐 | 페닐 | 페닐 | 페닐 | 페닐 |
6-3 | H,아세틸틸 | 알킬사이올 | 메틸 | 메틸 | 메틸 | 메틸 |
6-4 | 비닐,메틸 | POMMA | 도데실 | GlyP | EGCDX | GlyP |
6-5 | H,메틸 | POMMA | 알킬사이올 | POMMA | POMMA | POMMA |
6-6 | H, F | ECHE | 페닐 | 페닐 | ECHE | 페닐 |
6-7 | CF3,메틸 | ECHE | 옥틸 | 메틸 | ECHE | 메틸 |
6-8 | H,메틸 | F | 아미노프로필 | GlyP | ECHE | GlyP |
6-9 | H, CF3 | 아미노프로필 | POMMA | POMMA | ECHE | POMMA |
6-10 | H,메틸 | 페닐 | 알킬사이올 | ECHE | 페닐 | ECHE |
6-11 | 아릴,메틸 | 알킬사이올 | 메틸 | ECHE | 메틸 | ECHE |
6-12 | H,메타크릴 | 페닐 | GlyP | ECHE | GlyP | ECHE |
6-13 | H,메틸 | 옥틸 | POMMA | ECHE | POMMA | ECHE |
6-14 | H,옥틸 | 메틸 | ECHE | ECHE | 페닐 | ECHE |
6-15 | H,메틸 | 옥틸 | 알킬사이올 | 메틸 | 페닐 | 메틸 |
6-16 | H,메틸 | 옥틸 | GlyP | EGDCX | 페닐 | EGDCX |
6-17 | 알킬사이올,메틸 | 메틸 | POMMA | POMMA | 페닐 | POMMA |
6-18 | H,메틸 | GlyP | GlyP | 페닐 | ECHE | 페닐 |
6-19 | H, CF3 | POMMA | POMMA | 페닐 | 메틸 | 페닐 |
6-20 | H,메틸 | ECHE | 아미노프로필 | 페닐 | GlyP | 페닐 |
6-21 | C8F13,메틸 | 알킬사이올 | 페닐 | 페닐 | POMMA | 페닐 |
6-22 | H,프로필 | GlyP | GlyP | ECHE | 메틸 | ECHE |
6-23 | F,메틸 | POMMA | POMMA | 페닐 | 메틸 | 페닐 |
6-24 | H,메틸 | ECHE | 아미노프로필 | GlyP | 메틸 | GlyP |
6-25 | H,에틸 | 아미노프로필 | 페닐 | POMMA | 메틸 | POMMA |
6-26 | H,아세틸틸 | 메틸 | 옥틸 | 메틸 | ECHE | 메틸 |
6-27 | 비닐,메틸 | POMMA | POMMA | 메틸 | 페닐 | 메틸 |
6-28 | H,메틸 | 메틸 | 메틸 | 메틸 | GlyP | 메틸 |
6-29 | H, F | 도데실 | GlyP | 메틸 | POMMA | 메틸 |
6-30 | CF3,메틸 | 알킬사이올 | 옥틸 | ECHE | GlyP | ECHE |
6-31 | H,메틸 | 페닐 | POMMA | 페닐 | GlyP | 페닐 |
6-32 | H,옥틸 | 옥틸 | 메틸 | 메틸 | GlyP | 메틸 |
6-33 | H,메틸 | 아미노프로필 | GlyP | POMMA | GlyP | POMMA |
6-34 | H,메틸 | POMMA | 헥실 | GlyP | ECHE | GlyP |
6-35 | H,아세틸틸 | 알킬사이올 | ECHE | GlyP | 페닐 | GlyP |
6-36 | 비닐,메틸 | 메틸 | 헥실 | GlyP | 메틸 | GlyP |
6-37 | H,메틸 | GlyP | GlyP | GlyP | POMMA | GlyP |
6-38 | H, F | POMMA | POMMA | ECHE | POMMA | ECHE |
6-39 | CF3,메틸 | ECHE | 아미노프로필 | 페닐 | POMMA | 페닐 |
6-40 | H,메틸 | 알킬사이올 | 페닐 | 메틸 | POMMA | 메틸 |
6-41 | 비닐,메틸 | GlyP | GlyP | GlyP | POMMA | GlyP |
6-42 | H,메틸 | POMMA | POMMA | POMMA | ECHE | POMMA |
6-43 | H, F | ECHE | 아미노프로필 | POMMA | 페닐 | POMMA |
6-44 | CF3,메틸 | 아미노프로필 | 페닐 | POMMA | 메틸 | POMMA |
6-45 | H,메틸 | POMMA | GlyP | POMMA | GlyP | POMMA |
No | R5 | R16 | R19 | R20 | Y R | X, R |
6-1 | H, methyl | ECHE | ECHE | ECHE | ECHE | ECHE |
6-2 | H, ethyl | Phenyl | Phenyl | Phenyl | Phenyl | Phenyl |
6-3 | H, acetyltyl | Alkyl siol | methyl | methyl | methyl | methyl |
6-4 | Vinyl, methyl | POMMA | Dodecyl | GlyP | EGCDX | GlyP |
6-5 | H, methyl | POMMA | Alkyl siol | POMMA | POMMA | POMMA |
6-6 | H, F | ECHE | Phenyl | Phenyl | ECHE | Phenyl |
6-7 | CF 3 , methyl | ECHE | Octyl | methyl | ECHE | methyl |
6-8 | H, methyl | F | Aminopropyl | GlyP | ECHE | GlyP |
6-9 | H, CF 3 | Aminopropyl | POMMA | POMMA | ECHE | POMMA |
6-10 | H, methyl | Phenyl | Alkyl siol | ECHE | Phenyl | ECHE |
6-11 | Aryl, methyl | Alkyl siol | methyl | ECHE | methyl | ECHE |
6-12 | H, methacryl | Phenyl | GlyP | ECHE | GlyP | ECHE |
6-13 | H, methyl | Octyl | POMMA | ECHE | POMMA | ECHE |
6-14 | H, octyl | methyl | ECHE | ECHE | Phenyl | ECHE |
6-15 | H, methyl | Octyl | Alkyl siol | methyl | Phenyl | methyl |
6-16 | H, methyl | Octyl | GlyP | EGDCX | Phenyl | EGDCX |
6-17 | Alkyl siol, methyl | methyl | POMMA | POMMA | Phenyl | POMMA |
6-18 | H, methyl | GlyP | GlyP | Phenyl | ECHE | Phenyl |
6-19 | H, CF 3 | POMMA | POMMA | Phenyl | methyl | Phenyl |
6-20 | H, methyl | ECHE | Aminopropyl | Phenyl | GlyP | Phenyl |
6-21 | C 8 F 13 , methyl | Alkyl siol | Phenyl | Phenyl | POMMA | Phenyl |
6-22 | H, profile | GlyP | GlyP | ECHE | methyl | ECHE |
6-23 | F, methyl | POMMA | POMMA | Phenyl | methyl | Phenyl |
6-24 | H, methyl | ECHE | Aminopropyl | GlyP | methyl | GlyP |
6-25 | H, ethyl | Aminopropyl | Phenyl | POMMA | methyl | POMMA |
6-26 | H, acetyltyl | methyl | Octyl | methyl | ECHE | methyl |
6-27 | Vinyl, methyl | POMMA | POMMA | methyl | Phenyl | methyl |
6-28 | H, methyl | methyl | methyl | methyl | GlyP | methyl |
6-29 | H, F | Dodecyl | GlyP | methyl | POMMA | methyl |
6-30 | CF 3 , methyl | Alkyl siol | Octyl | ECHE | GlyP | ECHE |
6-31 | H, methyl | Phenyl | POMMA | Phenyl | GlyP | Phenyl |
6-32 | H, octyl | Octyl | methyl | methyl | GlyP | methyl |
6-33 | H, methyl | Aminopropyl | GlyP | POMMA | GlyP | POMMA |
6-34 | H, methyl | POMMA | Hexyl | GlyP | ECHE | GlyP |
6-35 | H, acetyltyl | Alkyl siol | ECHE | GlyP | Phenyl | GlyP |
6-36 | Vinyl, methyl | methyl | Hexyl | GlyP | methyl | GlyP |
6-37 | H, methyl | GlyP | GlyP | GlyP | POMMA | GlyP |
6-38 | H, F | POMMA | POMMA | ECHE | POMMA | ECHE |
6-39 | CF 3 , methyl | ECHE | Aminopropyl | Phenyl | POMMA | Phenyl |
6-40 | H, methyl | Alkyl siol | Phenyl | methyl | POMMA | methyl |
6-41 | Vinyl, methyl | GlyP | GlyP | GlyP | POMMA | GlyP |
6-42 | H, methyl | POMMA | POMMA | POMMA | ECHE | POMMA |
6-43 | H, F | ECHE | Aminopropyl | POMMA | Phenyl | POMMA |
6-44 | CF 3 , methyl | Aminopropyl | Phenyl | POMMA | methyl | POMMA |
6-45 | H, methyl | POMMA | GlyP | POMMA | GlyP | POMMA |
구체적인 예로 상기 화학식 4의 실세스퀴옥산 복합고분자는 하기 표 7 및 8에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
표 7
TABLE 7
No | R6 | R7 | R16 | R17 | R18 | R19 | X의 R | Y의 R |
7-1 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE |
7-2 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 |
7-3 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
7-4 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP |
7-5 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA |
7-6 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | 페닐 | ECHE | 페닐 |
7-7 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | 메틸 | ECHE | 메틸 |
7-8 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | GlyP | ECHE | GlyP |
7-9 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | POMMA | ECHE | POMMA |
7-10 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | ECHE |
7-11 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | 메틸 | 페닐 | 메틸 |
7-12 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | GlyP | 페닐 | GlyP |
7-13 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | POMMA | 페닐 | POMMA |
7-14 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | ECHE | 메틸 | ECHE |
7-15 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | 페닐 | 메틸 | 페닐 |
7-16 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
7-17 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | POMMA | 메틸 | POMMA |
7-18 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | ECHE | GlyP | ECHE |
7-19 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
7-20 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | 메틸 | GlyP | 메틸 |
7-21 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | POMMA | GlyP | POMMA |
7-22 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | ECHE | POMMA | ECHE |
7-23 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | 페닐 | POMMA | 페닐 |
7-24 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | 메틸 | POMMA | 메틸 |
7-25 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | GlyP | POMMA | GlyP |
No | R6 | R7 | R16 | R17 | R18 | R19 | X, R | Y R |
7-1 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE |
7-2 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl |
7-3 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | methyl | methyl | methyl |
7-4 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP |
7-5 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA |
7-6 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
7-7 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | methyl | ECHE | methyl |
7-8 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | GlyP | ECHE | GlyP |
7-9 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | POMMA | ECHE | POMMA |
7-10 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
7-11 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | methyl | Phenyl | methyl |
7-12 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | GlyP | Phenyl | GlyP |
7-13 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | POMMA | Phenyl | POMMA |
7-14 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | ECHE | methyl | ECHE |
7-15 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | Phenyl | methyl | Phenyl |
7-16 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | GlyP | methyl | GlyP |
7-17 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | POMMA | methyl | POMMA |
7-18 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | ECHE | GlyP | ECHE |
7-19 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
7-20 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | methyl | GlyP | methyl |
7-21 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | POMMA | GlyP | POMMA |
7-22 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | ECHE | POMMA | ECHE |
7-23 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | Phenyl | POMMA | Phenyl |
7-24 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | methyl | POMMA | methyl |
7-25 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
표 8
Table 8
No | R6 | R7 | R16 | R17 | R18 | R19 | X의 R | Y의 R |
8-1 | OH,메톡시 | H,메틸 | ECHE | 알킬사이올 | H,메틸 | ECHE | 알킬사이올 | ECHE |
8-2 | OH, CF3 | H,에틸 | ECHE | 페닐 | H,옥틸 | 페닐 | 페닐 | 페닐 |
8-3 | OH,메톡시 | H,아세틸틸 | ECHE | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
8-4 | CF3,메톡시 | 비닐,메틸 | 페닐 | GlyP | H,메틸 | GlyP | GlyP | GlyP |
8-5 | OH,메톡시 | H,메틸 | 페닐 | POMMA | 알킬사이올,메틸 | POMMA | POMMA | POMMA |
8-6 | OH, C8F13 | H, F | 페닐 | ECHE | H,메틸 | 페닐 | ECHE | 페닐 |
8-7 | OH, CF3 | CF3,메틸 | ECHE | ECHE | H, CF3 | 메틸 | ECHE | 메틸 |
8-8 | OH, C8F13 | H,메틸 | 헥실 | ECHE | H,에틸 | GlyP | ECHE | GlyP |
8-9 | OH,메톡시 | H, CF3 | GlyP | ECHE | H,아세틸틸 | POMMA | ECHE | POMMA |
8-10 | OH,메톡시 | H,메틸 | POMMA | 페닐 | 비닐,메틸 | ECHE | 페닐 | ECHE |
8-11 | OH, C8F13 | 아릴,메틸 | 아미노프로필 | 페닐 | H,메틸 | 헥실 | 페닐 | 헥실 |
8-12 | OH,알킬사이올 | H,메타크릴 | 페닐 | 페닐 | H, F | GlyP | 페닐 | GlyP |
8-13 | OH,메톡시 | H,메틸 | GlyP | ECHE | 비닐,메틸 | POMMA | 페닐 | POMMA |
8-14 | OH, 아크릴 | H,옥틸 | POMMA | 헥실 | H,메틸 | 아미노프로필 | 메틸 | 아미노프로필 |
8-15 | 비닐 ,메톡시 | H,메틸 | 아미노프로필 | GlyP | H, F | 페닐 | 메틸 | 페닐 |
8-16 | 알킬아민 | H,메틸 | 페닐 | POMMA | CF3,메틸 | GlyP | 메틸 | GlyP |
8-17 | OH,에틸,메틸 | 알킬사이올,메틸 | 옥틸 | 아미노프로필 | H,메틸 | POMMA | 메틸 | POMMA |
8-18 | 아세톡시,메톡시 | H,메틸 | POMMA | 페닐 | H, CF3 | 아미노프로필 | GlyP | 아미노프로필 |
8-19 | 프로폭시,메톡시 | H, CF3 | ECHE | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
8-20 | OH, 메톡시 | H,메틸 | 페닐 | POMMA | H,메틸 | 옥틸 | GlyP | 옥틸 |
8-21 | C8F13,메톡시 | C8F13,메틸 | 메틸 | 아미노프로필 | H,메틸 | POMMA | GlyP | POMMA |
8-22 | OH,아릴 | H,프로필 | GlyP | 페닐 | 알킬사이올,메틸 | ECHE | POMMA | ECHE |
8-23 | OH,메톡시 | F,메틸 | POMMA | 옥틸 | H,메틸 | 페닐 | POMMA | 페닐 |
8-24 | CF3,메타크릴 | H,메틸 | POMMA | POMMA | H, CF3 | 메틸 | POMMA | 메틸 |
8-25 | OH,메톡시 | H,에틸 | POMMA | ECHE | H,메틸 | GlyP | POMMA | GlyP |
No | R6 | R7 | R16 | R17 | R18 | R19 | X, R | Y R |
8-1 | OH, methoxy | H, methyl | ECHE | Alkyl siol | H, methyl | ECHE | Alkyl siol | ECHE |
8-2 | OH, CF 3 | H, ethyl | ECHE | Phenyl | H, octyl | Phenyl | Phenyl | Phenyl |
8-3 | OH, methoxy | H, acetyltyl | ECHE | methyl | H, methyl | methyl | methyl | methyl |
8-4 | CF 3 , methoxy | Vinyl, methyl | Phenyl | GlyP | H, methyl | GlyP | GlyP | GlyP |
8-5 | OH, methoxy | H, methyl | Phenyl | POMMA | Alkyl siol, methyl | POMMA | POMMA | POMMA |
8-6 | OH, C 8 F 13 | H, F | Phenyl | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
8-7 | OH, CF 3 | CF 3 , methyl | ECHE | ECHE | H, CF 3 | methyl | ECHE | methyl |
8-8 | OH, C 8 F 13 | H, methyl | Hexyl | ECHE | H, ethyl | GlyP | ECHE | GlyP |
8-9 | OH, methoxy | H, CF 3 | GlyP | ECHE | H, acetyltyl | POMMA | ECHE | POMMA |
8-10 | OH, methoxy | H, methyl | POMMA | Phenyl | Vinyl, methyl | ECHE | Phenyl | ECHE |
8-11 | OH, C 8 F 13 | Aryl, methyl | Aminopropyl | Phenyl | H, methyl | Hexyl | Phenyl | Hexyl |
8-12 | OH, alkyl siol | H, methacryl | Phenyl | Phenyl | H, F | GlyP | Phenyl | GlyP |
8-13 | OH, methoxy | H, methyl | GlyP | ECHE | Vinyl, methyl | POMMA | Phenyl | POMMA |
8-14 | OH, acrylic | H, octyl | POMMA | Hexyl | H, methyl | Aminopropyl | methyl | Aminopropyl |
8-15 | Vinyl, methoxy | H, methyl | Aminopropyl | GlyP | H, F | Phenyl | methyl | Phenyl |
8-16 | Alkylamine | H, methyl | Phenyl | POMMA | CF 3 , methyl | GlyP | methyl | GlyP |
8-17 | OH, ethyl, methyl | Alkyl siol, methyl | Octyl | Aminopropyl | H, methyl | POMMA | methyl | POMMA |
8-18 | Acetoxy, methoxy | H, methyl | POMMA | Phenyl | H, CF 3 | Aminopropyl | GlyP | Aminopropyl |
8-19 | Propoxy, methoxy | H, CF 3 | ECHE | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
8-20 | OH, methoxy | H, methyl | Phenyl | POMMA | H, methyl | Octyl | GlyP | Octyl |
8-21 | C 8 F 13 , methoxy | C 8 F 13 , methyl | methyl | Aminopropyl | H, methyl | POMMA | GlyP | POMMA |
8-22 | OH, aryl | H, profile | GlyP | Phenyl | Alkyl siol, methyl | ECHE | POMMA | ECHE |
8-23 | OH, methoxy | F, methyl | POMMA | Octyl | H, methyl | Phenyl | POMMA | Phenyl |
8-24 | CF 3 , methacryl | H, methyl | POMMA | POMMA | H, CF 3 | methyl | POMMA | methyl |
8-25 | OH, methoxy | H, ethyl | POMMA | ECHE | H, methyl | GlyP | POMMA | GlyP |
구체적인 예로 상기 화학식 5의 실세스퀴옥산 복합고분자는 하기 표 9 및 10에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
표 9
Table 9
No | R8 | R9 | R16 | R17 | R18 | R19 | X의 R | Y의 R |
9-1 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE |
9-2 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 |
9-3 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
9-4 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP |
9-5 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA |
9-6 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | 페닐 | ECHE | 페닐 |
9-7 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | 메틸 | ECHE | 메틸 |
9-8 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | GlyP | ECHE | GlyP |
9-9 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | POMMA | ECHE | POMMA |
9-10 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | ECHE |
9-11 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | 메틸 | 페닐 | 메틸 |
9-12 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | GlyP | 페닐 | GlyP |
9-13 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | POMMA | 페닐 | POMMA |
9-14 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | ECHE | 메틸 | ECHE |
9-15 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | 페닐 | 메틸 | 페닐 |
9-16 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
9-17 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | POMMA | 메틸 | POMMA |
9-18 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | ECHE | GlyP | ECHE |
9-19 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
9-20 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | 메틸 | GlyP | 메틸 |
9-21 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | POMMA | GlyP | POMMA |
9-22 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | ECHE | POMMA | ECHE |
9-23 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | 페닐 | POMMA | 페닐 |
9-24 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | 메틸 | POMMA | 메틸 |
9-25 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | GlyP | POMMA | GlyP |
No | R8 | R9 | R16 | R17 | R18 | R19 | X, R | Y R |
9-1 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE |
9-2 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl |
9-3 | H, methyl | H, methyl | methyl | methyl | H, methyl | methyl | methyl | methyl |
9-4 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP |
9-5 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA |
9-6 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
9-7 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | methyl | ECHE | methyl |
9-8 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | GlyP | ECHE | GlyP |
9-9 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | POMMA | ECHE | POMMA |
9-10 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
9-11 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | methyl | Phenyl | methyl |
9-12 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | GlyP | Phenyl | GlyP |
9-13 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | POMMA | Phenyl | POMMA |
9-14 | H, methyl | H, methyl | methyl | methyl | H, methyl | ECHE | methyl | ECHE |
9-15 | H, methyl | H, methyl | methyl | methyl | H, methyl | Phenyl | methyl | Phenyl |
9-16 | H, methyl | H, methyl | methyl | methyl | H, methyl | GlyP | methyl | GlyP |
9-17 | H, methyl | H, methyl | methyl | methyl | H, methyl | POMMA | methyl | POMMA |
9-18 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | ECHE | GlyP | ECHE |
9-19 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
9-20 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | methyl | GlyP | methyl |
9-21 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | POMMA | GlyP | POMMA |
