CN106062079A - Thermoplastic resin composition comprising silsesquioxane composite polymer - Google Patents
Thermoplastic resin composition comprising silsesquioxane composite polymer Download PDFInfo
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- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
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Abstract
The present invention relates to a thermoplastic resin composition containing a silsesquioxane composite polymer, and more particularly, to a thermoplastic resin composition having excellent heat resistance, chemical resistance, stain resistance, gas permeation prevention property, permeability, colorability, abrasion resistance, surface hardness, and the like, by containing a silsesquioxane composite polymer containing a linear silsesquioxane chain having a specific structure and a cage silsesquioxane in one polymer.
Description
Technical field
The present invention relates to the use of the thermoplastic resin composition of silsesquioxane composite high-molecular, more specifically, related to
And line style silsesquioxane chain and the sesquialter silicon of cage-type silsesquioxane of ad hoc structure it is contained within by comprising a macromolecule
Oxygen alkane composite high-molecular thus thermostability, chemical resistance, soil resistance, gas permeation prevent characteristic, permeability, coloring, wear-resisting
Property and the excellent thermoplastic resin composition such as case hardness.
Background technology
Thermoplastic resin is because of workability thus in various fields with by injection or the article shaped of extrusion, film, cellosilk
It is applied Deng variform and is applied flexibly, as representational thermoplastic resin, using PC (Merlon), PMMA (poly-
Methyl methacrylate), PES (polyether sulfone), PET (polyethylene terephthalate), PEN (poly-naphthalenedicarboxylic acid ethylene glycol
Ester), COC (cyclic olefine copolymer), PAc (polyacrylate), PE (polyethylene), PEEK (polyether-ether-ketone), PEI (polyetherimide
Amine), PI (polyimides), PSF (polysulfones), PVA (polyvinyl alcohol), (triacetyl is fine for PVCi (polyvinyl cinnamate), TAC
Dimension element), polysilicon (Poly Silicone), polyurethane (Polyurethane) and epoxy resin (Epoxy Resin) etc..
As mentioned above thermoplastic resin due to thermostability, chemical resistance, gas permeation prevent characteristic, water repellency, the transparency,
Coloring, wearability and case hardness etc. are low, are therefore meeting the physical characteristic side required by the scene gone forward side by side with industry development
Face Shortcomings, in order to solve this weak point, carries out following effort: by persistence by the mixing of various thermoplastic resins
Use, or add various functional additive to strengthen physical property.
Such as, Korean Patent Publication No. 10-2002-0034542 discloses and adds in thermoplastic polycarbonate resin
There is rubber-modified graft copolymer and in the matrix resin being made up of vinyl copolymer, be added with N-acyl group morpholine phosphoric acid
The thermoplastic resin composition of the excellent in flame retardance of ester compounds and fluorinated polyolefin, and Korean Patent Publication 10-2011-
No. 0069592 disclose with relative to polycarbonate resin 100 weight portion comprise organosilicon based compound 0.01-10 weight portion,
Mean diameter is the metal organic sulfonate 0.01-1.5 weight portion of 100-400 μm and polyfluoroethylene resin 0.01-1 weight portion is
The Polycarbonate flame retardant film resin combination of feature, but there are the following problems: it is insufficient for the high flame retardant of demander
And chemical resistance, and gas permeation cannot be solved prevent characteristic, soil resistance, water repellency, coloring, wearability and case hardness
Deng.
Summary of the invention
Problem to be solved
In order to solve problem as above, it is an object of the invention to, it is provided that include by being included in a macromolecule
There are line style silsesquioxane chain and the silsesquioxane composite high-molecular of cage-type silsesquioxane of ad hoc structure, thus heat-resisting
Property, chemical resistance, soil resistance, gas permeation prevent the heat that characteristic, permeability, coloring, wearability and case hardness etc. are excellent
Thermoplastic resin composition.
It is further an object that, it is provided that by being manufactured by above-mentioned thermoplastic resin composition, thus thermostability,
Chemical resistance, soil resistance, gas permeation prevent the article that characteristic, permeability, coloring, wearability and case hardness etc. are excellent.
