WO2015130143A1 - Polymère complexe de silsesquioxane et son procédé de préparation - Google Patents

Polymère complexe de silsesquioxane et son procédé de préparation Download PDF

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WO2015130143A1
WO2015130143A1 PCT/KR2015/001965 KR2015001965W WO2015130143A1 WO 2015130143 A1 WO2015130143 A1 WO 2015130143A1 KR 2015001965 W KR2015001965 W KR 2015001965W WO 2015130143 A1 WO2015130143 A1 WO 2015130143A1
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methyl
group
phenyl
composite polymer
pomma
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PCT/KR2015/001965
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English (en)
Korean (ko)
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최승석
유재원
남동진
김두식
박경민
황종원
오성연
최지식
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주식회사 동진쎄미켐
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Priority claimed from KR1020150027185A external-priority patent/KR20150102860A/ko
Application filed by 주식회사 동진쎄미켐 filed Critical 주식회사 동진쎄미켐
Priority to CN201580010948.8A priority Critical patent/CN106029747B/zh
Priority claimed from KR1020150028252A external-priority patent/KR102363820B1/ko
Publication of WO2015130143A1 publication Critical patent/WO2015130143A1/fr

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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
    • 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

Definitions

  • the present invention relates to a silsesquioxane composite polymer and a manufacturing method thereof, and more particularly, to a silsesquioxane composite in which various silsesquioxane structures are introduced into one silsesquioxane polymer to maximize processability and physical properties. It relates to a polymer.
  • Silsesquioxane is used for various purposes in various fields. In particular, several attempts have been made to improve processability and maximize mechanical and physical properties, and research and development continue to this day. However, the silsesquioxane polymers developed so far are still insufficient to satisfy both processability and mechanical and physical properties.
  • Cage silsesquioxane for example, has been applied to various aspects by showing physical properties that siloxane bonds can express.
  • the cage silsesquioxane is a crystalline structure in itself and has a limited solubility in solution processing.
  • molecular units such as recrystallization are generated in the product itself, which causes a problem that performance reproducibility is not guaranteed.
  • the linear silsesquioxane has excellent solution processability and can compensate for the shortcomings of the cage-like structure, but has a disadvantage in that the physical property is less than the cage-type structure of the crystalline structure.
  • the present inventors have studied to make up for the above disadvantages of silsesquioxane and to maximize the advantages, designing a polymer structure of a specific structure and inducing the introduction of an easy curing process using an organic functional group introduced into the side chain. As a result, it was confirmed that the excellent physical properties can be maintained for a long time, can be used in various industrial aspects, such as the main material, additive material, coating material to complete the present invention.
  • the present invention provides a silsesquioxane composite polymer that maximizes processability and physical properties, including linear silsesquioxane chain and cage-type silsesquioxane having a specific structure in one polymer. It aims to do it.
  • Another object of the present invention is to provide a method for producing the silsesquioxane composite polymer.
  • It is another object of the present invention to provide a silsesquioxane coating composition comprising the silsesquioxane composite polymer.
  • the present invention provides a silsesquioxane composite polymer represented by one of the following Chemical Formulas 1 to 3:
  • Each Y is independently O, NR 9 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 10 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 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 a
  • 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,
  • e is 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR 2 ) 2 structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound. 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 second step.
  • R 1 , R 2 , R 6 , D, a and d are as defined in formulas (1) to (3).
  • the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And after the first step, an excess organosilane compound is added in order to introduce Dd (OR 3 ) 2 and Dd (OR 4 ) 2 structures to Chemical Formula 4 as shown in Chemical Formula 2, and an acidic catalyst is added to the reactor to react the reaction solution. Adjusting the acidity and then stirring the second 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 removing the sole cage formation structure through a recrystallization and filtering process after the third step.
  • the method of preparing silsesquioxane composite polymer represented by Chemical Formula 2 is provided.
  • the present invention is a first step of preparing a general formula (4) by mixing a basic catalyst and an organic solvent in the reactor and then adding an organic silane compound and condensation; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid to introduce a Dd (OR 5 ) 2 structure into Chemical Formula 4 after the first step, and then adding and stirring an organic silane compound.
  • the present invention also provides a silsesquioxane coating composition comprising the silsesquioxane composite polymer.
  • the silsesquioxane composite polymer according to the present invention has excellent processability of linear silsesquioxane and excellent physical properties of cage-type silsesquioxane at the same time. , Heat resistance and the like can be given to various materials.
  • the present invention provides a silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1-3:
  • Each Y is independently O, NR 9 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 10 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 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 a
  • 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,