9-22 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | ECHE | POMMA | ECHE |
9-23 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | Phenyl | POMMA | Phenyl |
9-24 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | methyl | POMMA | methyl |
9-25 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
표 10
Table 10
No | R8 | R9 | R16 | R17 | R18 | R19 | B의 R | D의 R |
10-1 | H,메틸 | CF3,메틸 | ECHE | 알킬사이올 | H,메틸 | ECHE | 알킬사이올 | ECHE |
10-2 | H,에틸 | H,메틸 | ECHE | 페닐 | 알킬사이올,메틸 | 헥실 | 페닐 | 헥실 |
10-3 | H,아세틸틸 | H, CF3 | ECHE | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
10-4 | 비닐,메틸 | H,메틸 | 페닐 | GlyP | H, CF3 | POMMA | GlyP | POMMA |
10-5 | H,메틸 | H,메틸 | 페닐 | POMMA | H,에틸 | 아미노프로필 | POMMA | 아미노프로필 |
10-6 | H, F | H,옥틸 | 페닐 | ECHE | H, F | 페닐 | ECHE | 페닐 |
10-7 | CF3,메틸 | H,메틸 | ECHE | ECHE | 비닐,메틸 | GlyP | ECHE | GlyP |
10-8 | H,메틸 | H,메틸 | 헥실 | ECHE | H,메틸 | POMMA | ECHE | POMMA |
10-9 | H, CF3 | 알킬사이올,메틸 | GlyP | ECHE | H, F | 아미노프로필 | ECHE | 아미노프로필 |
10-10 | H,메틸 | H,메틸 | POMMA | 페닐 | CF3,메틸 | 페닐 | 페닐 | 페닐 |
10-11 | 아릴,메틸 | H,메틸 | 아미노프로필 | 페닐 | H,메틸 | 옥틸 | 페닐 | 옥틸 |
10-12 | H,메타크릴 | H,메틸 | 페닐 | 페닐 | H, CF3 | POMMA | 페닐 | POMMA |
10-13 | H,메틸 | 알킬사이올,메틸 | GlyP | ECHE | H,메틸 | ECHE | ECHE | ECHE |
10-14 | H,옥틸 | H,메틸 | POMMA | 헥실 | H,메틸 | 페닐 | 헥실 | 페닐 |
10-15 | H,메틸 | H, F | 아미노프로필 | GlyP | H,옥틸 | 메틸 | GlyP | 메틸 |
10-16 | H,메틸 | CF3,메틸 | 페닐 | POMMA | H,메틸 | GlyP | POMMA | GlyP |
10-17 | 알킬사이올,메틸 | H,메틸 | 옥틸 | 아미노프로필 | H,메틸 | POMMA | 아미노프로필 | POMMA |
10-18 | H,메틸 | H, CF3 | POMMA | 페닐 | 알킬사이올,메틸 | 아미노프로필 | 페닐 | 아미노프로필 |
10-19 | H, CF3 | H,메틸 | ECHE | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
10-20 | H,메틸 | H,메틸 | 페닐 | POMMA | H,메틸 | 옥틸 | POMMA | 옥틸 |
10-21 | C8F13,메틸 | H,메틸 | 메틸 | 아미노프로필 | H,메틸 | POMMA | 아미노프로필 | POMMA |
10-22 | H,프로필 | 알킬사이올,메틸 | GlyP | 페닐 | 알킬사이올,메틸 | ECHE | 페닐 | ECHE |
10-23 | F,메틸 | H,메틸 | POMMA | 옥틸 | H,메틸 | 페닐 | 옥틸 | 페닐 |
10-24 | H,메틸 | H, CF3 | POMMA | POMMA | H, CF3 | 메틸 | POMMA | 메틸 |
10-25 | H,에틸 | H,메틸 | POMMA | ECHE | H,메틸 | GlyP | ECHE | GlyP |
No | R8 | R9 | R16 | R17 | R18 | R19 | B, R | D, R |
10-1 | H, methyl | CF 3 , methyl | ECHE | Alkyl siol | H, methyl | ECHE | Alkyl siol | ECHE |
10-2 | H, ethyl | H, methyl | ECHE | Phenyl | Alkyl siol, methyl | Hexyl | Phenyl | Hexyl |
10-3 | H, acetyltyl | H, CF 3 | ECHE | methyl | H, methyl | GlyP | methyl | GlyP |
10-4 | Vinyl, methyl | H, methyl | Phenyl | GlyP | H, CF 3 | POMMA | GlyP | POMMA |
10-5 | H, methyl | H, methyl | Phenyl | POMMA | H, ethyl | Aminopropyl | POMMA | Aminopropyl |
10-6 | H, F | H, octyl | Phenyl | ECHE | H, F | Phenyl | ECHE | Phenyl |
10-7 | CF 3 , methyl | H, methyl | ECHE | ECHE | Vinyl, methyl | GlyP | ECHE | GlyP |
10-8 | H, methyl | H, methyl | Hexyl | ECHE | H, methyl | POMMA | ECHE | POMMA |
10-9 | H, CF 3 | Alkyl siol, methyl | GlyP | ECHE | H, F | Aminopropyl | ECHE | Aminopropyl |
10-10 | H, methyl | H, methyl | POMMA | Phenyl | CF 3 , methyl | Phenyl | Phenyl | Phenyl |
10-11 | Aryl, methyl | H, methyl | Aminopropyl | Phenyl | H, methyl | Octyl | Phenyl | Octyl |
10-12 | H, methacryl | H, methyl | Phenyl | Phenyl | H, CF 3 | POMMA | Phenyl | POMMA |
10-13 | H, methyl | Alkyl siol, methyl | GlyP | ECHE | H, methyl | ECHE | ECHE | ECHE |
10-14 | H, octyl | H, methyl | POMMA | Hexyl | H, methyl | Phenyl | Hexyl | Phenyl |
10-15 | H, methyl | H, F | Aminopropyl | GlyP | H, octyl | methyl | GlyP | methyl |
10-16 | H, methyl | CF 3 , methyl | Phenyl | POMMA | H, methyl | GlyP | POMMA | GlyP |
10-17 | Alkyl siol, methyl | H, methyl | Octyl | Aminopropyl | H, methyl | POMMA | Aminopropyl | POMMA |
10-18 | H, methyl | H, CF 3 | POMMA | Phenyl | Alkyl siol, methyl | Aminopropyl | Phenyl | Aminopropyl |
10-19 | H, CF 3 | H, methyl | ECHE | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
10-20 | H, methyl | H, methyl | Phenyl | POMMA | H, methyl | Octyl | POMMA | Octyl |
10-21 | C 8 F 13 , methyl | H, methyl | methyl | Aminopropyl | H, methyl | POMMA | Aminopropyl | POMMA |
10-22 | H, profile | Alkyl siol, methyl | GlyP | Phenyl | Alkyl siol, methyl | ECHE | Phenyl | ECHE |
10-23 | F, methyl | H, methyl | POMMA | Octyl | H, methyl | Phenyl | Octyl | Phenyl |
10-24 | H, methyl | H, CF 3 | POMMA | POMMA | H, CF 3 | methyl | POMMA | methyl |
10-25 | H, ethyl | H, methyl | POMMA | ECHE | H, methyl | GlyP | ECHE | GlyP |
구체적인 예로 상기 화학식 6의 실세스퀴옥산 복합고분자는 하기 표 11 및 12에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
표 11
Table 11
No | R16 | R17 | R18 | R19 | R20 | X의 R | Y의 R | E의 X의 R |
11-1 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE | ECHE | ECHE |
11-2 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 | 페닐 | 페닐 |
11-3 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 | 메틸 | 메틸 |
11-4 | GlyP | EGCDX | H,메틸 | EGCDX | GlyP | EGCDX | EGCDX | GlyP |
11-5 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA | POMMA | POMMA |
11-6 | ECHE | ECHE | H,메틸 | ECHE | 페닐 | ECHE | ECHE | 페닐 |
11-7 | ECHE | ECHE | H,메틸 | ECHE | 메틸 | ECHE | ECHE | 메틸 |
11-8 | ECHE | ECHE | H,메틸 | ECHE | GlyP | ECHE | ECHE | GlyP |
11-9 | ECHE | ECHE | H,메틸 | ECHE | POMMA | ECHE | ECHE | POMMA |
11-10 | ECHE | 페닐 | H,메틸 | 페닐 | ECHE | 페닐 | 페닐 | ECHE |
11-11 | ECHE | 메틸 | H,메틸 | 메틸 | ECHE | 메틸 | 메틸 | ECHE |
11-12 | ECHE | GlyP | H,메틸 | GlyP | ECHE | GlyP | GlyP | ECHE |
11-13 | ECHE | POMMA | H,메틸 | POMMA | ECHE | POMMA | POMMA | ECHE |
11-14 | 페닐 | 페닐 | H,메틸 | 페닐 | ECHE | 페닐 | 페닐 | ECHE |
11-15 | 페닐 | 페닐 | H,메틸 | 페닐 | 메틸 | 페닐 | 페닐 | 메틸 |
11-16 | 페닐 | 페닐 | H,메틸 | 페닐 | EGDCX | 페닐 | 페닐 | EGDCX |
11-17 | 페닐 | 페닐 | H,메틸 | 페닐 | POMMA | 페닐 | 페닐 | POMMA |
11-18 | 페닐 | ECHE | H,메틸 | ECHE | 페닐 | ECHE | ECHE | 페닐 |
11-19 | 페닐 | 메틸 | H,메틸 | 메틸 | 페닐 | 메틸 | 메틸 | 페닐 |
11-20 | 페닐 | GlyP | H,메틸 | GlyP | 페닐 | GlyP | GlyP | 페닐 |
11-21 | 페닐 | POMMA | H,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
11-22 | 메틸 | 메틸 | H,메틸 | 메틸 | ECHE | 메틸 | 메틸 | ECHE |
11-23 | 메틸 | 메틸 | H,메틸 | 메틸 | 페닐 | 메틸 | 메틸 | 페닐 |
11-24 | 메틸 | 메틸 | H,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
11-25 | 메틸 | 메틸 | H,메틸 | 메틸 | POMMA | 메틸 | 메틸 | POMMA |
11-26 | 메틸 | ECHE | H,메틸 | ECHE | 메틸 | ECHE | ECHE | 메틸 |
11-27 | 메틸 | 페닐 | H,메틸 | 페닐 | 메틸 | 페닐 | 페닐 | 메틸 |
11-28 | 메틸 | GlyP | H,메틸 | GlyP | 메틸 | GlyP | GlyP | 메틸 |
11-29 | 메틸 | POMMA | H,메틸 | POMMA | 메틸 | POMMA | POMMA | 메틸 |
11-30 | GlyP | GlyP | H,메틸 | GlyP | ECHE | GlyP | GlyP | ECHE |
11-31 | GlyP | GlyP | H,메틸 | GlyP | 페닐 | GlyP | GlyP | 페닐 |
11-32 | GlyP | GlyP | H,메틸 | GlyP | 메틸 | GlyP | GlyP | 메틸 |
11-33 | GlyP | GlyP | H,메틸 | GlyP | POMMA | GlyP | GlyP | POMMA |
11-34 | GlyP | ECHE | H,메틸 | ECHE | GlyP | ECHE | ECHE | GlyP |
11-35 | GlyP | 페닐 | H,메틸 | 페닐 | GlyP | 페닐 | 페닐 | GlyP |
11-36 | GlyP | 메틸 | H,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
11-37 | GlyP | POMMA | H,메틸 | POMMA | GlyP | POMMA | POMMA | GlyP |
11-38 | POMMA | POMMA | H,메틸 | POMMA | ECHE | POMMA | POMMA | ECHE |
11-39 | POMMA | POMMA | H,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
11-40 | POMMA | POMMA | H,메틸 | POMMA | 메틸 | POMMA | POMMA | 메틸 |
11-41 | POMMA | POMMA | H,메틸 | POMMA | GlyP | POMMA | POMMA | GlyP |
11-42 | POMMA | ECHE | H,메틸 | ECHE | POMMA | ECHE | ECHE | POMMA |
11-43 | POMMA | 페닐 | H,메틸 | 페닐 | POMMA | 페닐 | 페닐 | POMMA |
11-44 | POMMA | 메틸 | H,메틸 | 메틸 | POMMA | 메틸 | 메틸 | POMMA |
11-45 | POMMA | GlyP | H,메틸 | GlyP | POMMA | GlyP | GlyP | POMMA |
No | R16 | R17 | R18 | R19 | R20 | X, R | Y R | E x r |
11-1 | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE | ECHE | ECHE |
11-2 | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl | Phenyl | Phenyl |
11-3 | methyl | methyl | H, methyl | methyl | methyl | methyl | methyl | methyl |
11-4 | GlyP | EGCDX | H, methyl | EGCDX | GlyP | EGCDX | EGCDX | GlyP |
11-5 | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA | POMMA | POMMA |
11-6 | ECHE | ECHE | H, methyl | ECHE | Phenyl | ECHE | ECHE | Phenyl |
11-7 | ECHE | ECHE | H, methyl | ECHE | methyl | ECHE | ECHE | methyl |
11-8 | ECHE | ECHE | H, methyl | ECHE | GlyP | ECHE | ECHE | GlyP |
11-9 | ECHE | ECHE | H, methyl | ECHE | POMMA | ECHE | ECHE | POMMA |
11-10 | ECHE | Phenyl | H, methyl | Phenyl | ECHE | Phenyl | Phenyl | ECHE |
11-11 | ECHE | methyl | H, methyl | methyl | ECHE | methyl | methyl | ECHE |
11-12 | ECHE | GlyP | H, methyl | GlyP | ECHE | GlyP | GlyP | ECHE |
11-13 | ECHE | POMMA | H, methyl | POMMA | ECHE | POMMA | POMMA | ECHE |
11-14 | Phenyl | Phenyl | H, methyl | Phenyl | ECHE | Phenyl | Phenyl | ECHE |
11-15 | Phenyl | Phenyl | H, methyl | Phenyl | methyl | Phenyl | Phenyl | methyl |
11-16 | Phenyl | Phenyl | H, methyl | Phenyl | EGDCX | Phenyl | Phenyl | EGDCX |
11-17 | Phenyl | Phenyl | H, methyl | Phenyl | POMMA | Phenyl | Phenyl | POMMA |
11-18 | Phenyl | ECHE | H, methyl | ECHE | Phenyl | ECHE | ECHE | Phenyl |
11-19 | Phenyl | methyl | H, methyl | methyl | Phenyl | methyl | methyl | Phenyl |
11-20 | Phenyl | GlyP | H, methyl | GlyP | Phenyl | GlyP | GlyP | Phenyl |
11-21 | Phenyl | POMMA | H, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
11-22 | methyl | methyl | H, methyl | methyl | ECHE | methyl | methyl | ECHE |
11-23 | methyl | methyl | H, methyl | methyl | Phenyl | methyl | methyl | Phenyl |
11-24 | methyl | methyl | H, methyl | methyl | GlyP | methyl | methyl | GlyP |
11-25 | methyl | methyl | H, methyl | methyl | POMMA | methyl | methyl | POMMA |
11-26 | methyl | ECHE | H, methyl | ECHE | methyl | ECHE | ECHE | methyl |
11-27 | methyl | Phenyl | H, methyl | Phenyl | methyl | Phenyl | Phenyl | methyl |
11-28 | methyl | GlyP | H, methyl | GlyP | methyl | GlyP | GlyP | methyl |
11-29 | methyl | POMMA | H, methyl | POMMA | methyl | POMMA | POMMA | methyl |
11-30 | GlyP | GlyP | H, methyl | GlyP | ECHE | GlyP | GlyP | ECHE |
11-31 | GlyP | GlyP | H, methyl | GlyP | Phenyl | GlyP | GlyP | Phenyl |
11-32 | GlyP | GlyP | H, methyl | GlyP | methyl | GlyP | GlyP | methyl |
11-33 | GlyP | GlyP | H, methyl | GlyP | POMMA | GlyP | GlyP | POMMA |
11-34 | GlyP | ECHE | H, methyl | ECHE | GlyP | ECHE | ECHE | GlyP |
11-35 | GlyP | Phenyl | H, methyl | Phenyl | GlyP | Phenyl | Phenyl | GlyP |
11-36 | GlyP | methyl | H, methyl | methyl | GlyP | methyl | methyl | GlyP |
11-37 | GlyP | POMMA | H, methyl | POMMA | GlyP | POMMA | POMMA | GlyP |
11-38 | POMMA | POMMA | H, methyl | POMMA | ECHE | POMMA | POMMA | ECHE |
11-39 | POMMA | POMMA | H, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
11-40 | POMMA | POMMA | H, methyl | POMMA | methyl | POMMA | POMMA | methyl |
11-41 | POMMA | POMMA | H, methyl | POMMA | GlyP | POMMA | POMMA | GlyP |
11-42 | POMMA | ECHE | H, methyl | ECHE | POMMA | ECHE | ECHE | POMMA |
11-43 | POMMA | Phenyl | H, methyl | Phenyl | POMMA | Phenyl | Phenyl | POMMA |
11-44 | POMMA | methyl | H, methyl | methyl | POMMA | methyl | methyl | POMMA |
11-45 | POMMA | GlyP | H, methyl | GlyP | POMMA | GlyP | GlyP | POMMA |
표 12
Table 12
No | R16 | R17 | R18 | R19 | R20 | X의 R | Y의 R | E의 X의 R |
12-1 | ECHE | POMMA | H,메틸 | ECHE | POMMA | POMMA | ECHE | POMMA |
12-2 | 페닐 | POMMA | H,에틸 | 페닐 | POMMA | POMMA | 페닐 | POMMA |
12-3 | POMMA | ECHE | H,아세틸틸 | 메틸 | ECHE | ECHE | 메틸 | ECHE |
12-4 | 메틸 | ECHE | 비닐,메틸 | EGCDX | ECHE | ECHE | EGCDX | ECHE |
12-5 | POMMA | F | H,메틸 | POMMA | F | F | POMMA | F |
12-6 | 프로필 | 아미노프로필 | CF3,메틸 | ECHE | 아미노프로필 | 아미노프로필 | ECHE | 아미노프로필 |
12-7 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | 페닐 | ECHE | 페닐 |
12-8 | 메틸 | 알킬사이올 | H,아세틸틸 | ECHE | 알킬사이올 | 알킬사이올 | ECHE | 알킬사이올 |
12-9 | GlyP | 페닐 | 비닐,메틸 | ECHE | 페닐 | 페닐 | ECHE | 페닐 |
12-10 | ECHE | 옥틸 | H,메틸 | 페닐 | 옥틸 | 옥틸 | 페닐 | 옥틸 |
12-11 | 알킬사이올 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 | 메틸 | 메틸 |
12-12 | 페닐 | 옥틸 | 비닐,메틸 | GlyP | 옥틸 | 옥틸 | GlyP | 옥틸 |
12-13 | 옥틸 | 옥틸 | H,메틸 | POMMA | 옥틸 | 옥틸 | POMMA | 옥틸 |
12-14 | 메틸 | 메틸 | H, F | 페닐 | 메틸 | 메틸 | 페닐 | 메틸 |
12-15 | 옥틸 | GlyP | CF3,메틸 | 페닐 | ECHE | GlyP | 페닐 | ECHE |
12-16 | 옥틸 | GlyP | 비닐,메틸 | 페닐 | 페닐 | GlyP | 페닐 | 페닐 |
12-17 | 메틸 | 아미노프로필 | H,메틸 | 페닐 | POMMA | 아미노프로필 | 페닐 | POMMA |
12-18 | GlyP | GlyP | H, F | ECHE | 메틸 | GlyP | ECHE | 메틸 |
12-19 | GlyP | POMMA | CF3,메틸 | 메틸 | POMMA | POMMA | 메틸 | POMMA |
12-20 | 아미노프로필 | 메틸 | H,메틸 | GlyP | 프로필 | 메틸 | GlyP | 프로필 |
12-21 | GlyP | POMMA | 알킬사이올,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
12-22 | POMMA | 프로필 | H,아세틸틸 | 메틸 | 메틸 | 프로필 | 메틸 | 메틸 |
12-23 | POMMA | 메틸 | 비닐,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
12-24 | GlyP | GlyP | 비닐,메틸 | 메틸 | ECHE | GlyP | 메틸 | ECHE |
12-25 | 아미노프로필 | GlyP | H,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
12-26 | 메틸 | 아미노프로필 | H, F | ECHE | 아미노프로필 | 아미노프로필 | ECHE | 아미노프로필 |
12-27 | 메틸 | GlyP | CF3,메틸 | 페닐 | GlyP | GlyP | 페닐 | GlyP |
12-28 | 메틸 | 옥틸 | H,메틸 | GlyP | 옥틸 | 옥틸 | GlyP | 옥틸 |
12-29 | 메틸 | 메틸 | H,아세틸틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
12-30 | 아미노프로필 | GlyP | 비닐,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
12-31 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
12-32 | POMMA | 아미노프로필 | H,메틸 | GlyP | 아미노프로필 | 아미노프로필 | GlyP | 아미노프로필 |
12-33 | 메틸 | GlyP | 비닐,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
12-34 | POMMA | POMMA | H,메틸 | ECHE | POMMA | POMMA | ECHE | POMMA |
12-35 | 프로필 | POMMA | H, F | 페닐 | POMMA | POMMA | 페닐 | POMMA |
12-36 | 메틸 | GlyP | CF3,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
12-37 | GlyP | 아미노프로필 | 비닐,메틸 | POMMA | 아미노프로필 | 아미노프로필 | POMMA | 아미노프로필 |
12-38 | GlyP | 메틸 | H,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
12-39 | 아미노프로필 | 메틸 | H, F | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
12-40 | 아미노프로필 | 메틸 | CF3,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
12-41 | GlyP | 메틸 | H,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
12-42 | POMMA | GlyP | 알킬사이올,메틸 | ECHE | GlyP | GlyP | ECHE | GlyP |
12-43 | POMMA | 아미노프로필 | H,아세틸틸 | 페닐 | 아미노프로필 | 아미노프로필 | 페닐 | 아미노프로필 |
12-44 | POMMA | GlyP | 비닐,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
12-45 | POMMA | POMMA | H,메틸 | GlyP | POMMA | POMMA | GlyP | POMMA |
No | R16 | R17 | R18 | R19 | R20 | X, R | Y R | E x r |
12-1 | ECHE | POMMA | H, methyl | ECHE | POMMA | POMMA | ECHE | POMMA |
12-2 | Phenyl | POMMA | H, ethyl | Phenyl | POMMA | POMMA | Phenyl | POMMA |
12-3 | POMMA | ECHE | H, acetyltyl | methyl | ECHE | ECHE | methyl | ECHE |
12-4 | methyl | ECHE | Vinyl, methyl | EGCDX | ECHE | ECHE | EGCDX | ECHE |
12-5 | POMMA | F | H, methyl | POMMA | F | F | POMMA | F |
12-6 | profile | Aminopropyl | CF 3 , methyl | ECHE | Aminopropyl | Aminopropyl | ECHE | Aminopropyl |
12-7 | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | Phenyl | ECHE | Phenyl |
12-8 | methyl | Alkyl siol | H, acetyltyl | ECHE | Alkyl siol | Alkyl siol | ECHE | Alkyl siol |
12-9 | GlyP | Phenyl | Vinyl, methyl | ECHE | Phenyl | Phenyl | ECHE | Phenyl |
12-10 | ECHE | Octyl | H, methyl | Phenyl | Octyl | Octyl | Phenyl | Octyl |
12-11 | Alkyl siol | methyl | H, methyl | methyl | methyl | methyl | methyl | methyl |
12-12 | Phenyl | Octyl | Vinyl, methyl | GlyP | Octyl | Octyl | GlyP | Octyl |
12-13 | Octyl | Octyl | H, methyl | POMMA | Octyl | Octyl | POMMA | Octyl |
12-14 | methyl | methyl | H, F | Phenyl | methyl | methyl | Phenyl | methyl |
12-15 | Octyl | GlyP | CF 3 , methyl | Phenyl | ECHE | GlyP | Phenyl | ECHE |
12-16 | Octyl | GlyP | Vinyl, methyl | Phenyl | Phenyl | GlyP | Phenyl | Phenyl |
12-17 | methyl | Aminopropyl | H, methyl | Phenyl | POMMA | Aminopropyl | Phenyl | POMMA |
12-18 | GlyP | GlyP | H, F | ECHE | methyl | GlyP | ECHE | methyl |
12-19 | GlyP | POMMA | CF 3 , methyl | methyl | POMMA | POMMA | methyl | POMMA |
12-20 | Aminopropyl | methyl | H, methyl | GlyP | profile | methyl | GlyP | profile |
12-21 | GlyP | POMMA | Alkyl siol, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
12-22 | POMMA | profile | H, acetyltyl | methyl | methyl | profile | methyl | methyl |
12-23 | POMMA | methyl | Vinyl, methyl | methyl | GlyP | methyl | methyl | GlyP |
12-24 | GlyP | GlyP | Vinyl, methyl | methyl | ECHE | GlyP | methyl | ECHE |
12-25 | Aminopropyl | GlyP | H, methyl | methyl | GlyP | GlyP | methyl | GlyP |
12-26 | methyl | Aminopropyl | H, F | ECHE | Aminopropyl | Aminopropyl | ECHE | Aminopropyl |
12-27 | methyl | GlyP | CF 3 , methyl | Phenyl | GlyP | GlyP | Phenyl | GlyP |
12-28 | methyl | Octyl | H, methyl | GlyP | Octyl | Octyl | GlyP | Octyl |
12-29 | methyl | methyl | H, acetyltyl | POMMA | methyl | methyl | POMMA | methyl |
12-30 | Aminopropyl | GlyP | Vinyl, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
12-31 | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