The method solving problem
To achieve these goals, the present invention provides a kind of thermoplastic resin composition, it is characterised in that comprise followingization
The silsesquioxane composite high-molecular that in formula 1 to 9, any one is represented:
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
In above-mentioned chemical formula 1 to 9,
A isB isD isE is
Y is each independently O, NR21Or [(SiO3/2R)4+2nO], and at least one is [(SiO3/2R)4+2nO],
X is each independently R22Or [(SiO3/2R)4+2nR], and at least one is [(SiO3/2R)4+2nR],
R、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22
It is each independently hydrogen；Deuterium；Halogen；Amido；Epoxy radicals；Cyclohexyl ring epoxide；(methyl) acryloyl group；Mercapto；Carbimide.
Ester group；Itrile group；Nitro；Phenyl；By deuterium, halogen, amido, epoxy radicals, (methyl) acryloyl group, mercapto, NCO, nitrile
The C that base, nitro, phenyl are substituted or non-substituted1～C40Alkyl；C2～C40Thiazolinyl；C1～C40Alkoxyl；C3～C40Ring
Alkyl；C3～C40Heterocyclylalkyl；C6～C40Aryl；C3～C40Heteroaryl；C3～C40Aralkyl；C3～C40Fragrant oxygen
Base；Or C3～C40Aryl mercaptan base, preferably include by deuterium, halogen, amido, (methyl) acryloyl group, mercapto, isocyanates
The C that base, itrile group, nitro, phenyl, cyclohexyl ring epoxide are substituted or non-substituted1～C40Alkyl, C2～C40Thiazolinyl, amido, ring
Epoxide, cyclohexyl ring epoxide, (methyl) acryloyl group, mercapto, phenyl or NCO,
A and d is each independently 1 to 100, and the integer of 000, preferably a are 3 to 1000, and d is 1 to 500, and more preferably a is 5
To 300, d is 2 to 100,
B is each independently the integer of 1 to 500,
E is each independently 1 or 2, preferably 1,
N is each independently the integer of 1 to 20, and preferably 3 to 10.
Additionally, the present invention provides a kind of article, it is characterised in that manufactured by above-mentioned thermoplastic resin composition.
Invention effect
The thermoplastic resin composition of the present invention is contained within the line style sesquialter of ad hoc structure by being included in a macromolecule
The silsesquioxane composite high-molecular of siloxane chain and cage-type silsesquioxane, thus thermostability, chemical resistance, soil resistance, gas
Body is through preventing the excellences such as characteristic, permeability, coloring, wearability and case hardness.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
The thermoplastic resin composition of the present invention is characterised by, comprises in following chemical formula 1 to 9 any one represented
Silsesquioxane composite high-molecular:
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
In above-mentioned chemical formula 1 to 9,
A isB isD isE is
Y is each independently O, NR21Or [(SiO3/2R)4+2nO], and at least one is [(SiO3/2R)4+2nO],
X is each independently R22Or [(SiO3/2R)4+2nR], and at least one is [(SiO3/2R)4+2nR],
R、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22
It is each independently hydrogen；Deuterium；Halogen；Amido；Epoxy radicals；Cyclohexyl ring epoxide；(methyl) acryloyl group；Mercapto；Carbimide.
Ester group；Itrile group；Nitro；Phenyl；By deuterium, halogen, amido, epoxy radicals, (methyl) acryloyl group, mercapto, NCO, nitrile
The C that base, nitro, phenyl are substituted or non-substituted1～C40Alkyl；C2～C40Thiazolinyl；C1～C40Alkoxyl；C3～C40Ring
Alkyl；C3～C40Heterocyclylalkyl；C6～C40Aryl；C3～C40Heteroaryl；C3～C40Aralkyl；C3～C40Fragrant oxygen
Base；Or C3～C40Aryl mercaptan base, preferably include by deuterium, halogen, amido, (methyl) acryloyl group, mercapto, isocyanates
The C that base, itrile group, nitro, phenyl, cyclohexyl ring epoxide are substituted or non-substituted1～C40Alkyl, C2～C40Thiazolinyl, amido, ring
Epoxide, cyclohexyl ring epoxide, (methyl) acryloyl group, mercapto, phenyl or NCO,
A and d is each independently 1 to 100, and the integer of 000, preferably a are 3 to 1000, and d is 1 to 500, and more preferably a is 5
To 300, d is 2 to 100,
B is each independently the integer of 1 to 500,
E is each independently 1 or 2, preferably 1,
N is each independently the integer of 1 to 20, and preferably 3 to 10.