  • e is 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • the silsesquioxane composite polymer represented by any one of Formulas 1 to 3 may be represented by R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , or R 10 . It is a composite silsesquioxane polymer which has the indicated organic functional group, the repeating unit consists of a and d, and can selectively introduce e as a terminal unit.
  • N of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of Formula 1 or 2 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, and when n is 4, the substituted structure is represented by the following Formula 5:
  • R is as defined above.
  • n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating unit [E] e of Chemical Formula 3 may be substituted with an integer of 1 to 20, preferably 3 To 10, more preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by the following Chemical Formula 6:
  • R is as defined above.
  • the silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Tables 1 and 2 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 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 the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability and obtain broad applicability. 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 silsesquioxane composite polymer of the present invention may be prepared by continuously adjusting basicity and acidity using a basic catalyst and an acidic catalyst in one reactor, and one of the following manufacturing methods may be used.
  • the prepared silsesquioxane composite polymer has a structure as shown in Formula 1-1.
  • R, R 1 , R 2 , R 6 , R 7 , D, Y, a and d are as defined in Formulas 1 to 3.
  • R, R 3 , R 4 , R 6 , R 7 , D, Y, a and d are as defined in Chemical Formulas 1 to 3.
  • the prepared silsesquioxane composite polymer has a structure as shown in Chemical Formula 3-1.
  • R, R 5 , R 6 , R 7 , R 8 , D, Y, X, a, d and e are as defined in Formulas 1 to 3.
  • 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
  • organosilane-based compound of the silsesquioxane composite polymer of the present invention R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,
  • An organic silane containing R 9 or R 10 may be used, and in particular, an organic silane compound containing a phenyl group or an amino group having an effect of improving chemical resistance of the silsesquioxane composite polymer and improving non-swelling property, or a composite polymer
  • organosilane compound containing an epoxy group or a (meth) acryl group which has the effect of increasing the hardening density of and improving the mechanical strength and hardness of a hardened layer 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,
  • the pH of the reaction solution of the first step of the present invention is preferably 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 8 It is preferably 1 to 11.5, and the pH of the reaction solution of the fourth step of preparing Formula 3 is preferably 1.5 to 4.
  • the pH of the reaction solution of the fourth step of preparing Formula 3 is preferably 1.5 to 4.
  • the present invention provides a coating composition comprising a silsesquioxane composite polymer represented by any one of Formulas 1 to 3.
  • the coating composition may be coated alone as a solvent-free type when the silsesquioxane composite polymer is a liquid, and may be configured to 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 comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 3, an organic solvent commonly used in the art that is compatible with the composite polymer, an initiator, and optionally a curing agent. It may further include additives such as 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.
  • the initiator is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the composition, when included in the content within the above range, After transmission 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.
  • 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
  • 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 curing agent is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the composition.
  • 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 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, strength, and the like. It is preferably included in an amount of 0.1-10 parts by weight with respect to parts.
  • 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., BYK- 308, BYK-373, etc.), polymethylalkylsiloxanes (eg, BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxanes (eg, BYK-320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxanes (e.g., BYK-315, etc.), aralkyl modified methylalkyl polysiloxanes, e.g.
  • polyester hydroxy polydimethylsiloxane Polydimethylsiloxane (Polyester modified h ydroxy functional polydimethylsiloxane (e.g., BYK-370, etc.), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, e.g., 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, e.g.
  • BYK-380, etc. ionic polyacrylic (e.g., BYK- 381, etc.), polyacrylate (for example, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK -352, etc.), polymethacrylate type (Polymethacrylate, such as BYK-390, etc.), polyether acryl Lidimethylsiloxane (Polyether modified acryl functional polydimethylsiloxane, such as BYK-UV 3500, BYK-UV3530, etc.), Polyether siloxane (Polyether modified siloxane, such as BYK-347, etc.), Alcohol alkoxylates ( Alcohol alkoxylates, for example BYK-DYNWET 800, etc., acrylates (Acrylate, for example BYK-392, etc.), hydroxy silicone polyacryl
  • the coating composition of the present invention can be applied to a variety of materials to improve the high surface hardness, mechanical strength and heat resistance to the material.
  • the thickness of the coating may be arbitrarily controlled, and may be 0.01 to 500 um, preferably 0.1 to 300 um, more preferably 1 to 100 um.
  • the material may be metal, ceramic, plastic, wood, paper, glass, or fiber, and a specific article coated on a more specific material may be a protective film of a mobile phone or a display.
  • the method for coating the coating composition is known among spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like.
  • spin coating bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like.
  • those skilled in the art can arbitrarily select and apply.