12-32 | POMMA | Aminopropyl | H, methyl | GlyP | Aminopropyl | Aminopropyl | GlyP | Aminopropyl |
12-33 | methyl | GlyP | Vinyl, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
12-34 | POMMA | POMMA | H, methyl | ECHE | POMMA | POMMA | ECHE | POMMA |
12-35 | profile | POMMA | H, F | Phenyl | POMMA | POMMA | Phenyl | POMMA |
12-36 | methyl | GlyP | CF 3 , methyl | methyl | GlyP | GlyP | methyl | GlyP |
12-37 | GlyP | Aminopropyl | Vinyl, methyl | POMMA | Aminopropyl | Aminopropyl | POMMA | Aminopropyl |
12-38 | GlyP | methyl | H, methyl | POMMA | methyl | methyl | POMMA | methyl |
12-39 | Aminopropyl | methyl | H, F | POMMA | methyl | methyl | POMMA | methyl |
12-40 | Aminopropyl | methyl | CF 3 , methyl | POMMA | methyl | methyl | POMMA | methyl |
12-41 | GlyP | methyl | H, methyl | POMMA | methyl | methyl | POMMA | methyl |
12-42 | POMMA | GlyP | Alkyl siol, methyl | ECHE | GlyP | GlyP | ECHE | GlyP |
12-43 | POMMA | Aminopropyl | H, acetyltyl | Phenyl | Aminopropyl | Aminopropyl | Phenyl | Aminopropyl |
12-44 | POMMA | GlyP | Vinyl, methyl | methyl | GlyP | GlyP | methyl | GlyP |
12-45 | POMMA | POMMA | H, methyl | GlyP | POMMA | POMMA | GlyP | POMMA |
구체적인 예로 상기 화학식 7의 실세스퀴옥산 복합고분자는 하기 표 13 및 14에 기재된 고분자일 수 있다. As a specific example, the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
표 13
Table 13
No | R11 | R12 | R16 | R17 | R18 | R19 | X의R | Y의R |
13-1 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE |
13-2 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 |
13-3 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
13-4 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP |
13-5 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA |
13-6 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | 페닐 | ECHE | 페닐 |
13-7 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | 메틸 | ECHE | 메틸 |
13-8 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | GlyP | ECHE | GlyP |
13-9 | OH,메톡시 | H,메틸 | ECHE | ECHE | H,메틸 | POMMA | ECHE | POMMA |
13-10 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | ECHE |
13-11 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | 메틸 | 페닐 | 메틸 |
13-12 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | GlyP | 페닐 | GlyP |
13-13 | OH,메톡시 | H,메틸 | 페닐 | 페닐 | H,메틸 | POMMA | 페닐 | POMMA |
13-14 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | ECHE | 메틸 | ECHE |
13-15 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | 페닐 | 메틸 | 페닐 |
13-16 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
13-17 | OH,메톡시 | H,메틸 | 메틸 | 메틸 | H,메틸 | POMMA | 메틸 | POMMA |
13-18 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | ECHE | GlyP | ECHE |
13-19 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
13-20 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | 메틸 | GlyP | 메틸 |
13-21 | OH,메톡시 | H,메틸 | GlyP | GlyP | H,메틸 | POMMA | GlyP | POMMA |
13-22 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | ECHE | POMMA | ECHE |
13-23 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | 페닐 | POMMA | 페닐 |
13-24 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | 메틸 | POMMA | 메틸 |
13-25 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | GlyP | POMMA | GlyP |
No | R11 | R12 | R16 | R17 | R18 | R19 | X, R | Y, R |
13-1 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE |
13-2 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl |
13-3 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | methyl | methyl | methyl |
13-4 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP |
13-5 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA |
13-6 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
13-7 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | methyl | ECHE | methyl |
13-8 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | GlyP | ECHE | GlyP |
13-9 | OH, methoxy | H, methyl | ECHE | ECHE | H, methyl | POMMA | ECHE | POMMA |
13-10 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
13-11 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | methyl | Phenyl | methyl |
13-12 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | GlyP | Phenyl | GlyP |
13-13 | OH, methoxy | H, methyl | Phenyl | Phenyl | H, methyl | POMMA | Phenyl | POMMA |
13-14 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | ECHE | methyl | ECHE |
13-15 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | Phenyl | methyl | Phenyl |
13-16 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | GlyP | methyl | GlyP |
13-17 | OH, methoxy | H, methyl | methyl | methyl | H, methyl | POMMA | methyl | POMMA |
13-18 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | ECHE | GlyP | ECHE |
13-19 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
13-20 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | methyl | GlyP | methyl |
13-21 | OH, methoxy | H, methyl | GlyP | GlyP | H, methyl | POMMA | GlyP | POMMA |
13-22 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | ECHE | POMMA | ECHE |
13-23 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | Phenyl | POMMA | Phenyl |
13-24 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | methyl | POMMA | methyl |
13-25 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
표 14
Table 14
No | R11 | R12 | R16 | R17 | R18 | R19 | X의R | Y의R |
14-1 | OH,메톡시 | H,메틸 | ECHE | 알킬사이올 | H,메틸 | ECHE | 알킬사이올 | ECHE |
14-2 | OH, CF3 | H,에틸 | ECHE | 페닐 | H,에틸 | 페닐 | 페닐 | 페닐 |
14-3 | OH,메톡시 | H,아세틸틸 | ECHE | 메틸 | H,아세틸틸 | 메틸 | 메틸 | 메틸 |
14-4 | CF3,메톡시 | 비닐,메틸 | 페닐 | GlyP | 비닐,메틸 | GlyP | GlyP | GlyP |
14-5 | OH,메톡시 | H,메틸 | 페닐 | POMMA | H,메틸 | POMMA | POMMA | POMMA |
14-6 | OH, C8F13 | H, F | 페닐 | ECHE | H, F | 페닐 | ECHE | 페닐 |
14-7 | OH, CF3 | CF3,메틸 | ECHE | ECHE | CF3,메틸 | 메틸 | ECHE | 메틸 |
14-8 | OH, C8F13 | H,메틸 | 헥실 | ECHE | H,메틸 | GlyP | ECHE | GlyP |
14-9 | OH,메톡시 | H, CF3 | GlyP | ECHE | H, CF3 | POMMA | ECHE | POMMA |
14-10 | OH,메톡시 | H,메틸 | POMMA | 페닐 | H,메틸 | ECHE | 페닐 | ECHE |
14-11 | OH, C8F13 | 아릴,메틸 | 아미노프로필 | 페닐 | 아릴,메틸 | 헥실 | 페닐 | 헥실 |
14-12 | OH,알킬사이올 | H,메타크릴 | 페닐 | 페닐 | H,메타크릴 | GlyP | 페닐 | GlyP |
14-13 | OH,메톡시 | H,메틸 | GlyP | ECHE | H,메틸 | POMMA | ECHE | POMMA |
14-14 | OH, 아크릴 | H,옥틸 | POMMA | 헥실 | H,옥틸 | 아미노프로필 | 헥실 | 아미노프로필 |
14-15 | 비닐 ,메톡시 | H,메틸 | 아미노프로필 | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
14-16 | 알킬아민 | H,메틸 | 페닐 | POMMA | H,메틸 | GlyP | POMMA | GlyP |
14-17 | OH,에틸,메틸 | 알킬사이올,메틸 | 옥틸 | 아미노프로필 | 알킬사이올,메틸 | POMMA | 아미노프로필 | POMMA |
14-18 | 아세톡시,메톡시 | H,메틸 | POMMA | 페닐 | H,메틸 | 아미노프로필 | 페닐 | 아미노프로필 |
14-19 | 프로폭시,메톡시 | H, CF3 | ECHE | GlyP | H, CF3 | 페닐 | GlyP | 페닐 |
14-20 | OH, 메톡시 | H,메틸 | 페닐 | POMMA | H,메틸 | 옥틸 | POMMA | 옥틸 |
14-21 | C8F13,메톡시 | C8F13,메틸 | 메틸 | 아미노프로필 | C8F13,메틸 | POMMA | 아미노프로필 | POMMA |
14-22 | OH,아릴 | H,프로필 | GlyP | 페닐 | H,프로필 | ECHE | 페닐 | ECHE |
14-23 | OH,메톡시 | F,메틸 | POMMA | 옥틸 | F,메틸 | 페닐 | 옥틸 | 페닐 |
14-24 | CF3,메타크릴 | H,메틸 | POMMA | POMMA | H,메틸 | 메틸 | POMMA | 메틸 |
14-25 | OH,메톡시 | H,메틸 | POMMA | POMMA | H,메틸 | GlyP | POMMA | GlyP |
No | R11 | R12 | R16 | R17 | R18 | R19 | X, R | Y, R |
14-1 | OH, methoxy | H, methyl | ECHE | Alkyl siol | H, methyl | ECHE | Alkyl siol | ECHE |
14-2 | OH, CF 3 | H, ethyl | ECHE | Phenyl | H, ethyl | Phenyl | Phenyl | Phenyl |
14-3 | OH, methoxy | H, acetyltyl | ECHE | methyl | H, acetyltyl | methyl | methyl | methyl |
14-4 | CF 3 , methoxy | Vinyl, methyl | Phenyl | GlyP | Vinyl, methyl | GlyP | GlyP | GlyP |
14-5 | OH, methoxy | H, methyl | Phenyl | POMMA | H, methyl | POMMA | POMMA | POMMA |
14-6 | OH, C 8 F 13 | H, F | Phenyl | ECHE | H, F | Phenyl | ECHE | Phenyl |
14-7 | OH, CF 3 | CF 3 , methyl | ECHE | ECHE | CF 3 , methyl | methyl | ECHE | methyl |
14-8 | OH, C 8 F 13 | H, methyl | Hexyl | ECHE | H, methyl | GlyP | ECHE | GlyP |
14-9 | OH, methoxy | H, CF 3 | GlyP | ECHE | H, CF 3 | POMMA | ECHE | POMMA |
14-10 | OH, methoxy | H, methyl | POMMA | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
14-11 | OH, C 8 F 13 | Aryl, methyl | Aminopropyl | Phenyl | Aryl, methyl | Hexyl | Phenyl | Hexyl |
14-12 | OH, alkyl siol | H, methacryl | Phenyl | Phenyl | H, methacryl | GlyP | Phenyl | GlyP |
14-13 | OH, methoxy | H, methyl | GlyP | ECHE | H, methyl | POMMA | ECHE | POMMA |
14-14 | OH, acrylic | H, octyl | POMMA | Hexyl | H, octyl | Aminopropyl | Hexyl | Aminopropyl |
14-15 | Vinyl, methoxy | H, methyl | Aminopropyl | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
14-16 | Alkylamine | H, methyl | Phenyl | POMMA | H, methyl | GlyP | POMMA | GlyP |
14-17 | OH, ethyl, methyl | Alkyl siol, methyl | Octyl | Aminopropyl | Alkyl siol, methyl | POMMA | Aminopropyl | POMMA |
14-18 | Acetoxy, methoxy | H, methyl | POMMA | Phenyl | H, methyl | Aminopropyl | Phenyl | Aminopropyl |
14-19 | Propoxy, methoxy | H, CF 3 | ECHE | GlyP | H, CF 3 | Phenyl | GlyP | Phenyl |
14-20 | OH, methoxy | H, methyl | Phenyl | POMMA | H, methyl | Octyl | POMMA | Octyl |
14-21 | C 8 F 13 , methoxy | C 8 F 13 , methyl | methyl | Aminopropyl | C 8 F 13 , methyl | POMMA | Aminopropyl | POMMA |
14-22 | OH, aryl | H, profile | GlyP | Phenyl | H, profile | ECHE | Phenyl | ECHE |
14-23 | OH, methoxy | F, methyl | POMMA | Octyl | F, methyl | Phenyl | Octyl | Phenyl |
14-24 | CF 3 , methacryl | H, methyl | POMMA | POMMA | H, methyl | methyl | POMMA | methyl |
14-25 | OH, methoxy | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
구체적인 예로 상기 화학식 8의 실세스퀴옥산 복합고분자는 하기 표 15 및 16에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
표 15
Table 15
No | R13 | R14 | R16 | R17 | R18 | R19 | X의R | Y의 R |
15-1 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE |
15-2 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 |
15-3 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 |
15-4 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP |
15-5 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA |
15-6 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | 페닐 | ECHE | 페닐 |
15-7 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | 메틸 | ECHE | 메틸 |
15-8 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | GlyP | ECHE | GlyP |
15-9 | H,메틸 | H,메틸 | ECHE | ECHE | H,메틸 | POMMA | ECHE | POMMA |
15-10 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | ECHE |
15-11 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | 메틸 | 페닐 | 메틸 |
15-12 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | GlyP | 페닐 | GlyP |
15-13 | H,메틸 | H,메틸 | 페닐 | 페닐 | H,메틸 | POMMA | 페닐 | POMMA |
15-14 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | ECHE | 메틸 | ECHE |
15-15 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | 페닐 | 메틸 | 페닐 |
15-16 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
15-17 | H,메틸 | H,메틸 | 메틸 | 메틸 | H,메틸 | POMMA | 메틸 | POMMA |
15-18 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | ECHE | GlyP | ECHE |
15-19 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
15-20 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | 메틸 | GlyP | 메틸 |
15-21 | H,메틸 | H,메틸 | GlyP | GlyP | H,메틸 | POMMA | GlyP | POMMA |
15-22 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | ECHE | POMMA | ECHE |
15-23 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | 페닐 | POMMA | 페닐 |
15-24 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | 메틸 | POMMA | 메틸 |
15-25 | H,메틸 | H,메틸 | POMMA | POMMA | H,메틸 | GlyP | POMMA | GlyP |
No | R13 | R14 | R16 | R17 | R18 | R19 | X, R | Y R |
15-1 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE |
15-2 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl |
15-3 | H, methyl | H, methyl | methyl | methyl | H, methyl | methyl | methyl | methyl |
15-4 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP |
15-5 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA |
15-6 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
15-7 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | methyl | ECHE | methyl |
15-8 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | GlyP | ECHE | GlyP |
15-9 | H, methyl | H, methyl | ECHE | ECHE | H, methyl | POMMA | ECHE | POMMA |
15-10 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
15-11 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | methyl | Phenyl | methyl |
15-12 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | GlyP | Phenyl | GlyP |
15-13 | H, methyl | H, methyl | Phenyl | Phenyl | H, methyl | POMMA | Phenyl | POMMA |
15-14 | H, methyl | H, methyl | methyl | methyl | H, methyl | ECHE | methyl | ECHE |
15-15 | H, methyl | H, methyl | methyl | methyl | H, methyl | Phenyl | methyl | Phenyl |
15-16 | H, methyl | H, methyl | methyl | methyl | H, methyl | GlyP | methyl | GlyP |
15-17 | H, methyl | H, methyl | methyl | methyl | H, methyl | POMMA | methyl | POMMA |
15-18 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | ECHE | GlyP | ECHE |
15-19 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
15-20 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | methyl | GlyP | methyl |
15-21 | H, methyl | H, methyl | GlyP | GlyP | H, methyl | POMMA | GlyP | POMMA |
15-22 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | ECHE | POMMA | ECHE |
15-23 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | Phenyl | POMMA | Phenyl |
15-24 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | methyl | POMMA | methyl |
15-25 | H, methyl | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
표 16
Table 16
No | R13 | R14 | R16 | R17 | R18 | R19 | X의 R | Y의 R |
16-1 | H,메틸 | CF3,메틸 | ECHE | 알킬사이올 | H,메틸 | ECHE | 알킬사이올 | ECHE |
16-2 | H,에틸 | H,메틸 | ECHE | 페닐 | 알킬사이올,메틸 | 헥실 | 페닐 | 헥실 |
16-3 | H,아세틸틸 | H, CF3 | ECHE | 메틸 | H,메틸 | GlyP | 메틸 | GlyP |
16-4 | 비닐,메틸 | H,메틸 | 페닐 | GlyP | H, CF3 | POMMA | GlyP | POMMA |
16-5 | H,메틸 | H,메틸 | 페닐 | POMMA | H,에틸 | 아미노프로필 | POMMA | 아미노프로필 |
16-6 | H, F | H,옥틸 | 페닐 | ECHE | H, F | 페닐 | ECHE | 페닐 |
16-7 | CF3,메틸 | H,메틸 | ECHE | ECHE | 비닐,메틸 | GlyP | ECHE | GlyP |
16-8 | H,메틸 | H,메틸 | 헥실 | ECHE | H,메틸 | POMMA | ECHE | POMMA |
16-9 | H, CF3 | 알킬사이올,메틸 | GlyP | ECHE | H, F | 아미노프로필 | ECHE | 아미노프로필 |
16-10 | H,메틸 | H,메틸 | POMMA | 페닐 | CF3,메틸 | 페닐 | 페닐 | 페닐 |
16-11 | 아릴,메틸 | H,메틸 | 아미노프로필 | 페닐 | H,메틸 | 옥틸 | 페닐 | 옥틸 |
16-12 | H,메타크릴 | H,메틸 | 페닐 | 페닐 | H, CF3 | POMMA | 페닐 | POMMA |
16-13 | H,메틸 | 알킬사이올,메틸 | GlyP | ECHE | H,메틸 | ECHE | ECHE | ECHE |
16-14 | H,옥틸 | H,메틸 | POMMA | 헥실 | H,메틸 | 페닐 | 헥실 | 페닐 |
16-15 | H,메틸 | H, F | 아미노프로필 | GlyP | H,옥틸 | 메틸 | GlyP | 메틸 |
16-16 | H,메틸 | CF3,메틸 | 페닐 | POMMA | H,메틸 | GlyP | POMMA | GlyP |
16-17 | 알킬사이올,메틸 | H,메틸 | 옥틸 | 아미노프로필 | H,메틸 | POMMA | 아미노프로필 | POMMA |
16-18 | H,메틸 | H, CF3 | POMMA | 페닐 | 알킬사이올,메틸 | 아미노프로필 | 페닐 | 아미노프로필 |
16-19 | H, CF3 | H,메틸 | ECHE | GlyP | H,메틸 | 페닐 | GlyP | 페닐 |
16-20 | H,메틸 | H,메틸 | 페닐 | POMMA | H,메틸 | 옥틸 | POMMA | 옥틸 |
16-21 | C8F13,메틸 | H,메틸 | 메틸 | 아미노프로필 | H,메틸 | POMMA | 아미노프로필 | POMMA |
16-22 | H,프로필 | 알킬사이올,메틸 | GlyP | 페닐 | 알킬사이올,메틸 | ECHE | 페닐 | ECHE |
16-23 | F,메틸 | H,메틸 | POMMA | 옥틸 | H,메틸 | 페닐 | 옥틸 | 페닐 |
16-24 | H,메틸 | H, CF3 | POMMA | POMMA | H, CF3 | 메틸 | POMMA | 메틸 |
16-25 | H,에틸 | H,메틸 | POMMA | ECHE | H,메틸 | GlyP | ECHE | GlyP |
No | R13 | R14 | R16 | R17 | R18 | R19 | X, R | Y R |
16-1 | H, methyl | CF 3 , methyl | ECHE | Alkyl siol | H, methyl | ECHE | Alkyl siol | ECHE |
16-2 | H, ethyl | H, methyl | ECHE | Phenyl | Alkyl siol, methyl | Hexyl | Phenyl | Hexyl |
16-3 | H, acetyltyl | H, CF 3 | ECHE | methyl | H, methyl | GlyP | methyl | GlyP |
16-4 | Vinyl, methyl | H, methyl | Phenyl | GlyP | H, CF 3 | POMMA | GlyP | POMMA |
16-5 | H, methyl | H, methyl | Phenyl | POMMA | H, ethyl | Aminopropyl | POMMA | Aminopropyl |
16-6 | H, F | H, octyl | Phenyl | ECHE | H, F | Phenyl | ECHE | Phenyl |
16-7 | CF 3 , methyl | H, methyl | ECHE | ECHE | Vinyl, methyl | GlyP | ECHE | GlyP |
16-8 | H, methyl | H, methyl | Hexyl | ECHE | H, methyl | POMMA | ECHE | POMMA |
16-9 | H, CF 3 | Alkyl siol, methyl | GlyP | ECHE | H, F | Aminopropyl | ECHE | Aminopropyl |
16-10 | H, methyl | H, methyl | POMMA | Phenyl | CF 3 , methyl | Phenyl | Phenyl | Phenyl |
16-11 | Aryl, methyl | H, methyl | Aminopropyl | Phenyl | H, methyl | Octyl | Phenyl | Octyl |
16-12 | H, methacryl | H, methyl | Phenyl | Phenyl | H, CF 3 | POMMA | Phenyl | POMMA |
16-13 | H, methyl | Alkyl siol, methyl | GlyP | ECHE | H, methyl | ECHE | ECHE | ECHE |
16-14 | H, octyl | H, methyl | POMMA | Hexyl | H, methyl | Phenyl | Hexyl | Phenyl |
16-15 | H, methyl | H, F | Aminopropyl | GlyP | H, octyl | methyl | GlyP | methyl |
16-16 | H, methyl | CF 3 , methyl | Phenyl | POMMA | H, methyl | GlyP | POMMA | GlyP |
16-17 | Alkyl siol, methyl | H, methyl | Octyl | Aminopropyl | H, methyl | POMMA | Aminopropyl | POMMA |
16-18 | H, methyl | H, CF 3 | POMMA | Phenyl | Alkyl siol, methyl | Aminopropyl | Phenyl | Aminopropyl |
16-19 | H, CF 3 | H, methyl | ECHE | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
16-20 | H, methyl | H, methyl | Phenyl | POMMA | H, methyl | Octyl | POMMA | Octyl |
16-21 | C 8 F 13 , methyl | H, methyl | methyl | Aminopropyl | H, methyl | POMMA | Aminopropyl | POMMA |
16-22 | H, profile | Alkyl siol, methyl | GlyP | Phenyl | Alkyl siol, methyl | ECHE | Phenyl | ECHE |
16-23 | F, methyl | H, methyl | POMMA | Octyl | H, methyl | Phenyl | Octyl | Phenyl |
16-24 | H, methyl | H, CF 3 | POMMA | POMMA | H, CF 3 | methyl | POMMA | methyl |
16-25 | H, ethyl | H, methyl | POMMA | ECHE | H, methyl | GlyP | ECHE | GlyP |
구체적인 예로 상기 화학식 9의 실세스퀴옥산 복합고분자는 하기 표 17 및 18에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
표 17
Table 17
No | R16 | R17 | R18 | R19 | R20 | X의 R | Y의 R | E의 말단 R |
17-1 | ECHE | ECHE | H,메틸 | ECHE | ECHE | ECHE | ECHE | ECHE |
17-2 | 페닐 | 페닐 | H,메틸 | 페닐 | 페닐 | 페닐 | 페닐 | 페닐 |
17-3 | 메틸 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 | 메틸 | 메틸 |
17-4 | GlyP | EGCDX | H,메틸 | EGCDX | GlyP | EGCDX | EGCDX | GlyP |
17-5 | POMMA | POMMA | H,메틸 | POMMA | POMMA | POMMA | POMMA | POMMA |
17-6 | ECHE | ECHE | H,메틸 | ECHE | 페닐 | ECHE | ECHE | 페닐 |
17-7 | ECHE | ECHE | H,메틸 | ECHE | 메틸 | ECHE | ECHE | 메틸 |
17-8 | ECHE | ECHE | H,메틸 | ECHE | GlyP | ECHE | ECHE | GlyP |
17-9 | ECHE | ECHE | H,메틸 | ECHE | POMMA | ECHE | ECHE | POMMA |
17-10 | ECHE | 페닐 | H,메틸 | 페닐 | ECHE | 페닐 | 페닐 | ECHE |
17-11 | ECHE | 메틸 | H,메틸 | 메틸 | ECHE | 메틸 | 메틸 | ECHE |
17-12 | ECHE | GlyP | H,메틸 | GlyP | ECHE | GlyP | GlyP | ECHE |
17-13 | ECHE | POMMA | H,메틸 | POMMA | ECHE | POMMA | POMMA | ECHE |
17-14 | 페닐 | 페닐 | H,메틸 | 페닐 | ECHE | 페닐 | 페닐 | ECHE |
17-15 | 페닐 | 페닐 | H,메틸 | 페닐 | 메틸 | 페닐 | 페닐 | 메틸 |
17-16 | 페닐 | 페닐 | H,메틸 | 페닐 | EGDCX | 페닐 | 페닐 | EGDCX |
17-17 | 페닐 | 페닐 | H,메틸 | 페닐 | POMMA | 페닐 | 페닐 | POMMA |
17-18 | 페닐 | ECHE | H,메틸 | ECHE | 페닐 | ECHE | ECHE | 페닐 |
17-19 | 페닐 | 메틸 | H,메틸 | 메틸 | 페닐 | 메틸 | 메틸 | 페닐 |
17-20 | 페닐 | GlyP | H,메틸 | GlyP | 페닐 | GlyP | GlyP | 페닐 |
17-21 | 페닐 | POMMA | H,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
17-22 | 메틸 | 메틸 | H,메틸 | 메틸 | ECHE | 메틸 | 메틸 | ECHE |
17-23 | 메틸 | 메틸 | H,메틸 | 메틸 | 페닐 | 메틸 | 메틸 | 페닐 |
17-24 | 메틸 | 메틸 | H,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
17-25 | 메틸 | 메틸 | H,메틸 | 메틸 | POMMA | 메틸 | 메틸 | POMMA |
17-26 | 메틸 | ECHE | H,메틸 | ECHE | 메틸 | ECHE | ECHE | 메틸 |
17-27 | 메틸 | 페닐 | H,메틸 | 페닐 | 메틸 | 페닐 | 페닐 | 메틸 |
17-28 | 메틸 | GlyP | H,메틸 | GlyP | 메틸 | GlyP | GlyP | 메틸 |
17-29 | 메틸 | POMMA | H,메틸 | POMMA | 메틸 | POMMA | POMMA | 메틸 |
17-30 | GlyP | GlyP | H,메틸 | GlyP | ECHE | GlyP | GlyP | ECHE |
17-31 | GlyP | GlyP | H,메틸 | GlyP | 페닐 | GlyP | GlyP | 페닐 |
17-32 | GlyP | GlyP | H,메틸 | GlyP | 메틸 | GlyP | GlyP | 메틸 |
17-33 | GlyP | GlyP | H,메틸 | GlyP | POMMA | GlyP | GlyP | POMMA |
17-34 | GlyP | ECHE | H,메틸 | ECHE | GlyP | ECHE | ECHE | GlyP |
17-35 | GlyP | 페닐 | H,메틸 | 페닐 | GlyP | 페닐 | 페닐 | GlyP |
17-36 | GlyP | 메틸 | H,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
17-37 | GlyP | POMMA | H,메틸 | POMMA | GlyP | POMMA | POMMA | GlyP |
17-38 | POMMA | POMMA | H,메틸 | POMMA | ECHE | POMMA | POMMA | ECHE |
17-39 | POMMA | POMMA | H,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
17-40 | POMMA | POMMA | H,메틸 | POMMA | 메틸 | POMMA | POMMA | 메틸 |
17-41 | POMMA | POMMA | H,메틸 | POMMA | GlyP | POMMA | POMMA | GlyP |
17-42 | POMMA | ECHE | H,메틸 | ECHE | POMMA | ECHE | ECHE | POMMA |
17-43 | POMMA | 페닐 | H,메틸 | 페닐 | POMMA | 페닐 | 페닐 | POMMA |
17-44 | POMMA | 메틸 | H,메틸 | 메틸 | POMMA | 메틸 | 메틸 | POMMA |
17-45 | POMMA | GlyP | H,메틸 | GlyP | POMMA | GlyP | GlyP | POMMA |
No | R16 | R17 | R18 | R19 | R20 | X, R | Y R | Terminal R of E |
17-1 | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE | ECHE | ECHE |
17-2 | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl | Phenyl | Phenyl |
17-3 | methyl | methyl | H, methyl | methyl | methyl | methyl | methyl | methyl |
17-4 | GlyP | EGCDX | H, methyl | EGCDX | GlyP | EGCDX | EGCDX | GlyP |
17-5 | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA | POMMA | POMMA |
17-6 | ECHE | ECHE | H, methyl | ECHE | Phenyl | ECHE | ECHE | Phenyl |
17-7 | ECHE | ECHE | H, methyl | ECHE | methyl | ECHE | ECHE | methyl |
17-8 | ECHE | ECHE | H, methyl | ECHE | GlyP | ECHE | ECHE | GlyP |
17-9 | ECHE | ECHE | H, methyl | ECHE | POMMA | ECHE | ECHE | POMMA |
17-10 | ECHE | Phenyl | H, methyl | Phenyl | ECHE | Phenyl | Phenyl | ECHE |
17-11 | ECHE | methyl | H, methyl | methyl | ECHE | methyl | methyl | ECHE |
17-12 | ECHE | GlyP | H, methyl | GlyP | ECHE | GlyP | GlyP | ECHE |
17-13 | ECHE | POMMA | H, methyl | POMMA | ECHE | POMMA | POMMA | ECHE |
17-14 | Phenyl | Phenyl | H, methyl | Phenyl | ECHE | Phenyl | Phenyl | ECHE |
17-15 | Phenyl | Phenyl | H, methyl | Phenyl | methyl | Phenyl | Phenyl | methyl |
17-16 | Phenyl | Phenyl | H, methyl | Phenyl | EGDCX | Phenyl | Phenyl | EGDCX |
17-17 | Phenyl | Phenyl | H, methyl | Phenyl | POMMA | Phenyl | Phenyl | POMMA |
17-18 | Phenyl | ECHE | H, methyl | ECHE | Phenyl | ECHE | ECHE | Phenyl |
17-19 | Phenyl | methyl | H, methyl | methyl | Phenyl | methyl | methyl | Phenyl |
17-20 | Phenyl | GlyP | H, methyl | GlyP | Phenyl | GlyP | GlyP | Phenyl |
17-21 | Phenyl | POMMA | H, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
17-22 | methyl | methyl | H, methyl | methyl | ECHE | methyl | methyl | ECHE |
17-23 | methyl | methyl | H, methyl | methyl | Phenyl | methyl | methyl | Phenyl |
17-24 | methyl | methyl | H, methyl | methyl | GlyP | methyl | methyl | GlyP |
17-25 | methyl | methyl | H, methyl | methyl | POMMA | methyl | methyl | POMMA |
17-26 | methyl | ECHE | H, methyl | ECHE | methyl | ECHE | ECHE | methyl |
17-27 | methyl | Phenyl | H, methyl | Phenyl | methyl | Phenyl | Phenyl | methyl |
17-28 | methyl | GlyP | H, methyl | GlyP | methyl | GlyP | GlyP | methyl |
17-29 | methyl | POMMA | H, methyl | POMMA | methyl | POMMA | POMMA | methyl |
17-30 | GlyP | GlyP | H, methyl | GlyP | ECHE | GlyP | GlyP | ECHE |
17-31 | GlyP | GlyP | H, methyl | GlyP | Phenyl | GlyP | GlyP | Phenyl |
17-32 | GlyP | GlyP | H, methyl | GlyP | methyl | GlyP | GlyP | methyl |
17-33 | GlyP | GlyP | H, methyl | GlyP | POMMA | GlyP | GlyP | POMMA |
17-34 | GlyP | ECHE | H, methyl | ECHE | GlyP | ECHE | ECHE | GlyP |
17-35 | GlyP | Phenyl | H, methyl | Phenyl | GlyP | Phenyl | Phenyl | GlyP |
17-36 | GlyP | methyl | H, methyl | methyl | GlyP | methyl | methyl | GlyP |
17-37 | GlyP | POMMA | H, methyl | POMMA | GlyP | POMMA | POMMA | GlyP |
17-38 | POMMA | POMMA | H, methyl | POMMA | ECHE | POMMA | POMMA | ECHE |
17-39 | POMMA | POMMA | H, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
17-40 | POMMA | POMMA | H, methyl | POMMA | methyl | POMMA | POMMA | methyl |
17-41 | POMMA | POMMA | H, methyl | POMMA | GlyP | POMMA | POMMA | GlyP |
17-42 | POMMA | ECHE | H, methyl | ECHE | POMMA | ECHE | ECHE | POMMA |
17-43 | POMMA | Phenyl | H, methyl | Phenyl | POMMA | Phenyl | Phenyl | POMMA |
17-44 | POMMA | methyl | H, methyl | methyl | POMMA | methyl | methyl | POMMA |
17-45 | POMMA | GlyP | H, methyl | GlyP | POMMA | GlyP | GlyP | POMMA |
표 18
Table 18
No | R16 | R17 | R18 | R19 | R20 | X의 R | Y의 R | E의 말단R |
18-1 | ECHE | POMMA | H,메틸 | ECHE | POMMA | POMMA | ECHE | POMMA |
18-2 | 페닐 | POMMA | H,에틸 | 페닐 | POMMA | POMMA | 페닐 | POMMA |
18-3 | POMMA | ECHE | H,아세틸틸 | 메틸 | ECHE | ECHE | 메틸 | ECHE |
18-4 | 메틸 | ECHE | 비닐,메틸 | EGCDX | ECHE | ECHE | EGCDX | ECHE |
18-5 | POMMA | F | H,메틸 | POMMA | F | F | POMMA | F |
18-6 | 프로필 | 아미노프로필 | CF3,메틸 | ECHE | 아미노프로필 | 아미노프로필 | ECHE | 아미노프로필 |
18-7 | 페닐 | 페닐 | H,메틸 | ECHE | 페닐 | 페닐 | ECHE | 페닐 |
18-8 | 메틸 | 알킬사이올 | H,아세틸틸 | ECHE | 알킬사이올 | 알킬사이올 | ECHE | 알킬사이올 |
18-9 | GlyP | 페닐 | 비닐,메틸 | ECHE | 페닐 | 페닐 | ECHE | 페닐 |
18-10 | ECHE | 옥틸 | H,메틸 | 페닐 | 옥틸 | 옥틸 | 페닐 | 옥틸 |
18-11 | 알킬사이올 | 메틸 | H,메틸 | 메틸 | 메틸 | 메틸 | 메틸 | 메틸 |
18-12 | 페닐 | 옥틸 | 비닐,메틸 | GlyP | 옥틸 | 옥틸 | GlyP | 옥틸 |
18-13 | 옥틸 | 옥틸 | H,메틸 | POMMA | 옥틸 | 옥틸 | POMMA | 옥틸 |
18-14 | 메틸 | 메틸 | H, F | 페닐 | 메틸 | 메틸 | 페닐 | 메틸 |
18-15 | 옥틸 | GlyP | CF3,메틸 | 페닐 | ECHE | GlyP | 페닐 | ECHE |
18-16 | 옥틸 | GlyP | 비닐,메틸 | 페닐 | 페닐 | GlyP | 페닐 | 페닐 |
18-17 | 메틸 | 아미노프로필 | H,메틸 | 페닐 | POMMA | 아미노프로필 | 페닐 | POMMA |
18-18 | GlyP | GlyP | H, F | ECHE | 메틸 | GlyP | ECHE | 메틸 |
18-19 | GlyP | POMMA | CF3,메틸 | 메틸 | POMMA | POMMA | 메틸 | POMMA |
18-20 | 아미노프로필 | 메틸 | H,메틸 | GlyP | 프로필 | 메틸 | GlyP | 프로필 |
18-21 | GlyP | POMMA | 알킬사이올,메틸 | POMMA | 페닐 | POMMA | POMMA | 페닐 |
18-22 | POMMA | 프로필 | H,아세틸틸 | 메틸 | 메틸 | 프로필 | 메틸 | 메틸 |
18-23 | POMMA | 메틸 | 비닐,메틸 | 메틸 | GlyP | 메틸 | 메틸 | GlyP |
18-24 | GlyP | GlyP | 비닐,메틸 | 메틸 | ECHE | GlyP | 메틸 | ECHE |
18-25 | 아미노프로필 | GlyP | H,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
18-26 | 메틸 | 아미노프로필 | H, F | ECHE | 아미노프로필 | 아미노프로필 | ECHE | 아미노프로필 |
18-27 | 메틸 | GlyP | CF3,메틸 | 페닐 | GlyP | GlyP | 페닐 | GlyP |
18-28 | 메틸 | 옥틸 | H,메틸 | GlyP | 옥틸 | 옥틸 | GlyP | 옥틸 |
18-29 | 메틸 | 메틸 | H,아세틸틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
18-30 | 아미노프로필 | GlyP | 비닐,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
18-31 | GlyP | GlyP | H,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
18-32 | POMMA | 아미노프로필 | H,메틸 | GlyP | 아미노프로필 | 아미노프로필 | GlyP | 아미노프로필 |
18-33 | 메틸 | GlyP | 비닐,메틸 | GlyP | GlyP | GlyP | GlyP | GlyP |
18-34 | POMMA | POMMA | H,메틸 | ECHE | POMMA | POMMA | ECHE | POMMA |
18-35 | 프로필 | POMMA | H, F | 페닐 | POMMA | POMMA | 페닐 | POMMA |
18-36 | 메틸 | GlyP | CF3,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
18-37 | GlyP | 아미노프로필 | 비닐,메틸 | POMMA | 아미노프로필 | 아미노프로필 | POMMA | 아미노프로필 |
18-38 | GlyP | 메틸 | H,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
18-39 | 아미노프로필 | 메틸 | H, F | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
18-40 | 아미노프로필 | 메틸 | CF3,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
18-41 | GlyP | 메틸 | H,메틸 | POMMA | 메틸 | 메틸 | POMMA | 메틸 |
18-42 | POMMA | GlyP | 알킬사이올,메틸 | ECHE | GlyP | GlyP | ECHE | GlyP |
18-43 | POMMA | 아미노프로필 | H,아세틸틸 | 페닐 | 아미노프로필 | 아미노프로필 | 페닐 | 아미노프로필 |
18-44 | POMMA | GlyP | 비닐,메틸 | 메틸 | GlyP | GlyP | 메틸 | GlyP |
18-45 | POMMA | POMMA | H,메틸 | GlyP | POMMA | POMMA | GlyP | POMMA |
No | R16 | R17 | R18 | R19 | R20 | X, R | Y R | Terminal R of E |
18-1 | ECHE | POMMA | H, methyl | ECHE | POMMA | POMMA | ECHE | POMMA |
18-2 | Phenyl | POMMA | H, ethyl | Phenyl | POMMA | POMMA | Phenyl | POMMA |
18-3 | POMMA | ECHE | H, acetyltyl | methyl | ECHE | ECHE | methyl | ECHE |
18-4 | methyl | ECHE | Vinyl, methyl | EGCDX | ECHE | ECHE | EGCDX | ECHE |
18-5 | POMMA | F | H, methyl | POMMA | F | F | POMMA | F |
18-6 | profile | Aminopropyl | CF 3 , methyl | ECHE | Aminopropyl | Aminopropyl | ECHE | Aminopropyl |
18-7 | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | Phenyl | ECHE | Phenyl |
18-8 | methyl | Alkyl siol | H, acetyltyl | ECHE | Alkyl siol | Alkyl siol | ECHE | Alkyl siol |
18-9 | GlyP | Phenyl | Vinyl, methyl | ECHE | Phenyl | Phenyl | ECHE | Phenyl |
18-10 | ECHE | Octyl | H, methyl | Phenyl | Octyl | Octyl | Phenyl | Octyl |
18-11 | Alkyl siol | methyl | H, methyl | methyl | methyl | methyl | methyl | methyl |
18-12 | Phenyl | Octyl | Vinyl, methyl | GlyP | Octyl | Octyl | GlyP | Octyl |
18-13 | Octyl | Octyl | H, methyl | POMMA | Octyl | Octyl | POMMA | Octyl |
18-14 | methyl | methyl | H, F | Phenyl | methyl | methyl | Phenyl | methyl |
18-15 | Octyl | GlyP | CF 3 , methyl | Phenyl | ECHE | GlyP | Phenyl | ECHE |
18-16 | Octyl | GlyP | Vinyl, methyl | Phenyl | Phenyl | GlyP | Phenyl | Phenyl |
18-17 | methyl | Aminopropyl | H, methyl | Phenyl | POMMA | Aminopropyl | Phenyl | POMMA |
18-18 | GlyP | GlyP | H, F | ECHE | methyl | GlyP | ECHE | methyl |
18-19 | GlyP | POMMA | CF 3 , methyl | methyl | POMMA | POMMA | methyl | POMMA |
18-20 | Aminopropyl | methyl | H, methyl | GlyP | profile | methyl | GlyP | profile |
18-21 | GlyP | POMMA | Alkyl siol, methyl | POMMA | Phenyl | POMMA | POMMA | Phenyl |
18-22 | POMMA | profile | H, acetyltyl | methyl | methyl | profile | methyl | methyl |
18-23 | POMMA | methyl | Vinyl, methyl | methyl | GlyP | methyl | methyl | GlyP |
18-24 | GlyP | GlyP | Vinyl, methyl | methyl | ECHE | GlyP | methyl | ECHE |
18-25 | Aminopropyl | GlyP | H, methyl | methyl | GlyP | GlyP | methyl | GlyP |
18-26 | methyl | Aminopropyl | H, F | ECHE | Aminopropyl | Aminopropyl | ECHE | Aminopropyl |
18-27 | methyl | GlyP | CF 3 , methyl | Phenyl | GlyP | GlyP | Phenyl | GlyP |
18-28 | methyl | Octyl | H, methyl | GlyP | Octyl | Octyl | GlyP | Octyl |
18-29 | methyl | methyl | H, acetyltyl | POMMA | methyl | methyl | POMMA | methyl |
18-30 | Aminopropyl | GlyP | Vinyl, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
18-31 | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
18-32 | POMMA | Aminopropyl | H, methyl | GlyP | Aminopropyl | Aminopropyl | GlyP | Aminopropyl |
18-33 | methyl | GlyP | Vinyl, methyl | GlyP | GlyP | GlyP | GlyP | GlyP |
18-34 | POMMA | POMMA | H, methyl | ECHE | POMMA | POMMA | ECHE | POMMA |
18-35 | profile | POMMA | H, F | Phenyl | POMMA | POMMA | Phenyl | POMMA |
18-36 | methyl | GlyP | CF 3 , methyl | methyl | GlyP | GlyP | methyl | GlyP |
18-37 | GlyP | Aminopropyl | Vinyl, methyl | POMMA | Aminopropyl | Aminopropyl | POMMA | Aminopropyl |
18-38 | GlyP | methyl | H, methyl | POMMA | methyl | methyl | POMMA | methyl |
18-39 | Aminopropyl | methyl | H, F | POMMA | methyl | methyl | POMMA | methyl |
18-40 | Aminopropyl | methyl | CF 3 , methyl | POMMA | methyl | methyl | POMMA | methyl |
18-41 | GlyP | methyl | H, methyl | POMMA | methyl | methyl | POMMA | methyl |
18-42 | POMMA | GlyP | Alkyl siol, methyl | ECHE | GlyP | GlyP | ECHE | GlyP |
18-43 | POMMA | Aminopropyl | H, acetyltyl | Phenyl | Aminopropyl | Aminopropyl | Phenyl | Aminopropyl |
18-44 | POMMA | GlyP | Vinyl, methyl | methyl | GlyP | GlyP | methyl | GlyP |
18-45 | POMMA | POMMA | H, methyl | GlyP | POMMA | POMMA | GlyP | POMMA |
본 발명의 상기 실세스퀴옥산 복합 고분자는 우수한 보관 안정성을 확보하여 폭넓은 응용성을 얻기 위해, 축합도가 1 내지 99.9% 이상으로 조절될 수 있다. 즉, 말단 및 중앙의 Si에 결합된 알콕시 그룹의 함량이 전체 고분자의 결합기에 대해 50%에서 0.01%까지 조절될 수 있다.The silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
또한 본 발명에 실세스퀴옥산 복합 고분자의 중량평균분자량은 1,000 내지 1,000,000, 바람직하게는 5,000 내지 100,000이며, 더욱 바람직하게는 7,000 내지 50,000일 수 있다. 이 경우 실세스퀴옥산의 가공성 및 물리적 특성을 동시에 향상시킬 수 있다.In addition, the weight average molecular weight of the silsesquioxane composite polymer according to the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.
본 발명에서 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물은 2종 이상의 복합 고분자를 사용하는 것도 가능하며, 바람직하기로는 화학식 3 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 사용하는 것이 좋다. 이 경우 반복단위 [B]b 또는 [E]e를 포함함으로써 코팅의 물성을 더욱 향상시킬 수 있다.In the present invention, the metal coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more kinds of composite polymers, and is preferably represented by any one of Formulas 3 to 9. It is preferable to use a silsesquioxane composite polymer. In this case, the physical properties of the coating can be further improved by including the repeating unit [B] b or [E] e.
본 발명에서 상기 금속코팅조성물은 실세스퀴옥산 복합 고분자가 액상인 경우 무용제 타입으로 단독으로 코팅이 가능하며, 고상인 경우 유기용매를 포함하여 구성될 수 있다. 또한 코팅 조성물은 개시제 또는 경화제를 더욱 포함할 수 있다.In the present invention, the metal coating composition may be coated alone as a solventless type when the silsesquioxane composite polymer is in a liquid state, and may include an organic solvent in the case of a solid phase. In addition, the coating composition may further include an initiator or a curing agent.
바람직하기로 상기 코팅조성물은 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자, 상기 복합 고분자와 상용성이 있는 당분야에서 통상적으로 사용하는 유기용매, 개시제를 포함하는 것을 특징으로 하며, 선택적으로 경화제, 가소제, 자외선 차단제, 기타 기능성 첨가제 등의 첨가제를 추가로 포함하여 경화성, 내열특성, 자외선차단, 가소 효과 등을 향상시킬 수 있다.Preferably, the coating composition is characterized in that it comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art that is compatible with the composite polymer, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
본 발명의 코팅 조성물에 있어서 상기 실세스퀴옥산 복합 고분자는 코팅 조성물 100 중량부에 대하여 적어도 5 중량부 이상으로 포함되는 것이 좋으며, 바람직하게는 5 내지 90 중량부, 더욱 바람직하게는 10 내지 50 중량부의 양으로 포함되는 것이 바람직하다. 상기 범위 내인 경우 코팅 조성물의 경화막의 기계적 물성을 더욱 향상시킬 수 있다.In the coating composition of the present invention, the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
상기 유기용매로는 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜 류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 이용할 수 있으나, 이에 제한되지는 않는다. 상기 유기용매의 양은 복합고분자, 개시제, 및 선택적으로 추가되는 첨가제를 제외한 잔량으로 포함된다.Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, In addition to polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the composite polymer, the initiator, and optionally added additives.