  • the silsesquioxane composite polymer prepared according to the present invention includes a linear silsesquioxane chain and a cage silsesquioxane chain composed of linear silsesquioxane polymers, the processability of the linear polymer and the crystalline silsesquioxane It can have excellent physical properties of, and is easy to cure through the organic functional groups included in the structure, it can be widely applied to the industry to apply the organic-inorganic hybridized polymer.
  • the basic optical properties, physical properties, heat resistance properties of the silicon is basically provided, it can be widely used as a main material, an additive, or various coating materials.
  • 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 aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 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.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 7 below. In this case, the method used in Examples 1-b and 1-c was equally applied.
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di (Methyl) tetramethoxy disiloxane.
  • Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 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.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 8 below. At this time, the manufacturing method was equally applied to the method used in Example 2.
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di (Methyl) tetramethoxy disiloxane.
  • 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 an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. 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 in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C 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, in particular, the result of Formula 3 is as follows.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 9 below. In this case, the method used in Example 3 was equally applied.
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) tetraDSoxy Dimethoxyg ) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di (Methyl) tetramethoxy disiloxane.
  • Example 4 Preparation and process of coating composition using silsesquioxane composite polymer
  • Example 4-1 The coating composition prepared in Example 4-1 was applied to SKC-SG00L 250 um film, SKC PET film, and Mayer coating was performed by dividing No. 30-50 rod into 5 units. Thereafter, the solvent was removed at a temperature of 80 ° C. for 10 minutes, and UV was irradiated for 10 seconds in a 100 mW / cm 2 lamp using UV equipment to obtain a result.
  • thermosetting coating composition 50 g of the silsesquioxane composite polymer represented by Chemical Formula 3-1 prepared in Example was dissolved in 50% by weight in methyl ethyl ketone 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 4-3 The coating composition prepared in Example 4-3 was applied to a SKC-SG00L 250 um film, which is a SKC PET film, and No. 30 to 50 rods were divided into 5 units to perform Mayer coating. After coating, the resultant was obtained after curing for 10 minutes in a drying oven at 80 °C.
  • Example 1 The results obtained in Examples 1, 2 and 3 were cured through heat without any composition.
  • the weight average molecular weight and molecular weight distribution of the silsesquioxane resin prepared in Example 1 were used with a JASCO PU-2080 plus SEC system equipped with a RI-2031 plus refractive index detector and a UV-2075 plus UV detector (254 detection wavelength). It was measured by. THF was used at flow rate 1 at 40 ° C. and samples were separated through four columns (Shodex-GPC KF-802, KF-803, KF-804 and KF-805). As a result, the obtained silsesquioxane had a weight average molecular weight of 12,000 by SEC analysis and confirmed that the molecular weight distribution was 1.8.
  • IR was measured using the ATR mode of the Perkin-Elmer FT-IR system Spectrum-GX.
  • FT-IR analysis showed a broad bimodal (continuous double-shaped) absorption peak in the small amount of the structure obtained in Example 1-b at 950-1200 cm ⁇ 1 , which was perpendicular to the silsesquioxane chain ( It is derived from the stretching vibration of siloxane bonds in the -Si-O-Si-R and horizontal (-Si-O-Si-) directions.
  • the peak appearing at 1200 cm ⁇ 1 was further grown, thereby confirming the substitution of the cage structure.
  • This result was not found in cage type (generally, molecular weight of 1,000 ⁇ 5,000), which is low in actual molecular weight, despite the growth of cage characteristic peaks. From this, it was confirmed that the introduction into the expected structure in the chain.
  • the thermal stability of the structures prepared in Examples 1, 2 and 3 was confirmed using a thermal gravimetric analyzer (TGA), in particular, the composite polymer obtained in the formula of 3-1.
  • TGA thermal gravimetric analyzer
  • the measurement was measured via TGA at a 10 ° C./min scan rate of 50-800 ° C. under nitrogen.
  • the amount of decomposition of Si-OH and Si-OR which was decomposed between 100-200 ° C. was significantly reduced.
  • PC I component Glastic polycarbonate
  • SKC's PET and PMMA COPAN's OAS-800 transparent substrates using the polymer resins described in Tables 7 to 9 in the same manner as described in Example 4 Coating and curing were performed to determine the surface properties.
  • the following experimental results are the results using the polymer resin prepared in Example 3, the coating composition using the polymer resins described in Tables 7 to 9, although not shown in the table showed a result equivalent to the polymer resin of Example 3.
  • the pencil hardness method (JIS 5600-5-4) is generally rated at 500 g load, which is 3 kg horizontally at a rate of 0.5 mm per second at a 45-degree angle to the coating surface under a more severe 1 kgf load.
  • the coating film was moved to evaluate the scratches. If five traces do not confirm the scratches more than two times, the pencil of the upper hardness is selected. If the scratches are more than two times, the pencil is selected and the pencil hardness lower than the pencil hardness is evaluated as the pencil hardness of the coating film. It was.
  • the evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um or more.
  • the coating composition of the present invention not only shows a very good surface hardness and optical properties, but also excellent in other physical properties at the same time.
  • the silsesquioxane composite polymer according to the present invention has excellent processability of linear silsesquioxane and excellent physical properties of cage-type silsesquioxane at the same time. , Heat resistance and the like can be given to various materials.