또한 본 발명의 코팅 조성물에 있어서 상기 개시제 또는 경화제는 실세스퀴옥산 복합 고분자에 포함된 유기관능기에 따라 적절히 선택하여 사용할 수 있다.In the coating composition of the present invention, the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
구체적인 예로서 상기 유기관능기에 불포화 탄화수소, 사이올계, 에폭시계, 아민계, 이소시아네이트계 등의 후경화가 가능한 유기계가 도입될 경우, 열 또는 광을 이용한 다양한 경화가 가능하다. 이때 열 또는 광에 의한 변화를 고분자 자체 내에서 도모할 수 있지만, 바람직하게는 상기와 같은 유기용매에 희석함으로써 경화공정을 도모할 수 있다. As a specific example, when an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
또한 본 발명에서는 복합 고분자의 경화 및 후 반응을 위하여, 다양한 개시제를 사용할 수 있으며, 상기 개시제는 조성물 총중량 100 중량부에 대하여 0.1-20 중량부로 포함되는 것이 바람직하며, 상기 범위 내의 함량으로 포함될 때, 경화 후 투과도 및 코팅안정성을 동시에 만족시킬 수 있다.In addition, in the present invention, for curing and post-reaction of the composite polymer, various initiators may be used, and the initiator may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
또한 상기 유기관능기에 불포화 탄화수소 등이 도입될 경우에는 라디칼 개시제를 사용할 수 있으며, 상기 라디칼 개시제로는 트리클로로 아세토페논(trichloro acetophenone), 디에톡시 아세토페논(diethoxy acetophenone), 1-페닐-2-히드록시-2-메틸프로판-1-온(1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-히드록시사이클로헥실페닐케톤, 2-메틸-1-(4-메틸 티오페닐)-2-모르폴리노프로판-1-온(2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-트리메틸 벤조일 디페닐포스핀 옥사이드(trimethyl benzoyl diphenylphosphine oxide), 캠퍼 퀴논(camphor quinine), 2,2'-아조비스(2-메틸부티로니트릴), 디메틸-2,2'-아조비스(2-메틸 부틸레이트), 3,3-디메틸-4-메톡시-벤조페논, p-메톡시벤조페논, 2,2-디에톡시 아세토페논, 2,2-디메톡시-1,2-디페닐 에탄-1-온 등의 광 래디컬 개시제, t-부틸파옥시 말레인산, t-부틸하이드로퍼옥사이드, 2,4'-디클로로벤조일퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, N-부틸-4,4'-디(t-부틸퍼옥시)발레레이트 등의 열 라디칼 개시제 및 이들의 다양한 혼합물 등이 사용될 수 있다. In addition, when an unsaturated hydrocarbon or the like is introduced into the organic functional group, a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride. Hydroxy-2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl) 2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Optical radical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylpaoxy maleic acid, t-butyl Iroperoxide, 2,4'-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t- Thermal radical initiators such as butylperoxy) valerate and various mixtures thereof and the like can be used.
또한, 상기 유기관능기에 에폭시 등이 포함되는 경우에는, 광중합 개시제(양이온)로서 트리페닐술포늄, 디페닐-4-(페닐티오)페닐술포늄 등의 술포늄계, 디페닐요오드늄이나 비스(도데실페닐)요오드늄 등의 요오드늄, 페닐디아조늄 등의 디아조늄, 1-벤질-2-시아노피리니늄이나 1-(나프틸메틸)-2-시아노프리디늄 등의 암모늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]-헥사플루오로포스페이트 요오드늄, 비스(4-t-부틸페닐)헥사플루오로포스페이트 요오드늄, 디페닐헥사플루오로포스페이트 요오드늄, 디페닐트리플루오로메탄술포네이트 요오드늄, 트리페닐술포늄 테트라풀루오로보레이트, 트리-p-토일술포늄 헥사풀루오로포스페이트, 트리-p-토일술포늄 트리풀루오로메탄술포네이트 및 (2,4-시클로펜타디엔-1-일)[(1-메틸에틸)벤젠]-Fe 등의 Fe 양이온들과 BF4
-, PF6
-, SbF6
- 등의 [BQ4]- 오늄염 조합을 이용할 수 있다(여기서, Q는 적어도 2개 이상의 불소 또는 트리플루오로메틸기로 치환된 페닐기이다.). When the organic functional group contains an epoxy or the like, sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations). Iodonium, such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopentadiene-1-yl) s Fe cations such as [(1-methylethyl) benzene] -Fe and BF 4 -, PF 6 -, SbF 6 - [BQ 4 ] , such as-may be used in combination with onium salts (here, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.).
또한, 열에 의해 작용하는 양이온 개시제로는 트리플산염, 3불화 붕소 에테르착화합물, 3불화 붕소 등과 같은 양이온계 또는 프로톤산 촉매, 암모늄염, 포스포늄염 및 술포늄염 등의 각종 오늄염 및 메틸트리페닐포스포늄 브롬화물, 에틸트리페닐포스포늄 브롬화물, 페닐트리페닐포스포늄 브롬화물 등을 제한 없이 사용할 수 있으며, 이들 개시제 또한 다양한 혼합형태로 첨가할 수 있으며, 상기에 명시한 다양한 라디칼 개시제들과의 혼용도 가능하다. In addition, the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
또한, 상기 유기관능기의 종류에 따라, 아민 경화제류인 에틸렌디아민, 트리에틸렌 테트라민, 테트라에틸렌 펜타민, 1,3-디아미노프로판, 디프로필렌트리아민, 3-(2-아미노에틸)아미노-프로필아민, N,N'-비스(3-아미노프로필)-에틸렌디아민, 4,9-디옥사도테칸-1,12-디아민, 4,7,10-트리옥사트리데칸-1,13-디아민, 헥사메틸렌디아민, 2-메틸펜타메틸렌디아민, 1,3-비스아미노메틸시클로헥산, 비스(4-아니모시클로헥실)메탄, 노르보르넨디아민, 1,2-디아미노시클로헥산 등을 이용할 수 있다. Moreover, according to the kind of said organic functional group, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1, 3- diamino propane, dipropylene triamine, 3- (2-amino ethyl) amino-propyl Amines, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like can be used. .
아울러, 무수프탈산, 무수트리멜리트산, 무수피로멜리트산, 무수말레산, 테트라히드로 무수프탈산, 메틸헥사히드로 무수프탈산, 메틸테트라히드로 무수프탈산, 메틸나드산 무수물, 수소화메틸나드산 무수물, 트리알킬테트라히드로 무수프탈산, 도데세닐 무수숙신산, 무수2,4-디에틸글루타르산 등의 산무수경화제류도 폭넓게 사용될 수 있다.In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
상기 경화제는 조성물 100 중량부에 대하여 0.1-20 중량부로 포함되는 것이 좋다. The hardener is preferably included in 0.1-20 parts by weight based on 100 parts by weight of the composition.
또한 상기 경화작용을 촉진하기 위한 경화 촉진제로, 아세토구아나민, 벤조구아나민, 2,4-디아미노-6-비닐-s-트리아진 등의 트리아진계 화합물, 이미다졸, 2-메틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 비닐이미다졸, 1-메틸이미다졸 등의 이미다졸계 화합물, 1,5-디아자비시클로[4.3.0]논엔-5,1,8-디아자비시클로[5.4.0]운데센-7, 트리페닐포스핀, 디페닐(p-트릴)포스핀, 트리스(알킬페닐)포스핀, 트리스(알콕시페닐)포스핀, 에틸트리페닐포스포늄포스페이트, 테트라부틸포스포늄히드록시드, 테트라부틸포스포늄아세테이트, 테트라부틸포스포늄하이드로젠디플루오라이드, 테트라부틸포스포늄디하이드로젠트리플루오르 등도 사용될 수 있다.In addition, as a curing accelerator for promoting the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, tetrabutylphosphonium dihydrogen tree Fluorine and the like can also be used.
본 발명에서는 또한 경화공정 또는 후반응을 통한 경도, 강도, 내구성, 성형성 등을 개선하는 목적으로 자외선 흡수제, 산화 방지제, 소포제, 레벨링제, 발수제, 난연제, 접착개선제 등의 첨가제를 추가로 포함할 수 있다. 이러한 첨가제는 그 사용에 있어 특별하게 제한은 없으나 기판의 특성 즉, 유연성, 투광성, 내열성, 경도, 강도 등의 물성을 해치지 않는 범위 내에서 적절히 첨가할 수 있다. 상기 첨가제는 각각 독립적으로 조성물 100 중량부에 대하여 0.01-10 중량부로 포함되는 것이 좋다.The present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction. Can be. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
본 발명에서 사용가능한 첨가제로는 폴리에테르 디메틸폴리실록산계 (Polyether-modified polydimethylsiloxane, 예를 들어, BYK 사 제품인 BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310 등), 폴리에테르 하이드록시 폴리디메틸실록산계 (Polyether modified hydroxyfunctional poly-dimethyl-siloxane, 예를 들어, BYK 사의 BYK-308, BYK-373 등), 폴리메틸알킬실록산계 (Methylalkylpolysiloxane, 예를 들어, BYK-077, BYK-085 등), 폴리에테르 폴리메틸알킬실록산계 (Polyether modified methylalkylpolysiloxane, 예를 들어, BYK-320, BYK-325 등), 폴리에스테르 폴리메틸알킬실록산계 (Polyester modified poly-methyl-alkyl-siloxane, 예를 들어, BYK-315 등), 알랄킬 폴리메틸알킬실록산계 (Aralkyl modified methylalkyl polysiloxane, 예를 들어, BYK-322, BYK-323 등), 폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-370 등), 폴리에스테르 아크릴 폴리디메틸실록산계 (Acrylic functional polyester modified polydimethylsiloxane, 예를 들어, BYK-371, BYK-UV 3570 등), 폴리에테르-폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyeher-polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-375 등), 폴리에테르 폴리디메틸실록산계 (Polyether modified dimethylpolysiloxane, 예를 들어, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337 등), 비이온 폴리아크릴계 (Non-ionic acrylic copolymer, 예를 들어, BYK-380 등), 이온성 폴리아크릴계 (Ionic acrylic copolymer, 예를 들어, BYK-381 등), 폴리아크릴레이트계 (Polyacrylate, 예를 들어, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 등), 폴리메타아크릴레이트계 (Polymethacrylate, 예를 들어, BYK-390 등), 폴리에테르 아크릴 폴리디메틸실록산계 (Polyether modified acryl functional polydimethylsiloxane, 예를 들어, BYK-UV 3500, BYK-UV3530 등), 폴리에테르 실록산계 (Polyether modified siloxane, 예를 들어, BYK-347 등), 알코올 알콕시레이트계 (Alcohol alkoxylates, 예를 들어, BYK-DYNWET 800 등), 아크릴레이트계 (Acrylate, 예를 들어, BYK-392 등), 하이드록시 실리콘 폴리아크릴레이트계 (Silicone modified polyacrylate (OH-functional), 예를 들어, BYK-Silclean 3700 등) 등을 들 수 있다.Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aralkyl modified methylalkyl polysiloxane, e.g. For example, BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc.), polyacrylates (e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 etc.), polymethacrylate type (Polymethacrylate, for example, BYK-390 etc.), polyether Polyether modified acryl functional polydimethylsiloxane (eg, BYK-UV 3500, BYK-UV3530, etc.), polyether siloxane (polyether modified siloxane, eg, BYK-347, etc.), alcohol alkoxylates (Alcohol alkoxylates, eg BYK-DYNWET 800, etc.), acrylates (Acrylate, eg, BYK-392, etc.), hydroxy silicone polyacrylates (Silicone modified polyacrylate (OH-functional), eg BYK-Silclean 3700, etc. are mentioned, for example.
본 발명에 있어서, 상기 금속코팅조성물을 금속 표면 위에 코팅하는 방법은 스핀코팅, 바코팅, 슬릿코팅, 딥 코팅, 내츄럴 코팅, 리버스 코팅, 롤 코팅, 스핀코팅, 커텐코팅, 스프레이 코팅, 침지법, 함침법, 그라비어 코팅 등 공지된 방법 중에서 당업자가 임의로 선택하여 적용할 수 있음은 물론이며, 경화방법에 있어도 광경화 또는 열경화를 복합고분자의 관능기에 따라 적절하게 선택하여 적용할 수 있음은 물론이다. 바람직하기로 열경화의 경우 경화온도는 80 내지 120 이다.In the present invention, the method of coating the metal coating composition on the metal surface is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping, Of course, those skilled in the art can arbitrarily select and apply among known methods such as impregnation and gravure coating, and of course, photocuring or thermal curing can be appropriately selected and applied according to the functional group of the composite polymer. . Preferably the curing temperature in the case of thermosetting is 80 to 120.
본 발명에서 상기 코팅 조성물의 코팅 두께는 임의로 조절 가능하며, 바람직하게는 0.01 내지 500 um이며, 더욱 바람직하게는 0.1 내지 300 um, 더더욱 바람직하기로는 1 내지 100 um 범위가 좋다. 상기 범위 내인 경우 7H 이상의 표면경도를 안정적으로 확보할 수 있을 뿐만 아니라 기판 표면 특성에 있어서도 우수한 물성을 나타낸다. 특히 10 um 이상의 두께로 코팅층이 적층된 경우 표면경도가 9H를 안정적으로 나타낼 수 있다.In the present invention, the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, even more preferably 1 to 100 um. Within the above range, not only can the surface hardness of 7H or more be stably secured, but also excellent physical properties of the substrate surface properties. In particular, when the coating layer is laminated to a thickness of 10um or more, the surface hardness can be represented stably 9H.
또한 본 발명은 표면 위에 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물이 코팅되어 경화된 경화물을 포함하는 것을 특징으로 실세스퀴옥산 복합 고분자 코팅 금속과 상기 실세스퀴옥산 복합 고분자 코팅 금속을 포함하는 제품을 제공하는 바, 상기 실세스퀴옥산 복합 고분자 코팅 금속은 상기 금속코팅방법에 의하여 제조될 수 있다.In addition, the present invention is a silsesquioxane composite polymer coating metal, characterized in that it comprises a cured hardened by coating a metal coating composition comprising a silsesquioxane composite polymer represented by any one of the above formulas (1) to (9) When the product containing the silsesquioxane composite polymer coating metal is provided, the silsesquioxane composite polymer coating metal may be prepared by the metal coating method.
본 발명에 따른 실세스퀴옥산 복합 고분자 코팅 금속은 실세스퀴옥산 복합 고분자 코팅층과 금속과의 접착력이 우수하며, 형성된 실세스퀴옥산 복합 고분자 코팅층이 금속 표면에 우수한 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성을 부여한다. 본 발명의 실세스퀴옥산 복합 고분자 코팅 금속을 포함하는 물품은 상기 실세스퀴옥산 복합 고분자 코팅 금속을 포함하는 제품으로 다양한 분야에서 유용하게 사용될 수 있으며, 특히 자동차, 주방용품, 금속관(상수도관 포함), 금속조형물, 가로등, 교통표지판, 태양전지 외관프레임, 도로분리대, 건축물 등에 유용하게 사용할 수 있을 뿐만 아니라 금속 배선이 사용되는 반도체, 디스플레이 분야에도 효율적으로 사용될 수 있다.The silsesquioxane composite polymer coating metal according to the present invention has excellent adhesion between the silsesquioxane composite polymer coating layer and the metal, and the formed silsesquioxane composite polymer coating layer has excellent rust resistance, scratch resistance, It imparts water repellent properties, moisture shielding properties, antifouling properties, glossiness, surface strength, and thermal stability. Articles containing the silsesquioxane composite polymer coating metal of the present invention is a product containing the silsesquioxane composite polymer coating metal can be usefully used in various fields, in particular, automobiles, kitchen appliances, metal pipes (including water pipes) ), As well as metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc., as well as can be efficiently used in the field of semiconductors and displays where metal wiring is used.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 하기 본 발명의 실시예에서 ECHETMS는 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, GPTMS는 Glycidoxypropytrimethoxysilane, MAPTMS는 (methacryloyloxy)propyltrimethoxysilane, PTMS는 Phenyltrimethoxysilane, MTMS는 Methyltrimethoxysilane, ECHETMDS는 Di(epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS는 Di(glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS는 Di(methacryloyloxy)propy, PTMDS는 Di(phenyl) tetramethoxy disiloxane, MTMDS는 Di(Methyl) tetramethoxy disiloxane을 의미한다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples. In the embodiment of the present invention, ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy) propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, and ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS stands for Di (methacryloyloxy) propy, PTMDS stands for Di (phenyl) tetramethoxy disiloxane, and MTMDS stands for Di (Methyl) tetramethoxy disiloxane.
[실시예 1] 공중합체 1 및 9을 포함하는 코팅조성물의 제조Example 1 Preparation of a Coating Composition Comprising Copolymers 1 and 9
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였다. In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows.
[실시예 1-a] 촉매의 제조Example 1-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 1-b] 선형 실세스퀴옥산 구조의 합성Example 1-b Synthesis of Linear Silsesquioxane Structure
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 1-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 화학식 4구조와 같은 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
[실시예 1-c] 연속적 cage 구조의 생성Example 1-c Generation of a continuous cage structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 50% 이상 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 11,000으로 측정되었으며, n 값은 4-6이었다. 29Si-NMR (CDCl3)δTo the mixed solution of Example 1-b 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced by using a phenyl group appeared as two sharp forms, and 50% of the AD polymer of Formula 1 without remaining by-products remained. It was confirmed that the above was manufactured. In addition, the styrene reduced molecular weight was measured to 11,000, n value was 4-6. 29 Si-NMR (CDCl 3 ) δ
[실시예 1-d] 광경화형 수지 조성물 제조Example 1-d Photocurable Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 30 g을 메틸아이소부틸케톤에 30 중량%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 코팅 조성물 100 중량부에 클로로 아세토페논(chloro acetophenone) 3 중량부와 BYK-347 1 중량부, BYK-UV 3500 1 중량부를 각각 첨가하고 10분간 교반하여 광경화형 코팅 조성물을 제조하였다.30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare a coating composition of 100 g. Thereafter, 3 parts by weight of chloro acetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV 3500 were added to 100 parts of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
[실시예 1-e] 열경화형 수지 조성물의 제조Example 1-e Preparation of Thermosetting Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 50 g을 메틸에틸케톤에 50 중량%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 준비된 코팅 조성물 100 중량부에 1,3-디아미노프로판 3 중량부와 BYK-357 및 BYK-348을 각 1 중량부씩 첨가하고 10분간 교반하여 열경화형 코팅 조성물을 제조하였다.50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
[실시예 1-f] 고분자 자체로 구성된 코팅 조성물Example 1-f Coating composition composed of polymer itself
실시예 1-c 만으로 별도의 조성 없이 코팅 조성물을 구성하였다.Example 1-c alone constitute a coating composition without a separate composition.
또한, 하기 표 19에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 1-b, 1-c, 1-d, 1-e 및 1-f에서 사용한 방법을 대등하게 적용하였다.In addition, by applying the monomers described in Table 19 to prepare a silsesquioxane composite polymer and to prepare a coating composition. In this case, the method used in Examples 1-b, 1-c, 1-d, 1-e, and 1-f was equally applied.
표 19
Table 19
실시방법 | 1-b 방법적용 단량체 | 1-c 방법적용 단량체 | 분자량(Mw) | |
전구체 | cage도입 | |||
1 | ECHETMS | PTMDS | PTMS | 11,000 |
1-1 | PTMS | PTMDS | PTMS | 8,000 |
1-2 | MTMS | MTMDS | MTMS | 48,000 |
1-3 | GPTMS | GPTMDS | GPTMS | 25,000 |
1-4 | MAPTMS | MAPTMDS | MAPTMS | 21,000 |
1-5 | ECHETMS | ECHETMDS | ECHETMS | 3,000 |
1-6 | ECHETMS | MTMDS | MTMS | 9,000 |
1-7 | ECHETMS | GPTMDS | GPTMS | 11,000 |
1-8 | ECHETMS | MAPTMDS | MAPTMS | 18,000 |
1-9 | PTMS | ECHETMDS | ECHETMS | 36,000 |
1-10 | PTMS | MTMDS | MTMS | 120,000 |
1-11 | PTMS | GPTMDS | GPTMS | 11,000 |
1-12 | PTMS | MAPTMDS | MAPTMS | 110,000 |
1-13 | MTMS | ECHETMDS | ECHETMS | 18,000 |
1-14 | MTMS | PTMDS | PTMS | 5,000 |
1-15 | MTMS | GPTMDS | GPTMS | 80,000 |
1-16 | MTMS | MAPTMDS | MAPTMS | 35,000 |
1-17 | GPTMS | ECHETMDS | ECHETMS | 7,000 |
1-18 | GPTMS | PTMDS | PTMS | 120,000 |
1-19 | GPTMS | MTMDS | MTMS | 100,000 |
1-20 | GPTMS | MAPTMDS | MAPTMS | 4,000 |
1-21 | MAPTMS | ECHETMDS | ECHETMS | 35,000 |
1-22 | MAPTMS | PTMDS | PTMS | 2,800 |
1-23 | MAPTMS | MTMDS | MTMS | 8,000 |
1-24 | MAPTMS | GPTMDS | GPTMS | 180,000 |
Method of implementation | 1-b Method Applicable Monomer | 1-c method applied monomer | Molecular Weight (Mw) | |
Precursor | Introduction of cage | |||
One | ECHETMS | PTMDS | PTMS | 11,000 |
1-1 | PTMS | PTMDS | PTMS | 8,000 |
1-2 | MTMS | MTMDS | MTMS | 48,000 |
1-3 | GPTMS | GPTMDS | GPTMS | 25,000 |
1-4 | MAPTMS | MAPTMDS | MAPTMS | 21,000 |
1-5 | ECHETMS | ECHETMDS | ECHETMS | 3,000 |
1-6 | ECHETMS | MTMDS | MTMS | 9,000 |
1-7 | ECHETMS | GPTMDS | GPTMS | 11,000 |
1-8 | ECHETMS | MAPTMDS | MAPTMS | 18,000 |
1-9 | PTMS | ECHETMDS | ECHETMS | 36,000 |
1-10 | PTMS | MTMDS | MTMS | 120,000 |
1-11 | PTMS | GPTMDS | GPTMS | 11,000 |
1-12 | PTMS | MAPTMDS | MAPTMS | 110,000 |
1-13 | MTMS | ECHETMDS | ECHETMS | 18,000 |
1-14 | MTMS | PTMDS | PTMS | 5,000 |
1-15 | MTMS | GPTMDS | GPTMS | 80,000 |
1-16 | MTMS | MAPTMDS | MAPTMS | 35,000 |
1-17 | GPTMS | ECHETMDS | ECHETMS | 7,000 |
1-18 | GPTMS | PTMDS | PTMS | 120,000 |
1-19 | GPTMS | MTMDS | MTMS | 100,000 |
1-20 | GPTMS | MAPTMDS | MAPTMS | 4,000 |
1-21 | MAPTMS | ECHETMDS | ECHETMS | 35,000 |
1-22 | MAPTMS | PTMDS | PTMS | 2,800 |
1-23 | MAPTMS | MTMDS | MTMS | 8,000 |
1-24 | MAPTMS | GPTMDS | GPTMS | 180,000 |
실시예 2Example 2
: 실세스퀴옥산 D-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane D-A-D Structured Polymer
D-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1-a 및 1-b의 방법을 동일하게 사용하였으며, 이후 연속적 D-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
[실시예 2-a] 과량의 연속적 cage 구조의 생성Example 2-a Generation of Excess Continuous Cage Structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 실시예 1-b에서 사용된 Diphenyltetramethoxydisiloxane의 5배인 25 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 14,000으로 측정되었으며, n 값은 4-6이었다. 또한, Si-NMR 분석에서 A-D구조와는 달리 A구조의 말단에서 보이던 -68ppm 근방의 피크가 사라져, A구조의 말단이 D구조로 모두 변환되어 D-A-D구조로 생성됨을 확인 하였다. 29Si-NMR (CDCl3) δ -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad)To the mixed solution of Example 1-b 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was analyzed and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the AD polymer of Formula 1 was prepared without any remaining by-products. I could confirm it. In addition, the styrene reduced molecular weight was measured as 14,000, n value was 4-6. In addition, unlike the AD structure in the Si-NMR analysis, the peak around -68ppm, which was seen at the end of the A structure, disappeared, and the end of the A structure was converted into the D structure, thereby confirming that the DAD structure was generated. 29 Si-NMR (CDCl 3 ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 20에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 2에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Example 2.
표 20
Table 20
실시방법 | 1-b 방법적용 단량체 | 2-a 방법적용 단량체 | 분자량(Mw) | |
전구체 | cage도입 | |||
2 | ECHETMS | PTMDS | PTMS | 14,000 |
2-1 | PTMS | PTMDS | PTMS | 9,000 |
2-2 | MTMS | MTMDS | MTMS | 52,000 |
2-3 | GPTMS | GPTMDS | GPTMS | 30,000 |
2-4 | MAPTMS | MAPTMDS | MAPTMS | 24,000 |
2-5 | ECHETMS | ECHETMDS | ECHETMS | 6,000 |
2-6 | ECHETMS | MTMDS | MTMS | 12,000 |
2-7 | ECHETMS | GPTMDS | GPTMS | 13,000 |
2-8 | ECHETMS | MAPTMDS | MAPTMS | 21,000 |
2-9 | PTMS | ECHETMDS | ECHETMS | 38,000 |
2-10 | PTMS | MTMDS | MTMS | 150,000 |
2-11 | PTMS | GPTMDS | GPTMS | 18,000 |
2-12 | PTMS | MAPTMDS | MAPTMS | 123,000 |
2-13 | MTMS | ECHETMDS | ECHETMS | 23,000 |
2-14 | MTMS | PTMDS | PTMS | 9,000 |
2-15 | MTMS | GPTMDS | GPTMS | 91,000 |
2-16 | MTMS | MAPTMDS | MAPTMS | 41,000 |
2-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
2-18 | GPTMS | PTMDS | PTMS | 131,000 |
2-19 | GPTMS | MTMDS | MTMS | 110,000 |
2-20 | GPTMS | MAPTMDS | MAPTMS | 6,000 |
2-21 | MAPTMS | ECHETMDS | ECHETMS | 38,000 |
2-22 | MAPTMS | PTMDS | PTMS | 5,000 |
2-23 | MAPTMS | MTMDS | MTMS | 12,000 |
2-24 | MAPTMS | GPTMDS | GPTMS | 192,000 |
Method of implementation | 1-b Method Applicable Monomer | 2-a method applied monomer | Molecular Weight (Mw) | |
Precursor | Introduction of cage | |||
2 | ECHETMS | PTMDS | PTMS | 14,000 |
2-1 | PTMS | PTMDS | PTMS | 9,000 |
2-2 | MTMS | MTMDS | MTMS | 52,000 |
2-3 | GPTMS | GPTMDS | GPTMS | 30,000 |
2-4 | MAPTMS | MAPTMDS | MAPTMS | 24,000 |
2-5 | ECHETMS | ECHETMDS | ECHETMS | 6,000 |
2-6 | ECHETMS | MTMDS | MTMS | 12,000 |
2-7 | ECHETMS | GPTMDS | GPTMS | 13,000 |
2-8 | ECHETMS | MAPTMDS | MAPTMS | 21,000 |
2-9 | PTMS | ECHETMDS | ECHETMS | 38,000 |
2-10 | PTMS | MTMDS | MTMS | 150,000 |
2-11 | PTMS | GPTMDS | GPTMS | 18,000 |
2-12 | PTMS | MAPTMDS | MAPTMS | 123,000 |
2-13 | MTMS | ECHETMDS | ECHETMS | 23,000 |
2-14 | MTMS | PTMDS | PTMS | 9,000 |
2-15 | MTMS | GPTMDS | GPTMS | 91,000 |
2-16 | MTMS | MAPTMDS | MAPTMS | 41,000 |
2-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
2-18 | GPTMS | PTMDS | PTMS | 131,000 |
2-19 | GPTMS | MTMDS | MTMS | 110,000 |
2-20 | GPTMS | MAPTMDS | MAPTMS | 6,000 |
2-21 | MAPTMS | ECHETMDS | ECHETMS | 38,000 |
2-22 | MAPTMS | PTMDS | PTMS | 5,000 |
2-23 | MAPTMS | MTMDS | MTMS | 12,000 |
2-24 | MAPTMS | GPTMDS | GPTMS | 192,000 |
실시예 3Example 3
: 실세스퀴옥산 E-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-D Structured Composite Polymer
E-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1의 방법을 동일하게 사용하였으며, 이후 E-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
[실시예 3-a] 사슬 말단 E구조의 생성Example 3-a Generation of Chain Terminal E Structure
실시예 1-c 에서 얻어진 A-D 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and the mixture was adjusted to a temperature of 4 for 30 minutes. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 3-b] 말단 E 구조에 cage 도입Example 3-b Introduction of a Cage to the Terminal E Structure
상기 실시예 3-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 3-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 3과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 3-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 3-c] Removal of By-products by Precipitation and Recrystallization, Obtaining the Result
상기 실시예 3-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 3의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 17,000이었으며, n 값은 4-6이었으며, 특히 화학식 3의 결과는 다음과 같다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, n value was 4-6, in particular, the results of formula (3) are as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 21에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 3에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
표 21
Table 21
실시방법 | 1-b 방법적용 단량체 | 1-c 방법적용 단량체 | 3-a방법적용 단량체 | 3-b방법적용단량체 | Mw | |
전구체 | cage도입 | |||||
3 | ECHETMS | PTMDS | PTMS | MTMDS | MAPTMS | 17,000 |
3-1 | ECHETMS | ECHETMDS | ECHETMS | ECHETMDS | ECHETMS | 12,000 |
3-2 | PTMS | PTMDS | PTMS | PTMDS | PTMS | 18,000 |
3-3 | MTMS | MTMDS | MTMS | MTMDS | MTMS | 59,000 |
3-4 | GPTMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 41,000 |
3-5 | MAPTMS | MAPTMDS | MAPTMS | MAPTMDS | MAPTMS | 31,000 |
3-6 | ECHETMS | ECHETMDS | ECHETMS | PTMDS | PTMS | 16,000 |
3-7 | ECHETMS | ECHETMDS | ECHETMS | MTMDS | MTMS | 12,000 |
3-8 | ECHETMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 16,000 |
3-9 | ECHETMS | ECHETMDS | ECHETMS | MAPTMDS | MAPTMS | 92,000 |
3-10 | ECHETMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 25,000 |
3-11 | ECHETMS | MTMDS | MTMS | ECHETMDS | ECHETMS | 38,000 |
3-12 | ECHETMS | GPTMDS | GPTMS | ECHETMDS | ECHETMS | 56,000 |
3-13 | ECHETMS | MAPTMDS | MAPTMS | ECHETMDS | ECHETMS | 97,000 |
3-14 | PTMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 24,000 |
3-15 | PTMS | PTMDS | PTMS | MTMDS | MTMS | 31,000 |
3-16 | PTMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 21,000 |
3-17 | PTMS | PTMDS | PTMS | MAPTMDS | MAPTMS | 64,000 |
3-18 | PTMS | ECHETMDS | ECHETMS | PTMDS | PTMS | 120,000 |
3-19 | PTMS | MTMDS | MTMS | PTMDS | PTMS | 210,000 |
3-20 | PTMS | GPTMDS | GPTMS | PTMDS | PTMS | 23,000 |
3-21 | PTMS | MAPTMDS | MAPTMS | PTMDS | PTMS | 160,000 |
3-22 | MTMS | MTMDS | MTMS | ECHETMDS | ECHETMS | 63,000 |
3-23 | MTMS | MTMDS | MTMS | PTMDS | PTMS | 52,000 |
3-24 | MTMS | MTMDS | MTMS | GPTMDS | GPTMS | 73,000 |
3-25 | MTMS | MTMDS | MTMS | MAPTMDS | MAPTMS | 98,000 |
3-26 | MTMS | ECHETMDS | ECHETMS | MTMDS | MTMS | 41,000 |
3-27 | MTMS | PTMDS | PTMS | MTMDS | MTMS | 15,000 |
3-28 | MTMS | GPTMDS | GPTMS | MTMDS | MTMS | 110,000 |
3-29 | MTMS | MAPTMDS | MAPTMS | MTMDS | MTMS | 45,000 |
3-30 | GPTMS | GPTMDS | GPTMS | ECHETMDS | ECHETMS | 35,000 |
3-31 | GPTMS | GPTMDS | GPTMS | PTMDS | PTMS | 33,000 |
3-32 | GPTMS | GPTMDS | GPTMS | MTMDS | MTMS | 48,000 |
3-33 | GPTMS | GPTMDS | GPTMS | MAPTMDS | MAPTMS | 29,000 |
3-34 | GPTMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 19,000 |
3-35 | GPTMS | PTMDS | PTMS | GPTMDS | GPTMS | 156,000 |
3-36 | GPTMS | MTMDS | MTMS | GPTMDS | GPTMS | 116,000 |
3-37 | GPTMS | MAPTMDS | MAPTMS | GPTMDS | GPTMS | 12,000 |
3-38 | MAPTMS | MAPTMDS | MAPTMS | ECHETMDS | ECHETMS | 31,000 |
3-39 | MAPTMS | MAPTMDS | MAPTMS | PTMDS | PTMS | 28,000 |
3-40 | MAPTMS | MAPTMDS | MAPTMS | MTMDS | MTMS | 35,000 |
3-41 | MAPTMS | MAPTMDS | MAPTMS | GPTMDS | GPTMS | 31,000 |
3-42 | MAPTMS | ECHETMDS | ECHETMS | MAPTMDS | MAPTMS | 57,000 |
3-43 | MAPTMS | PTMDS | PTMS | MAPTMDS | MAPTMS | 9,000 |
3-44 | MAPTMS | MTMDS | MTMS | MAPTMDS | MAPTMS | 19,000 |
3-45 | MAPTMS | GPTMDS | GPTMS | MAPTMDS | MAPTMS | 213,000 |
Method of implementation | 1-b Method Applicable Monomer | 1-c method applied monomer | 3-a method applied monomer | 3-b method applied monomer | Mw | |
Precursor | Introduction of cage | |||||
3 | ECHETMS | PTMDS | PTMS | MTMDS | MAPTMS | 17,000 |
3-1 | ECHETMS | ECHETMDS | ECHETMS | ECHETMDS | ECHETMS | 12,000 |
3-2 | PTMS | PTMDS | PTMS | PTMDS | PTMS | 18,000 |
3-3 | MTMS | MTMDS | MTMS | MTMDS | MTMS | 59,000 |
3-4 | GPTMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 41,000 |
3-5 | MAPTMS | MAPTMDS | MAPTMS | MAPTMDS | MAPTMS | 31,000 |
3-6 | ECHETMS | ECHETMDS | ECHETMS | PTMDS | PTMS | 16,000 |
3-7 | ECHETMS | ECHETMDS | ECHETMS | MTMDS | MTMS | 12,000 |
3-8 | ECHETMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 16,000 |
3-9 | ECHETMS | ECHETMDS | ECHETMS | MAPTMDS | MAPTMS | 92,000 |
3-10 | ECHETMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 25,000 |
3-11 | ECHETMS | MTMDS | MTMS | ECHETMDS | ECHETMS | 38,000 |
3-12 | ECHETMS | GPTMDS | GPTMS | ECHETMDS | ECHETMS | 56,000 |
3-13 | ECHETMS | MAPTMDS | MAPTMS | ECHETMDS | ECHETMS | 97,000 |
3-14 | PTMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 24,000 |
3-15 | PTMS | PTMDS | PTMS | MTMDS | MTMS | 31,000 |
3-16 | PTMS | PTMDS | PTMS | ECHETMDS | ECHETMS | 21,000 |
3-17 | PTMS | PTMDS | PTMS | MAPTMDS | MAPTMS | 64,000 |
3-18 | PTMS | ECHETMDS | ECHETMS | PTMDS | PTMS | 120,000 |
3-19 | PTMS | MTMDS | MTMS | PTMDS | PTMS | 210,000 |
3-20 | PTMS | GPTMDS | GPTMS | PTMDS | PTMS | 23,000 |
3-21 | PTMS | MAPTMDS | MAPTMS | PTMDS | PTMS | 160,000 |
3-22 | MTMS | MTMDS | MTMS | ECHETMDS | ECHETMS | 63,000 |
3-23 | MTMS | MTMDS | MTMS | PTMDS | PTMS | 52,000 |
3-24 | MTMS | MTMDS | MTMS | GPTMDS | GPTMS | 73,000 |
3-25 | MTMS | MTMDS | MTMS | MAPTMDS | MAPTMS | 98,000 |
3-26 | MTMS | ECHETMDS | ECHETMS | MTMDS | MTMS | 41,000 |
3-27 | MTMS | PTMDS | PTMS | MTMDS | MTMS | 15,000 |
3-28 | MTMS | GPTMDS | GPTMS | MTMDS | MTMS | 110,000 |
3-29 | MTMS | MAPTMDS | MAPTMS | MTMDS | MTMS | 45,000 |
3-30 | GPTMS | GPTMDS | GPTMS | ECHETMDS | ECHETMS | 35,000 |
3-31 | GPTMS | GPTMDS | GPTMS | PTMDS | PTMS | 33,000 |
3-32 | GPTMS | GPTMDS | GPTMS | MTMDS | MTMS | 48,000 |
3-33 | GPTMS | GPTMDS | GPTMS | MAPTMDS | MAPTMS | 29,000 |
3-34 | GPTMS | ECHETMDS | ECHETMS | GPTMDS | GPTMS | 19,000 |
3-35 | GPTMS | PTMDS | PTMS | GPTMDS | GPTMS | 156,000 |
3-36 | GPTMS | MTMDS | MTMS | GPTMDS | GPTMS | 116,000 |
3-37 | GPTMS | MAPTMDS | MAPTMS | GPTMDS | GPTMS | 12,000 |
3-38 | MAPTMS | MAPTMDS | MAPTMS | ECHETMDS | ECHETMS | 31,000 |
3-39 | MAPTMS | MAPTMDS | MAPTMS | PTMDS | PTMS | 28,000 |
3-40 | MAPTMS | MAPTMDS | MAPTMS | MTMDS | MTMS | 35,000 |
3-41 | MAPTMS | MAPTMDS | MAPTMS | GPTMDS | GPTMS | 31,000 |
3-42 | MAPTMS | ECHETMDS | ECHETMS | MAPTMDS | MAPTMS | 57,000 |
3-43 | MAPTMS | PTMDS | PTMS | MAPTMDS | MAPTMS | 9,000 |
3-44 | MAPTMS | MTMDS | MTMS | MAPTMDS | MAPTMS | 19,000 |
3-45 | MAPTMS | GPTMDS | GPTMS | MAPTMDS | MAPTMS | 213,000 |
실시예 4Example 4
: A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of A-B-D Structured Composite Silsesquioxane Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하여 E-A-D구조의 복합 고분자를 제조하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다.In the synthesis step, a continuous hydrolysis and condensation were carried out stepwise to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent to that described in Example 1.
[실시예 4-a] 가수분해 및 축합 반응을 위한 촉매의 제조Example 4-a Preparation of Catalysts for Hydrolysis and Condensation Reactions
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 wt% 수용액에 10 wt% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.To adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 4-b] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 4-b Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 4-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
1H-NMR (CDCl3) 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 4-c] 사슬 내 cage 구조의 생성을 위한 pH 변환 반응 (B,D 구조의 도입)[Example 4-c] pH conversion reaction for generation of cage structure in chain (introduction of B, D structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 DiPhenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 1시간 교반 후 실시예 4-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형구조체와는 별도로 cage 형태의 구조체가 생성되어 고분자 사슬에 도입됨을 확인 할 수 있었으며, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.025 mmol/g으로 변화되어 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 10,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.Example 6-b 0.35 wt% HCl aqueous solution was added dropwise very slowly to the mixed solution of Example 4-b, the pH was adjusted to have acidity, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, it could be confirmed that the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 4-d] B 구조내 X도입 (B,D 구조의 도입)[Example 4-d] X introduction into B structure (introduction of B and D structure)
상기 실시예 4-c에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 4-c에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 4와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 4-c without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 4-e] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 4-e] Removal of By-products by Precipitation and Recrystallization, Obtained Result
상기 실시예 4-d에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 4-d, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 4의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 12,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 4의 결과는 다음과 같다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 4 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 22에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 4에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
표 22
Table 22
실시방법 | 4-b 방법적용 단량체 | 4-c 방법적용 단량체 | 4-d 방법적용 단량체 | 분자량(Mw) |
4 | ECHETMS | PTMDS | MTMS | 12,000 |
4-1 | PTMS | PTMDS | PTMS | 15,000 |
4-2 | MTMS | MTMDS | MTMS | 16,000 |
4-3 | GPTMS | GPTMDS | GPTMS | 56,000 |
4-4 | MAPTMS | MAPTMDS | MAPTMS | 9,500 |
4-5 | ECHETMS | ECHETMDS | ECHETMS | 7,500 |
4-6 | ECHETMS | MTMDS | MTMS | 16,000 |
4-7 | ECHETMS | GPTMDS | GPTMS | 23,000 |
4-8 | ECHETMS | MAPTMDS | MAPTMS | 9,500 |
4-9 | PTMS | ECHETMDS | ECHETMS | 72,000 |
4-10 | PTMS | MTMDS | MTMS | 68,000 |
4-11 | PTMS | GPTMDS | GPTMS | 11,000 |
4-12 | PTMS | MAPTMDS | MAPTMS | 110,000 |
4-13 | MTMS | ECHETMDS | ECHETMS | 23,000 |
4-14 | MTMS | PTMDS | PTMS | 9,500 |
4-15 | MTMS | GPTMDS | GPTMS | 64,000 |
4-16 | MTMS | MAPTMDS | MAPTMS | 12,000 |
4-17 | GPTMS | ECHETMDS | ECHETMS | 8,000 |
4-18 | GPTMS | PTMDS | PTMS | 451,000 |
4-19 | GPTMS | MTMDS | MTMS | 320,000 |
4-20 | GPTMS | MAPTMDS | MAPTMS | 15,000 |
4-21 | MAPTMS | ECHETMDS | ECHETMS | 45,000 |
4-22 | MAPTMS | PTMDS | PTMS | 351,000 |
4-23 | MAPTMS | MTMDS | MTMS | 14,000 |
4-24 | MAPTMS | GPTMDS | GPTMS | 160,000 |
Method of implementation | 4-b method applied monomer | 4-c method applied monomer | 4-d method applied monomer | Molecular Weight (Mw) |
4 | ECHETMS | PTMDS | MTMS | 12,000 |
4-1 | PTMS | PTMDS | PTMS | 15,000 |
4-2 | MTMS | MTMDS | MTMS | 16,000 |
4-3 | GPTMS | GPTMDS | GPTMS | 56,000 |
4-4 | MAPTMS | MAPTMDS | MAPTMS | 9,500 |
4-5 | ECHETMS | ECHETMDS | ECHETMS | 7,500 |
4-6 | ECHETMS | MTMDS | MTMS | 16,000 |
4-7 | ECHETMS | GPTMDS | GPTMS | 23,000 |
4-8 | ECHETMS | MAPTMDS | MAPTMS | 9,500 |
4-9 | PTMS | ECHETMDS | ECHETMS | 72,000 |
4-10 | PTMS | MTMDS | MTMS | 68,000 |
4-11 | PTMS | GPTMDS | GPTMS | 11,000 |
4-12 | PTMS | MAPTMDS | MAPTMS | 110,000 |
4-13 | MTMS | ECHETMDS | ECHETMS | 23,000 |
4-14 | MTMS | PTMDS | PTMS | 9,500 |
4-15 | MTMS | GPTMDS | GPTMS | 64,000 |
4-16 | MTMS | MAPTMDS | MAPTMS | 12,000 |
4-17 | GPTMS | ECHETMDS | ECHETMS | 8,000 |
4-18 | GPTMS | PTMDS | PTMS | 451,000 |
4-19 | GPTMS | MTMDS | MTMS | 320,000 |
4-20 | GPTMS | MAPTMDS | MAPTMS | 15,000 |
4-21 | MAPTMS | ECHETMDS | ECHETMS | 45,000 |
4-22 | MAPTMS | PTMDS | PTMS | 351,000 |
4-23 | MAPTMS | MTMDS | MTMS | 14,000 |
4-24 | MAPTMS | GPTMDS | GPTMS | 160,000 |
실시예 5Example 5
: D-A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-D Structured Composite Silsesquioxane Polymer
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
[실시예 5-a] D구조의 과량 생성을 위한 pH 변환 반응 (B,D 구조의 도입)Example 5-a pH Conversion Reaction for Excess Production of D Structure (Introduction of B, D Structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 4-b의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.012 mmol/g으로 변화되고 B 와 D의 반복단위가 약 1:9 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 24,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.To the mixture of Example 4-b during the reaction, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.012 mmol / g and the repeating units of B and D were about It was confirmed that the 1: 9 ratio was introduced. In addition, styrene conversion molecular weight was measured as 24,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 5-b] B 구조내 X도입 (B,D 구조의 도입)[Example 5-b] X Introduction in B Structure (Introduction of B, D Structure)
상기 실시예 5-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 5-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 5와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 5-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 5-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 5-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 5-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 5의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 16,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 5의 결과는 다음과 같다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 23에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 5에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Example 5.
표 23
Table 23
실시방법No. | 4-b 방법적용 단량체 | 4-a 방법적용 단량체 | 5-b 방법적용 단량체 | 분자량(Mw) |
2 | ECHETMS | PTMDS | MTMS | 16,000 |
5-1 | PTMS | PTMDS | PTMS | 19,000 |
5-2 | MTMS | MTMDS | MTMS | 20,000 |
5-3 | GPTMS | GPTMDS | GPTMS | 63,000 |
5-4 | MAPTMS | MAPTMDS | MAPTMS | 12,000 |
5-5 | ECHETMS | ECHETMDS | ECHETMS | 14,500 |
5-6 | ECHETMS | MTMDS | MTMS | 19,000 |
5-7 | ECHETMS | GPTMDS | GPTMS | 25,000 |
5-8 | ECHETMS | MAPTMDS | MAPTMS | 11,500 |
5-9 | PTMS | ECHETMDS | ECHETMS | 78,000 |
5-10 | PTMS | MTMDS | MTMS | 79,000 |
5-11 | PTMS | GPTMDS | GPTMS | 15,000 |
5-12 | PTMS | MAPTMDS | MAPTMS | 124,000 |
5-13 | MTMS | ECHETMDS | ECHETMS | 30,000 |
5-14 | MTMS | PTMDS | PTMS | 12,000 |
5-15 | MTMS | GPTMDS | GPTMS | 64,000 |
5-16 | MTMS | MAPTMDS | MAPTMS | 13,000 |
5-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
5-18 | GPTMS | PTMDS | PTMS | 631,000 |
5-19 | GPTMS | MTMDS | MTMS | 421,000 |
5-20 | GPTMS | MAPTMDS | MAPTMS | 18,000 |
5-21 | MAPTMS | ECHETMDS | ECHETMS | 65,000 |
2-22 | MAPTMS | PTMDS | PTMS | 425,000 |
5-23 | MAPTMS | MTMDS | MTMS | 25,000 |
5-24 | MAPTMS | GPTMDS | GPTMS | 213,000 |
Method of implementation | 4-b method applied monomer | 4-a method applied monomer | 5-b method applied monomer | Molecular Weight (Mw) |
2 | ECHETMS | PTMDS | MTMS | 16,000 |
5-1 | PTMS | PTMDS | PTMS | 19,000 |
5-2 | MTMS | MTMDS | MTMS | 20,000 |
5-3 | GPTMS | GPTMDS | GPTMS | 63,000 |
5-4 | MAPTMS | MAPTMDS | MAPTMS | 12,000 |
5-5 | ECHETMS | ECHETMDS | ECHETMS | 14,500 |
5-6 | ECHETMS | MTMDS | MTMS | 19,000 |
5-7 | ECHETMS | GPTMDS | GPTMS | 25,000 |
5-8 | ECHETMS | MAPTMDS | MAPTMS | 11,500 |
5-9 | PTMS | ECHETMDS | ECHETMS | 78,000 |
5-10 | PTMS | MTMDS | MTMS | 79,000 |
5-11 | PTMS | GPTMDS | GPTMS | 15,000 |
5-12 | PTMS | MAPTMDS | MAPTMS | 124,000 |
5-13 | MTMS | ECHETMDS | ECHETMS | 30,000 |
5-14 | MTMS | PTMDS | PTMS | 12,000 |
5-15 | MTMS | GPTMDS | GPTMS | 64,000 |
5-16 | MTMS | MAPTMDS | MAPTMS | 13,000 |
5-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
5-18 | GPTMS | PTMDS | PTMS | 631,000 |
5-19 | GPTMS | MTMDS | MTMS | 421,000 |
5-20 | GPTMS | MAPTMDS | MAPTMS | 18,000 |
5-21 | MAPTMS | ECHETMDS | ECHETMS | 65,000 |
2-22 | MAPTMS | PTMDS | PTMS | 425,000 |
5-23 | MAPTMS | MTMDS | MTMS | 25,000 |
5-24 | MAPTMS | GPTMDS | GPTMS | 213,000 |
실시예 6Example 6
: 실세스퀴옥산 E-A-B-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-D Structured Composite Polymer
E-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.