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Abstract

La présente invention concerne un polymère complexe de silsesquioxane et un procédé de préparation de celui-ci, et plus spécifiquement, un polymère complexe de silsesquioxane dont l'aptitude au traitement et les caractéristiques physiques sont maximisées par inclusion, dans un polymère unique, d'une chaîne à barettes de silsesquioxane et d'un silsesquioxane de type cage qui ont une structure spécifique.
PCT/KR2015/001965 2014-02-28 2015-02-27 Polymère complexe de silsesquioxane et son procédé de préparation WO2015130143A1 (fr)

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KR10-2014-0024574 2014-02-28
KR20140024574 2014-02-28
KR1020150027185A KR20150102860A (ko) 2014-02-28 2015-02-26 실세스퀴옥산 복합 고분자 및 이의 제조방법
KR10-2015-0027185 2015-02-26
KR10-2015-0028252 2015-02-27
KR1020150028252A KR102363820B1 (ko) 2014-02-28 2015-02-27 실세스퀴옥산 복합 고분자 및 이의 제조방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251407A (ja) * 1997-03-14 1998-09-22 Nippon Steel Chem Co Ltd シリコーン化合物及びその製造方法
US20040068075A1 (en) * 1999-12-23 2004-04-08 Hybrid Plastics Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities
US20040138355A1 (en) * 2001-01-24 2004-07-15 Hideo Saito Polyphentlene ether resin composition containing silicon compounds
JP2008512498A (ja) * 2004-09-13 2008-04-24 ロレアル 改善された付着性及び／又は柔軟性を有するｐｏｓｓ含有化粧品用組成物と改善された化粧品用組成物の製造方法
KR20130125224A (ko) * 2012-05-08 2013-11-18 주식회사 동진쎄미켐 사다리형 사이올계 실세스퀴옥산 고분자 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251407A (ja) * 1997-03-14 1998-09-22 Nippon Steel Chem Co Ltd シリコーン化合物及びその製造方法
US20040068075A1 (en) * 1999-12-23 2004-04-08 Hybrid Plastics Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities
US20040138355A1 (en) * 2001-01-24 2004-07-15 Hideo Saito Polyphentlene ether resin composition containing silicon compounds
JP2008512498A (ja) * 2004-09-13 2008-04-24 ロレアル 改善された付着性及び／又は柔軟性を有するｐｏｓｓ含有化粧品用組成物と改善された化粧品用組成物の製造方法
KR20130125224A (ko) * 2012-05-08 2013-11-18 주식회사 동진쎄미켐 사다리형 사이올계 실세스퀴옥산 고분자 및 이의 제조방법

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