[실시예 6-a] 사슬 말단 E구조의 생성Example 6-a Generation of Chain Terminal E Structure
실시예 4-c 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the mixture obtained in Example 4-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to be acidic, and stirred at a temperature of 4 for 30 minutes. It was. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 6-b] B구조 및 말단 E 구조의 X에 cage 도입[Example 6-b] Cage introduction into X of B structure and terminal E structure
상기 실시예 6-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 6-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 6과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 6-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 6-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 6-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. In Example 6-b, the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 6의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 21,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 6의 결과는 다음과 같다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 21,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 24에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 6에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Example 6.
표 24
Table 24
실시방법 | 4-b 방법적용 단량체 | 4-c 방법적용 단량체 | 6-a방법적용 단량체 | 6-b방법적용단량체 | Mw |
6 | ECHETMS | PTMDS | MTMDS | MAPTMS | 21,000 |
6-1 | ECHETMS | ECHETMDS | ECHETMDS | ECHETMS | 18,000 |
6-2 | PTMS | PTMDS | PTMDS | PTMS | 19,000 |
6-3 | MTMS | MTMDS | MTMDS | MTMS | 31,000 |
6-4 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 63,000 |
6-5 | MAPTMS | MAPTMDS | MAPTMDS | MAPTMS | 125,000 |
6-6 | ECHETMS | ECHETMDS | PTMDS | PTMS | 18,000 |
6-7 | ECHETMS | ECHETMDS | MTMDS | MTMS | 14,000 |
6-8 | ECHETMS | ECHETMDS | GPTMDS | GPTMS | 20,000 |
6-9 | ECHETMS | ECHETMDS | MAPTMDS | MAPTMS | 91,000 |
6-10 | ECHETMS | PTMDS | ECHETMDS | ECHETMS | 18,000 |
6-11 | ECHETMS | MTMDS | ECHETMDS | ECHETMS | 121,000 |
6-12 | ECHETMS | GPTMDS | ECHETMDS | ECHETMS | 80,000 |
6-13 | ECHETMS | MAPTMDS | ECHETMDS | ECHETMS | 112,000 |
6-14 | PTMS | PTMDS | ECHETMDS | ECHETMS | 35,000 |
6-15 | PTMS | PTMDS | MTMDS | MTMS | 91,000 |
6-16 | PTMS | PTMDS | ECHETMDS | ECHETMS | 45,000 |
6-17 | PTMS | PTMDS | MAPTMDS | MAPTMS | 75,000 |
6-18 | PTMS | ECHETMDS | PTMDS | PTMS | 140,000 |
6-19 | PTMS | MTMDS | PTMDS | PTMS | 220,000 |
6-20 | PTMS | GPTMDS | PTMDS | PTMS | 51,000 |
6-21 | PTMS | MAPTMDS | PTMDS | PTMS | 73,000 |
6-22 | MTMS | MTMDS | ECHETMDS | ECHETMS | 69,000 |
6-23 | MTMS | MTMDS | PTMDS | PTMS | 51,000 |
6-24 | MTMS | MTMDS | GPTMDS | GPTMS | 91,000 |
6-25 | MTMS | MTMDS | MAPTMDS | MAPTMS | 128,000 |
6-26 | MTMS | ECHETMDS | MTMDS | MTMS | 68,000 |
6-27 | MTMS | PTMDS | MTMDS | MTMS | 45,000 |
6-28 | MTMS | GPTMDS | MTMDS | MTMS | 265,000 |
6-29 | MTMS | MAPTMDS | MTMDS | MTMS | 105,000 |
6-30 | GPTMS | GPTMDS | ECHETMDS | ECHETMS | 101,000 |
6-31 | GPTMS | GPTMDS | PTMDS | PTMS | 95,000 |
6-32 | GPTMS | GPTMDS | MTMDS | MTMS | 73,000 |
6-33 | GPTMS | GPTMDS | MAPTMDS | MAPTMS | 51,000 |
6-34 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 31,000 |
6-35 | GPTMS | PTMDS | GPTMDS | GPTMS | 315,000 |
6-36 | GPTMS | MTMDS | GPTMDS | GPTMS | 125,000 |
6-37 | GPTMS | MAPTMDS | GPTMDS | GPTMS | 45,000 |
6-38 | MAPTMS | MAPTMDS | ECHETMDS | ECHETMS | 94,000 |
6-39 | MAPTMS | MAPTMDS | PTMDS | PTMS | 35,000 |
6-40 | MAPTMS | MAPTMDS | MTMDS | MTMS | 80,000 |
6-41 | MAPTMS | MAPTMDS | GPTMDS | GPTMS | 83,000 |
6-42 | MAPTMS | ECHETMDS | MAPTMDS | MAPTMS | 74,000 |
6-43 | MAPTMS | PTMDS | MAPTMDS | MAPTMS | 10,000 |
6-44 | MAPTMS | MTMDS | MAPTMDS | MAPTMS | 65,000 |
6-45 | MAPTMS | GPTMDS | MAPTMDS | MAPTMS | 418,000 |
Method of implementation | 4-b method applied monomer | 4-c method applied monomer | 6-a method applied monomer | 6-b method applied monomer | Mw |
6 | ECHETMS | PTMDS | MTMDS | MAPTMS | 21,000 |
6-1 | ECHETMS | ECHETMDS | ECHETMDS | ECHETMS | 18,000 |
6-2 | PTMS | PTMDS | PTMDS | PTMS | 19,000 |
6-3 | MTMS | MTMDS | MTMDS | MTMS | 31,000 |
6-4 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 63,000 |
6-5 | MAPTMS | MAPTMDS | MAPTMDS | MAPTMS | 125,000 |
6-6 | ECHETMS | ECHETMDS | PTMDS | PTMS | 18,000 |
6-7 | ECHETMS | ECHETMDS | MTMDS | MTMS | 14,000 |
6-8 | ECHETMS | ECHETMDS | GPTMDS | GPTMS | 20,000 |
6-9 | ECHETMS | ECHETMDS | MAPTMDS | MAPTMS | 91,000 |
6-10 | ECHETMS | PTMDS | ECHETMDS | ECHETMS | 18,000 |
6-11 | ECHETMS | MTMDS | ECHETMDS | ECHETMS | 121,000 |
6-12 | ECHETMS | GPTMDS | ECHETMDS | ECHETMS | 80,000 |
6-13 | ECHETMS | MAPTMDS | ECHETMDS | ECHETMS | 112,000 |
6-14 | PTMS | PTMDS | ECHETMDS | ECHETMS | 35,000 |
6-15 | PTMS | PTMDS | MTMDS | MTMS | 91,000 |
6-16 | PTMS | PTMDS | ECHETMDS | ECHETMS | 45,000 |
6-17 | PTMS | PTMDS | MAPTMDS | MAPTMS | 75,000 |
6-18 | PTMS | ECHETMDS | PTMDS | PTMS | 140,000 |
6-19 | PTMS | MTMDS | PTMDS | PTMS | 220,000 |
6-20 | PTMS | GPTMDS | PTMDS | PTMS | 51,000 |
6-21 | PTMS | MAPTMDS | PTMDS | PTMS | 73,000 |
6-22 | MTMS | MTMDS | ECHETMDS | ECHETMS | 69,000 |
6-23 | MTMS | MTMDS | PTMDS | PTMS | 51,000 |
6-24 | MTMS | MTMDS | GPTMDS | GPTMS | 91,000 |
6-25 | MTMS | MTMDS | MAPTMDS | MAPTMS | 128,000 |
6-26 | MTMS | ECHETMDS | MTMDS | MTMS | 68,000 |
6-27 | MTMS | PTMDS | MTMDS | MTMS | 45,000 |
6-28 | MTMS | GPTMDS | MTMDS | MTMS | 265,000 |
6-29 | MTMS | MAPTMDS | MTMDS | MTMS | 105,000 |
6-30 | GPTMS | GPTMDS | ECHETMDS | ECHETMS | 101,000 |
6-31 | GPTMS | GPTMDS | PTMDS | PTMS | 95,000 |
6-32 | GPTMS | GPTMDS | MTMDS | MTMS | 73,000 |
6-33 | GPTMS | GPTMDS | MAPTMDS | MAPTMS | 51,000 |
6-34 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 31,000 |
6-35 | GPTMS | PTMDS | GPTMDS | GPTMS | 315,000 |
6-36 | GPTMS | MTMDS | GPTMDS | GPTMS | 125,000 |
6-37 | GPTMS | MAPTMDS | GPTMDS | GPTMS | 45,000 |
6-38 | MAPTMS | MAPTMDS | ECHETMDS | ECHETMS | 94,000 |
6-39 | MAPTMS | MAPTMDS | PTMDS | PTMS | 35,000 |
6-40 | MAPTMS | MAPTMDS | MTMDS | MTMS | 80,000 |
6-41 | MAPTMS | MAPTMDS | GPTMDS | GPTMS | 83,000 |
6-42 | MAPTMS | ECHETMDS | MAPTMDS | MAPTMS | 74,000 |
6-43 | MAPTMS | PTMDS | MAPTMDS | MAPTMS | 10,000 |
6-44 | MAPTMS | MTMDS | MAPTMDS | MAPTMS | 65,000 |
6-45 | MAPTMS | GPTMDS | MAPTMDS | MAPTMS | 418,000 |
실시예 7Example 7
: 실세스퀴옥산 A-B-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane A-B-A-D Structured Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Example 1.
[실시예 7-a] 촉매의 제조Example 7-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 7-b] 선형 실세스퀴옥산 합성 (A 전구체)Example 7-b Linear Silsesquioxane Synthesis (A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 7-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20 중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
[실시예 7-c] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 7-c Synthesis of Linear Silsesquioxane Structures (Synthesis of A-B Precursors)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 7-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.
[실시예 7-d] 선형 실세스퀴옥산 구조의 합성 (A-B-A전구체의 합성)Example 7-d Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B-A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 5 중량부, 제조된 실시예 7-a 촉매를 10 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 실시예 7-b 전구체와 7-c 전구체를 20 중량부씩 각각 적가하고, 다시 테트라하이드로류란을 10 중량부 적가하여 24시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 15,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
1H-NMR (CDCl3) δ 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 7-e] 연속적 cage 구조의 생성 (D 구조의 도입)Example 7-e Generation of Continuous Cage Structure (Introduction of D Structure)
상기 실시예 7-d 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 10% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 7과 같은 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 18,000으로 측정되었다.To the mixed solution of Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 for 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 10%, 10 parts by weight of 0.36 wt% aqueous HCl solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the polymer of formula 7 was prepared without any remaining by-products. Could. In addition, styrene conversion molecular weight was measured as 18,000.
29Si-NMR (CDCl3) δ -68.2, -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
[실시예 7-f] B 구조내 X도입 (A-B-A-D구조의 완성)[Example 7-f] X introduction in B structure (completion of A-B-A-D structure)
상기 실시예 7-e에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 7-e에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 7과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 7-e without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 7-g] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 7-g] Removal of by-products by precipitation and recrystallization, yield of the result
상기 실시예 7-f에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 7-f, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 7의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 24,000의 값이었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was a styrene conversion value of 24,000, the n value of X was 4-6, the n value of Y was 4-6.
또한, 하기 표 25에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 7에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Example 7.
표 25
Table 25
실시방법 | 7-b,c 방법적용 단량체 | 7-e 방법적용 단량체 | 7-f 방법적용 단량체 | 분자량(Mw) |
7 | ECHETMS | PTMDS | MTMS | 24,000 |
7-1 | PTMS | PTMDS | PTMS | 11,000 |
7-2 | MTMS | MTMDS | MTMS | 13,000 |
7-3 | GPTMS | GPTMDS | GPTMS | 23,000 |
7-4 | MAPTMS | MAPTMDS | MAPTMS | 14,500 |
7-5 | ECHETMS | ECHETMDS | ECHETMS | 12,500 |
7-6 | ECHETMS | MTMDS | MTMS | 53,000 |
7-7 | ECHETMS | GPTMDS | GPTMS | 11,000 |
7-8 | ECHETMS | MAPTMDS | MAPTMS | 9,000 |
7-9 | PTMS | ECHETMDS | ECHETMS | 48,000 |
7-10 | PTMS | MTMDS | MTMS | 90,000 |
7-11 | PTMS | GPTMDS | GPTMS | 32,000 |
7-12 | PTMS | MAPTMDS | MAPTMS | 150,000 |
7-13 | MTMS | ECHETMDS | ECHETMS | 17,000 |
7-14 | MTMS | PTMDS | PTMS | 38,500 |
7-15 | MTMS | GPTMDS | GPTMS | 15,000 |
7-16 | MTMS | MAPTMDS | MAPTMS | 17,000 |
7-17 | GPTMS | ECHETMDS | ECHETMS | 6,000 |
7-18 | GPTMS | PTMDS | PTMS | 18,000 |
7-19 | GPTMS | MTMDS | MTMS | 457,000 |
7-20 | GPTMS | MAPTMDS | MAPTMS | 16,000 |
7-21 | MAPTMS | ECHETMDS | ECHETMS | 97,000 |
7-22 | MAPTMS | PTMDS | PTMS | 951,000 |
7-23 | MAPTMS | MTMDS | MTMS | 15,000 |
7-24 | MAPTMS | GPTMDS | GPTMS | 12,000 |
Method of implementation | 7-b, c method applied monomer | 7-e method applied monomer | 7-f method applied monomer | Molecular Weight (Mw) |
7 | ECHETMS | PTMDS | MTMS | 24,000 |
7-1 | PTMS | PTMDS | PTMS | 11,000 |
7-2 | MTMS | MTMDS | MTMS | 13,000 |
7-3 | GPTMS | GPTMDS | GPTMS | 23,000 |
7-4 | MAPTMS | MAPTMDS | MAPTMS | 14,500 |
7-5 | ECHETMS | ECHETMDS | ECHETMS | 12,500 |
7-6 | ECHETMS | MTMDS | MTMS | 53,000 |
7-7 | ECHETMS | GPTMDS | GPTMS | 11,000 |
7-8 | ECHETMS | MAPTMDS | MAPTMS | 9,000 |
7-9 | PTMS | ECHETMDS | ECHETMS | 48,000 |
7-10 | PTMS | MTMDS | MTMS | 90,000 |
7-11 | PTMS | GPTMDS | GPTMS | 32,000 |
7-12 | PTMS | MAPTMDS | MAPTMS | 150,000 |
7-13 | MTMS | ECHETMDS | ECHETMS | 17,000 |
7-14 | MTMS | PTMDS | PTMS | 38,500 |
7-15 | MTMS | GPTMDS | GPTMS | 15,000 |
7-16 | MTMS | MAPTMDS | MAPTMS | 17,000 |
7-17 | GPTMS | ECHETMDS | ECHETMS | 6,000 |
7-18 | GPTMS | PTMDS | PTMS | 18,000 |
7-19 | GPTMS | MTMDS | MTMS | 457,000 |
7-20 | GPTMS | MAPTMDS | MAPTMS | 16,000 |
7-21 | MAPTMS | ECHETMDS | ECHETMS | 97,000 |
7-22 | MAPTMS | PTMDS | PTMS | 951,000 |
7-23 | MAPTMS | MTMDS | MTMS | 15,000 |
7-24 | MAPTMS | GPTMDS | GPTMS | 12,000 |
실시예 8Example 8
: D-A-B-A-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-A-D Structured Composite Silsesquioxane Polymers
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.In order to manufacture a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
[실시예 8-a] D구조의 과량 생성을 위한 pH 변환 반응 Example 8-a pH Conversion Reaction for Excess Production of D Structure
반응이 진행 중인 실시예 7-d 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 15 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 7-e의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 20 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.006 mmol/g으로 변화되고 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 32,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.15 parts by weight of 0.36 wt% HCl aqueous solution was added very slowly to the mixed solution of Example 7-d, which was in progress, adjusted to have an acidic pH, and stirred at a temperature of 4 for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.006 mmol / g and the repeating units of B and D were about It was confirmed that the ratio was introduced at 5: 5. In addition, styrene conversion molecular weight was measured as 32,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 8-b] B 구조내 X도입Example 8-b Introducing X in B Structure
상기 실시예 8-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 8-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 8와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 8-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 8-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 8-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 8-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 8-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 1의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 36,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 8의 결과는 다음과 같다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 26에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 8에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 26 below. At this time, the manufacturing method was equally applied to the method used in Example 8.
표 26
Table 26
실시방법 | 7-b,c 방법적용 단량체 | 8-a 방법적용 단량체 | 8-b 방법적용 단량체 | 분자량(Mw) |
8 | ECHETMS | PTMDS | MTMS | 36,000 |
8-1 | PTMS | PTMDS | PTMS | 14,000 |
8-2 | MTMS | MTMDS | MTMS | 18,000 |
8-3 | GPTMS | GPTMDS | GPTMS | 27,000 |
8-4 | MAPTMS | MAPTMDS | MAPTMS | 19,500 |
8-5 | ECHETMS | ECHETMDS | ECHETMS | 19,500 |
8-6 | ECHETMS | MTMDS | MTMS | 58,000 |
8-7 | ECHETMS | GPTMDS | GPTMS | 19,000 |
8-8 | ECHETMS | MAPTMDS | MAPTMS | 12,000 |
8-9 | PTMS | ECHETMDS | ECHETMS | 53,000 |
8-10 | PTMS | MTMDS | MTMS | 113,000 |
8-11 | PTMS | GPTMDS | GPTMS | 42,000 |
8-12 | PTMS | MAPTMDS | MAPTMS | 173,000 |
8-13 | MTMS | ECHETMDS | ECHETMS | 19,000 |
8-14 | MTMS | PTMDS | PTMS | 45,000 |
8-15 | MTMS | GPTMDS | GPTMS | 32,000 |
8-16 | MTMS | MAPTMDS | MAPTMS | 34,000 |
8-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
8-18 | GPTMS | PTMDS | PTMS | 24,000 |
8-19 | GPTMS | MTMDS | MTMS | 486,000 |
8-20 | GPTMS | MAPTMDS | MAPTMS | 32,000 |
8-21 | MAPTMS | ECHETMDS | ECHETMS | 181,000 |
8-22 | MAPTMS | PTMDS | PTMS | 981,000 |
8-23 | MAPTMS | MTMDS | MTMS | 21,000 |
8-24 | MAPTMS | GPTMDS | GPTMS | 20,000 |
Method of implementation | 7-b, c method applied monomer | 8-a Method Applicable Monomer | 8-b Method Applicable Monomer | Molecular Weight (Mw) |
8 | ECHETMS | PTMDS | MTMS | 36,000 |
8-1 | PTMS | PTMDS | PTMS | 14,000 |
8-2 | MTMS | MTMDS | MTMS | 18,000 |
8-3 | GPTMS | GPTMDS | GPTMS | 27,000 |
8-4 | MAPTMS | MAPTMDS | MAPTMS | 19,500 |
8-5 | ECHETMS | ECHETMDS | ECHETMS | 19,500 |
8-6 | ECHETMS | MTMDS | MTMS | 58,000 |
8-7 | ECHETMS | GPTMDS | GPTMS | 19,000 |
8-8 | ECHETMS | MAPTMDS | MAPTMS | 12,000 |
8-9 | PTMS | ECHETMDS | ECHETMS | 53,000 |
8-10 | PTMS | MTMDS | MTMS | 113,000 |
8-11 | PTMS | GPTMDS | GPTMS | 42,000 |
8-12 | PTMS | MAPTMDS | MAPTMS | 173,000 |
8-13 | MTMS | ECHETMDS | ECHETMS | 19,000 |
8-14 | MTMS | PTMDS | PTMS | 45,000 |
8-15 | MTMS | GPTMDS | GPTMS | 32,000 |
8-16 | MTMS | MAPTMDS | MAPTMS | 34,000 |
8-17 | GPTMS | ECHETMDS | ECHETMS | 12,000 |
8-18 | GPTMS | PTMDS | PTMS | 24,000 |
8-19 | GPTMS | MTMDS | MTMS | 486,000 |
8-20 | GPTMS | MAPTMDS | MAPTMS | 32,000 |
8-21 | MAPTMS | ECHETMDS | ECHETMS | 181,000 |
8-22 | MAPTMS | PTMDS | PTMS | 981,000 |
8-23 | MAPTMS | MTMDS | MTMS | 21,000 |
8-24 | MAPTMS | GPTMDS | GPTMS | 20,000 |
실시예 9Example 9
: 실세스퀴옥산 E-A-B-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-A-D Structured Polymer
E-A-B-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
[실시예 9-a] 사슬 말단 E구조의 생성Example 9-a Generation of Chain Terminal E Structure
실시예 7-g 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, the pH was adjusted to have an acidity, and the mixture was stirred at a temperature of 4 for 30 minutes. It was. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 9-b] B구조 및 말단 E 구조의 X에 cage 도입Example 9-b Introducing cage to X of B structure and terminal E structure
상기 실시예 9-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 9-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 9과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 9-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 9-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 9-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved at 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5 and stored at a temperature of -20 for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 9의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 28,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었다. After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.
또한, 하기 표 27에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 9에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
표 27
Table 27
실시방법 | 7-b,c 방법적용 단량체 | 7-e 방법적용 단량체 | 9-a방법적용 단량체 | 9-b방법적용단량체 | Mw |
9 | ECHETMS | PTMDS | MTMDS | MAPTMS | 28,000 |
9-1 | ECHETMS | ECHETMDS | ECHETMDS | ECHETMS | 24,000 |
9-2 | PTMS | PTMDS | PTMDS | PTMS | 21,000 |
9-3 | MTMS | MTMDS | MTMDS | MTMS | 36,000 |
9-4 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 62,000 |
9-5 | MAPTMS | MAPTMDS | MAPTMDS | MAPTMS | 153,000 |
9-6 | ECHETMS | ECHETMDS | PTMDS | PTMS | 24,000 |
9-7 | ECHETMS | ECHETMDS | MTMDS | MTMS | 19,000 |
9-8 | ECHETMS | ECHETMDS | GPTMDS | GPTMS | 26,000 |
9-9 | ECHETMS | ECHETMDS | MAPTMDS | MAPTMS | 99,000 |
9-10 | ECHETMS | PTMDS | ECHETMDS | ECHETMS | 21,000 |
9-11 | ECHETMS | MTMDS | ECHETMDS | ECHETMS | 142,000 |
9-12 | ECHETMS | GPTMDS | ECHETMDS | ECHETMS | 70,000 |
9-13 | ECHETMS | MAPTMDS | ECHETMDS | ECHETMS | 72,000 |
9-14 | PTMS | PTMDS | ECHETMDS | ECHETMS | 15,000 |
9-15 | PTMS | PTMDS | MTMDS | MTMS | 51,000 |
9-16 | PTMS | PTMDS | ECHETMDS | ECHETMS | 85,000 |
9-17 | PTMS | PTMDS | MAPTMDS | MAPTMS | 95,000 |
9-18 | PTMS | ECHETMDS | PTMDS | PTMS | 160,000 |
9-19 | PTMS | MTMDS | PTMDS | PTMS | 240,000 |
9-20 | PTMS | GPTMDS | PTMDS | PTMS | 56,000 |
9-21 | PTMS | MAPTMDS | PTMDS | PTMS | 71,000 |
9-22 | MTMS | MTMDS | ECHETMDS | ECHETMS | 81,000 |
9-23 | MTMS | MTMDS | PTMDS | PTMS | 63,000 |
9-24 | MTMS | MTMDS | GPTMDS | GPTMS | 121,000 |
9-25 | MTMS | MTMDS | MAPTMDS | MAPTMS | 153,000 |
9-26 | MTMS | ECHETMDS | MTMDS | MTMS | 82,000 |
9-27 | MTMS | PTMDS | MTMDS | MTMS | 63,000 |
9-28 | MTMS | GPTMDS | MTMDS | MTMS | 310,000 |
9-29 | MTMS | MAPTMDS | MTMDS | MTMS | 125,000 |
9-30 | GPTMS | GPTMDS | ECHETMDS | ECHETMS | 97,000 |
9-31 | GPTMS | GPTMDS | PTMDS | PTMS | 45,000 |
9-32 | GPTMS | GPTMDS | MTMDS | MTMS | 61,000 |
9-33 | GPTMS | GPTMDS | MAPTMDS | MAPTMS | 52,000 |
9-34 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 37,000 |
9-35 | GPTMS | PTMDS | GPTMDS | GPTMS | 365,000 |
9-36 | GPTMS | MTMDS | GPTMDS | GPTMS | 85,000 |
9-37 | GPTMS | MAPTMDS | GPTMDS | GPTMS | 75,000 |
9-38 | MAPTMS | MAPTMDS | ECHETMDS | ECHETMS | 144,000 |
9-39 | MAPTMS | MAPTMDS | PTMDS | PTMS | 85,000 |
9-40 | MAPTMS | MAPTMDS | MTMDS | MTMS | 60,000 |
9-41 | MAPTMS | MAPTMDS | GPTMDS | GPTMS | 53,000 |
9-42 | MAPTMS | ECHETMDS | MAPTMDS | MAPTMS | 12,000 |
9-43 | MAPTMS | PTMDS | MAPTMDS | MAPTMS | 10,000 |
9-44 | MAPTMS | MTMDS | MAPTMDS | MAPTMS | 32,000 |
9-45 | MAPTMS | GPTMDS | MAPTMDS | MAPTMS | 231,000 |
Method of implementation | 7-b, c method applied monomer | 7-e method applied monomer | 9-a method applied monomer | 9-b method applied monomer | Mw |
9 | ECHETMS | PTMDS | MTMDS | MAPTMS | 28,000 |
9-1 | ECHETMS | ECHETMDS | ECHETMDS | ECHETMS | 24,000 |
9-2 | PTMS | PTMDS | PTMDS | PTMS | 21,000 |
9-3 | MTMS | MTMDS | MTMDS | MTMS | 36,000 |
9-4 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 62,000 |
9-5 | MAPTMS | MAPTMDS | MAPTMDS | MAPTMS | 153,000 |
9-6 | ECHETMS | ECHETMDS | PTMDS | PTMS | 24,000 |
9-7 | ECHETMS | ECHETMDS | MTMDS | MTMS | 19,000 |
9-8 | ECHETMS | ECHETMDS | GPTMDS | GPTMS | 26,000 |
9-9 | ECHETMS | ECHETMDS | MAPTMDS | MAPTMS | 99,000 |
9-10 | ECHETMS | PTMDS | ECHETMDS | ECHETMS | 21,000 |
9-11 | ECHETMS | MTMDS | ECHETMDS | ECHETMS | 142,000 |
9-12 | ECHETMS | GPTMDS | ECHETMDS | ECHETMS | 70,000 |
9-13 | ECHETMS | MAPTMDS | ECHETMDS | ECHETMS | 72,000 |
9-14 | PTMS | PTMDS | ECHETMDS | ECHETMS | 15,000 |
9-15 | PTMS | PTMDS | MTMDS | MTMS | 51,000 |
9-16 | PTMS | PTMDS | ECHETMDS | ECHETMS | 85,000 |
9-17 | PTMS | PTMDS | MAPTMDS | MAPTMS | 95,000 |
9-18 | PTMS | ECHETMDS | PTMDS | PTMS | 160,000 |
9-19 | PTMS | MTMDS | PTMDS | PTMS | 240,000 |
9-20 | PTMS | GPTMDS | PTMDS | PTMS | 56,000 |
9-21 | PTMS | MAPTMDS | PTMDS | PTMS | 71,000 |
9-22 | MTMS | MTMDS | ECHETMDS | ECHETMS | 81,000 |
9-23 | MTMS | MTMDS | PTMDS | PTMS | 63,000 |
9-24 | MTMS | MTMDS | GPTMDS | GPTMS | 121,000 |
9-25 | MTMS | MTMDS | MAPTMDS | MAPTMS | 153,000 |
9-26 | MTMS | ECHETMDS | MTMDS | MTMS | 82,000 |
9-27 | MTMS | PTMDS | MTMDS | MTMS | 63,000 |
9-28 | MTMS | GPTMDS | MTMDS | MTMS | 310,000 |
9-29 | MTMS | MAPTMDS | MTMDS | MTMS | 125,000 |
9-30 | GPTMS | GPTMDS | ECHETMDS | ECHETMS | 97,000 |
9-31 | GPTMS | GPTMDS | PTMDS | PTMS | 45,000 |
9-32 | GPTMS | GPTMDS | MTMDS | MTMS | 61,000 |
9-33 | GPTMS | GPTMDS | MAPTMDS | MAPTMS | 52,000 |
9-34 | GPTMS | ECHETMDS | GPTMDS | GPTMS | 37,000 |
9-35 | GPTMS | PTMDS | GPTMDS | GPTMS | 365,000 |
9-36 | GPTMS | MTMDS | GPTMDS | GPTMS | 85,000 |
9-37 | GPTMS | MAPTMDS | GPTMDS | GPTMS | 75,000 |
9-38 | MAPTMS | MAPTMDS | ECHETMDS | ECHETMS | 144,000 |
9-39 | MAPTMS | MAPTMDS | PTMDS | PTMS | 85,000 |
9-40 | MAPTMS | MAPTMDS | MTMDS | MTMS | 60,000 |
9-41 | MAPTMS | MAPTMDS | GPTMDS | GPTMS | 53,000 |
9-42 | MAPTMS | ECHETMDS | MAPTMDS | MAPTMS | 12,000 |
9-43 | MAPTMS | PTMDS | MAPTMDS | MAPTMS | 10,000 |
9-44 | MAPTMS | MTMDS | MAPTMDS | MAPTMS | 32,000 |
9-45 | MAPTMS | GPTMDS | MAPTMDS | MAPTMS | 231,000 |
[실험] [Experiment]
아연도금강판, 스테인레스 및 구리배선에 상기 실시예 1 내지 9에서 제조한 코팅 조성물을 코팅하고, 경화시켜 표면특성을 측정하였다.The coating composition prepared in Examples 1 to 9 was coated on a galvanized steel sheet, stainless steel, and copper wiring, and cured to measure surface properties.
- 표면경도측정 : 일반적으로 연필경도법(JIS 5600-5-4)은 일반적으로 750 g 하중으로 평가하는데 이보다 가혹조건인 1 kgf 하중으로 코팅면에 45도 각도로 연필을 매초 0.5 mm의 속도로 수평으로 10 mm 이동해서 코팅막을 긁어서 긁힌 흔적으로 평가하였다. 5회 실험 중 3 mm 이상 긁힌 흔적이 2회 이상 확인되지 않으면 상위의 경도의 연필을 선택하고, 긁힌 흔적이 2회 이상 되면 연필을 선정하고 그 연필경도보다 한단 하위의 연필경도가 해당 코팅막의 연필경도로 평가하여 하기 표 28에 나타내었다.-Surface hardness measurement In general, the pencil hardness method (JIS 5600-5-4) is generally rated at 750 g load, which is 10 mm horizontal at a rate of 0.5 mm per second at a 45-degree angle to the coating surface at a more severe 1 kgf load. The coating film was moved to evaluate the scratches. If the scratches are not confirmed more than 3 mm more than 3 times in 5 experiments, select the pencil of the higher hardness, and if the scratches are more than 2 times, select the pencil and the pencil hardness lower than the pencil hardness is the pencil of the coating film. The hardness is shown in Table 28 below.
표 28
Table 28
실시예(코팅두께 10 um) | 아연도금강판 | 스테인레스 | 구리배선 |
실시예 1의 광경화코팅조성물 | 9H | 9H | 9H |
실시예 2의 열경화코팅조성물 | 9H | 9H | 9H |
실시예 3의 광경화코팅조성물 | 9H | 9H | 9H |
실시예 4의 열경화코팅조성물 | 9H | 9H | 9H |
실시예 5의 광경화코팅조성물 | 9H | 9H | 9H |
실시예 6의 열경화코팅조성물 | 9H | 9H | 9H |
실시예 6의 고분자자체코팅조성물 | 9H | 9H | 9H |
실시예 7의 열경화코팅조성물 | 9H | 9H | 9H |
실시예 8의 광경화코팅조성물 | 9H | 9H | 9H |
실시예 9의 열경화코팅조성물 | 9H | 9H | 9H |
Example (Coating Thickness 10um) | galvanized steel | stainless | Copper wiring |
Photocuring coating composition of Example 1 | 9H | 9H | 9H |
Thermosetting Coating Composition of Example 2 | 9H | 9H | 9H |
Photocuring coating composition of Example 3 | 9H | 9H | 9H |
Thermosetting Coating Composition of Example 4 | 9H | 9H | 9H |
Photocuring coating composition of Example 5 | 9H | 9H | 9H |
Thermosetting Coating Composition of Example 6 | 9H | 9H | 9H |
Polymer self coating composition of Example 6 | 9H | 9H | 9H |
Thermosetting Coating Composition of Example 7 | 9H | 9H | 9H |
Photocuring coating composition of Example 8 | 9H | 9H | 9H |
Thermosetting Coating Composition of Example 9 | 9H | 9H | 9H |
- 염수분무시험 : JIS-K5621 준거하여 염화나트륨 용액 96시간 방치하여 평가하였으며, 그 결과를 표 29에 나타내었다. 평가기준은 평가 완료 후의 코팅 막을 상온에서 48시간 건조 후 육안으로 관찰해서 도막이 부풀어 오르거나 깨져서 벗겨진 부분이 없고, 강판의 변색 및 광택의 차이가 없는 경우를 양호, 그렇지 않은 경우를 불량으로 나타내었다.-Salt spray test : Sodium chloride solution was left to stand for 96 hours and evaluated according to JIS-K5621, and the results are shown in Table 29. Evaluation criteria showed that the coating film after the completion of evaluation was visually observed after drying for 48 hours at room temperature, and the coating film was not swollen or cracked, and there was no peeling part, and there was no discoloration and gloss difference of the steel sheet.
표 29
Table 29
실시예(코팅두께 10 um) | 아연도금강판 | 스테린레스 | 구리배선 | |||
코팅전 | 코팅후 | 코팅전 | 코팅후 | 코팅전 | 코팅후 | |
실시예 1-1의 광경화코팅조성물 | 불량 | 양호 | 양호 | 양호 | 불량 | 양호 |
실시예 2-1의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 3-1의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 4-1의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 5-1의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 6-1의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 6의 고분자자체코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 7-1의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 8-1의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 9-1의 열경화코팅조성물 | 양호 | 양호 | 양호 |
Example (Coating Thickness 10um) | galvanized steel | Sterin | Copper wiring | |||
Before coating | After coating | Before coating | After coating | Before coating | After coating | |
Photocuring coating composition of Example 1-1 | Bad | Good | Good | Good | Bad | Good |
Thermosetting Coating Composition of Example 2-1 | Good | Good | Good | |||
Photocuring coating composition of Example 3-1 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 4-1 | Good | Good | Good | |||
Photocuring coating composition of Example 5-1 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 6-1 | Good | Good | Good | |||
Polymer self coating composition of Example 6 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 7-1 | Good | Good | Good | |||
Photocuring coating composition of Example 8-1 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 9-1 | Good | Good | Good |
- 내오염성 : 0.5% Carbon Black 용액을 제조하여 코팅 막 표면에 Spot형태로 떨구어 80 에서 24시간 접촉시킨 후 물로 닦아 낸 표면의 얼룩 변화를 평가하였으며, 그 결과를 표 30에 나타내었다. 평가기준은 검은 얼룩이 없이 물로 깨끗이 닦인 경우를 양호, 그렇지 않고 Spot 형태의 자국이 남은경우를 불량으로 나타내었다-Pollution resistance: 0.5% Carbon Black solution was prepared, and the surface of the coating film was dropped in the form of spot and contacted at 80 hours for 24 hours, and the staining change of the surface wiped with water was evaluated, and the results are shown in Table 30. The evaluation criteria indicated that the case of wiping with water without black stains was good, and the case of spot-shaped marks left as defective.
표 30
Table 30
실시예(코팅두께 10 um) | 아연도금강판 | 스테린레스 | 구리배선 | |||
코팅전 | 코팅후 | 코팅전 | 코팅후 | 코팅전 | 코팅후 | |
실시예 1-2의 광경화코팅조성물 | 불량 | 양호 | 양호 | 양호 | 불량 | 양호 |
실시예 2-2의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 3-2의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 4-2의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 5-2의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 6-2의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 6의 고분자자체코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 7-2의 열경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 8-2의 광경화코팅조성물 | 양호 | 양호 | 양호 | |||
실시예 9-2의 열경화코팅조성물 | 양호 | 양호 | 양호 |
Example (Coating Thickness 10um) | galvanized steel | Sterin | Copper wiring | |||
Before coating | After coating | Before coating | After coating | Before coating | After coating | |
Photocuring coating composition of Example 1-2 | Bad | Good | Good | Good | Bad | Good |
Thermosetting Coating Composition of Example 2-2 | Good | Good | Good | |||
Photocuring coating composition of Example 3-2 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 4-2 | Good | Good | Good | |||
Photocuring coating composition of Example 5-2 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 6-2 | Good | Good | Good | |||
Polymer self coating composition of Example 6 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 7-2 | Good | Good | Good | |||
Photocuring coating composition of Example 8-2 | Good | Good | Good | |||
Thermosetting Coating Composition of Example 9-2 | Good | Good | Good |
상기 표 28 내지 30에 나타난 바와 같이 본 발명의 금속코팅조성물을 사용하여 코팅한 경우 매우 우수한 방청특성, 방오특성, 표면경도 및 내스크레치성을 동시에 나타내었다. 표 28 내지 표 30에 기재되지 않았지만 본 발명의 다른 실시예의 코팅조성물들도 상기 표 28 내지 표 30에 기재된 코팅조성물들과 대등한 결과를 나타내었다.As shown in Tables 28 to 30, when the coating using the metal coating composition of the present invention showed very excellent anti-rust properties, antifouling properties, surface hardness and scratch resistance. Although not described in Tables 28 to 30, the coating compositions of other embodiments of the present invention also showed comparable results with the coating compositions described in Tables 28 to 30 above.
본 발명에 따른 금속코팅방법은 금속 표면 위에 코팅용액을 이용하여 코팅함으로써 코팅공정이 용이할 뿐만 아니라 형성된 코팅층의 방청지속능력, 내스크레치성, 발수특성, 수분차폐특성, 방오특성, 광택성, 표면강도, 및 열안정성이 우수하며 동시에 접착성이 우수하여 자동차, 주방용품, 금속관(상수도관 포함), 금속조형물, 가로등, 교통표지판, 태양전지 외관프레임, 도로분리대, 건축물 등에 유용하게 사용할 수 있을 뿐만 아니라 금속 배선이 사용되는 반도체, 디스플레이 분야에도 효율적으로 사용될 수 있다.The metal coating method according to the present invention not only facilitates the coating process by coating with a coating solution on the metal surface, but also the rust resistance, scratch resistance, water repellency, water shielding property, antifouling property, glossiness, surface of the formed coating layer. Excellent strength, thermal stability, and adhesiveness make it useful for automobiles, kitchen utensils, metal pipes (including water pipes), metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators, buildings, etc. In addition, it can be efficiently used in the field of semiconductor and display where metal wiring is used.
Claims (17)
- 금속 표면 위에 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 금속코팅방법:A metal coating method comprising coating and curing a metal coating composition comprising a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9 on a metal surface:[화학식 1][Formula 1][화학식 2][Formula 2][화학식 3][Formula 3][화학식 4][Formula 4][화학식 5][Formula 5][화학식 6][Formula 6][화학식 7][Formula 7][화학식 8][Formula 8][화학식 9][Formula 9]상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or an C 3 ~ C 40 aryl siol group,a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고,a and d are each independently an integer of 1 to 100,000,b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,e는 각각 독립적으로 1 또는 2이며,e are each independently 1 or 2,n은 각각 독립적으로 1 내지 20의 정수이다.n is independently an integer of 1-20.
- 제1항에 있어서,The method of claim 1,상기 금속은 도금 또는 합금 금속인 것을 특징으로 하는 금속코팅방법.The metal coating method, characterized in that the plating or alloy metal.
- 제1항에 있어서,The method of claim 1,상기 금속은 스테인레스인 것을 특징으로 하는 금속코팅방법.The metal coating method, characterized in that the stainless steel.
- 제1항에 있어서,The method of claim 1,상기 금속은 전자제품의 배선인 것을 특징으로 하는 금속코팅방법.The metal is a metal coating method, characterized in that the wiring of the electronic product.
- 제5항에 있어서,The method of claim 5,상기 코팅 두께는 0.01 내지 500 um인 것을 특징으로 하는 금속코팅방법.The coating thickness is a metal coating method, characterized in that 0.01 to 500 um.
- 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물:Metal coating composition comprising a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9:[화학식 1][Formula 1][화학식 2][Formula 2][화학식 3][Formula 3][화학식 4][Formula 4][화학식 5][Formula 5][화학식 6][Formula 6][화학식 7][Formula 7][화학식 8][Formula 8][화학식 9][Formula 9]상기 화학식 1 내지 9에서,In Chemical Formulas 1 to 9,Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or an C 3 ~ C 40 aryl siol group,a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고,a and d are each independently an integer of 1 to 100,000,b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,e는 각각 독립적으로 1 또는 2이며,e are each independently 1 or 2,n은 각각 독립적으로 1 내지 20의 정수이다.n is independently an integer of 1-20.
- 제6항에 있어서,The method of claim 6,a는 3 내지 1000이고, b는 1 내지 500, d는 1 내지 500인 것을 특징으로 하는 금속코팅조성물.a is 3 to 1000, b is 1 to 500, d is 1 to 500, the metal coating composition.
- 제6항에 있어서,The method of claim 6,n 값의 평균이 4 내지 5인 것을 특징으로 하는 금속코팅조성물.Metal coating composition, characterized in that the average value of n to 4 to 5.
- 제6항에 있어서,The method of claim 6,상기 실세스퀴옥산 복합 고분자의 중량평균분자량이 1,000 내지 1,000,000인 것을 특징으로 하는 금속코팅조성물.Metal coating composition, characterized in that the weight average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000.
- 제6항에 있어서,The method of claim 6,상기 코팅 조성물은 무용제 타입인 것을 특징으로 하는 금속코팅조성물.The coating composition is a metal coating composition, characterized in that the solvent-free type.
- 제6항에 있어서,The method of claim 6,상기 코팅조성물은 The coating composition is상기 실세스퀴옥산 복합 고분자;The silsesquioxane composite polymer;개시제; 및Initiator; And유기용매;Organic solvents;를 포함하는 것을 특징으로 금속코팅조성물.Metal coating composition comprising a.
- 제6항에 있어서,The method of claim 6,상기 코팅조성물이 경화제, 자외선 흡수제, 산화 방지제, 소포제, 레벨링제, 발수제, 난연제, 또는 접착개선제를 더욱 포함하는 것을 특징으로 하는 금속코팅조성물.The coating composition is a metal coating composition further comprises a curing agent, ultraviolet absorber, antioxidant, antifoaming agent, leveling agent, water repellent, flame retardant, or adhesion improving agent.
- 표면 위에 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 금속코팅조성물이 코팅되어 경화된 경화물을 포함하는 것을 특징으로 실세스퀴옥산 복합 고분자 코팅 금속.The silsesquioxane composite polymer coated metal, comprising a cured product coated with a metal coating composition containing the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 on the surface thereof and cured.
- 제13항에 있어서,The method of claim 13,상기 실세스퀴옥산 복합 고분자 코팅 금속은 제1항 기재의 금속코팅방법에 의하여 형성된 것을 특징으로 실세스퀴옥산 복합 고분자 코팅 금속.The silsesquioxane composite polymer coated metal is formed by the metal coating method of claim 1.
- 제13항 기재의 실세스퀴옥산 복합 고분자 코팅 금속을 포함하는 물품.An article comprising the silsesquioxane composite polymer coated metal of claim 13.
- 제15항에 있어서,The method of claim 15,상기 물품은 자동차, 주방용품, 금속관(상수도관 포함), 금속조형물, 가로등, 교통표지판, 태양전지 외관프레임, 도로분리대 또는 건축물인 것을 특징으로 물품.The article is an automobile, kitchen utensils, metal pipes (including water pipes), metal sculptures, street lights, traffic signs, solar cell exterior frames, road separators or buildings, characterized in that the article.
- 제15항에 있어서,The method of claim 15,상기 물품은 반도체 또는 전자제품인 것을 특징으로 하는 물품.And said article is a semiconductor or electronics.
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KR101067283B1 (en) * | 2003-03-11 | 2011-09-23 | 제이엔씨 주식회사 | Polymer obtained with silsesquioxane derivative |
US20130072609A1 (en) * | 2011-09-21 | 2013-03-21 | Government Of The United States As Represented By The Secretary Of The Air Force | Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss) |
KR101249798B1 (en) * | 2010-08-18 | 2013-04-03 | 한국과학기술연구원 | A Method for Preparing a Controlled Structure of Polysilsesquioxane and Polysilsesquioxane Prepared by the Same |
-
2015
- 2015-03-06 WO PCT/KR2015/002174 patent/WO2015133857A1/en active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2001010871A1 (en) * | 1999-08-04 | 2001-02-15 | Hybrid Plastics | Process for the formation of polyhedral oligomeric silsesquioxanes |
KR101067283B1 (en) * | 2003-03-11 | 2011-09-23 | 제이엔씨 주식회사 | Polymer obtained with silsesquioxane derivative |
KR100966193B1 (en) * | 2007-09-18 | 2010-06-25 | 한국세라믹기술원 | Nano-composite comprising poss and method for manufacturing the same |
KR101249798B1 (en) * | 2010-08-18 | 2013-04-03 | 한국과학기술연구원 | A Method for Preparing a Controlled Structure of Polysilsesquioxane and Polysilsesquioxane Prepared by the Same |
US20130072609A1 (en) * | 2011-09-21 | 2013-03-21 | Government Of The United States As Represented By The Secretary Of The Air Force | Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss) |
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