The thermoplastic resin composition of the present invention repeats by having above-mentioned [A] a and [D] d in being included in above-mentioned macromolecule
Unit, selectivity have the silsesquioxane of the ad hoc structure of [B] b or [E] e repetitive such that it is able to make by thermoplastic resin
The article of oil/fat composition manufacture have thermostability, chemical resistance, soil resistance, gas permeation prevent characteristic, permeability, coloring,
Wearability and case hardness.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 1 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound is also condensed, and manufactures following chemical formula 10；Second step, after above-mentioned first step, in order to by [D] d (OR2)2Structure is led
Enter in chemical formula 10, in reactor, add acidic catalyst, reactant liquor is adjusted to acidity, be then added with organic silane and close
Thing also stirs；And third step, after the second step described above, in reactor, add base catalyst, reactant liquor is changed
For alkalescence, implement condensation reaction.
[chemical formula 10]
In above-mentioned formula, R1、R2、R16, D, a identical with the definition in above-mentioned chemical formula 1 to 9 with d.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 2 of the present invention can be by carrying out following steps
Manufacture: first step, in the reactor after mixed-alkali catalyst and organic solvent, be added with organic silane compound and be condensed,
Manufacture above-mentioned chemical formula 10；Second step, after above-mentioned first step, in order to as chemical formula 2 by [D] d (OR3)2With
[D]d(OR4)2Structure imports chemical formula 10, adds acidic catalyst, reactant liquor is adjusted to acidity, then adds in reactor
Add the organic silane compound of excess and stir；Third step, after the second step described above, adds alkalescence in reactor and urges
Agent, is changed into alkalescence by reactant liquor, implements condensation reaction；And purification step, removed as through the 3rd step by recrystallization
Cage modle (cage) structure of the by-product being suddenly individually created.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 3 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound is also condensed, and manufactures above-mentioned chemical formula 10；Second step, after above-mentioned first step, in order to by [D] d (OR5)2Structure is led
Enter in chemical formula 10, in reactor, add acidic catalyst, reactant liquor is adjusted to acidity, be then added with organic silane and close
Thing also stirs；Third step, after the second step described above, adds base catalyst in reactor, is changed into by reactant liquor
Alkalescence, implements condensation reaction；And the 4th step, after above-mentioned third step, in order to by [E] eX2Structure imports compound high score
The end of son, adds acidic catalyst in reactor, reactant liquor is changed into acidic atmosphere, is mixed with organic silane compound also
Stirring.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 4 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound also regulates condensation degree, manufactures above-mentioned chemical formula 10；Second step, after above-mentioned first step, in order to by [B] b structure
[D] d (OR7)2Structure imports chemical formula 10, adds acidic catalyst, reactant liquor is adjusted to acidity, then in reactor
It is added with organic silane compound and stirs；And third step, after the second step described above, in reactor, add base catalysis
Agent, is changed into alkalescence by reactant liquor, implements condensation reaction.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 5 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound is also condensed, and manufactures above-mentioned chemical formula 10；Second step, after above-mentioned first step, in order to by [B] b structure and [D] d
(OR8)2、[D]d(OR9)2Structure imports chemical formula 10, adds acidic catalyst, reactant liquor is adjusted to acidity in reactor,
Then add the organic silane compound of excess and stir；Third step, after the second step described above, adds in reactor
Base catalyst, is changed into alkalescence by reactant liquor, implements condensation reaction；And the 4th step, after the third step, by tying again
Crystalline substance and filter process, remove the cagelike structure being individually created.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 6 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound is also condensed, and manufactures above-mentioned chemical formula 10；Second step, after above-mentioned first step, in order to by [B] b structure and [D] d
(OR10)2Structure imports chemical formula 10, adds acidic catalyst, reactant liquor is adjusted to acidity, is then added with in reactor
Organic silane compound also stirs；Third step, after the second step described above, adds base catalyst in reactor, will be anti-
Answer liquid to be changed into alkalescence, implement condensation reaction；And the 4th step, after the third step, in order to by [E] eX2Structure imports multiple
Close high molecular end, in reactor, add acidic catalyst, reactant liquor is changed into acidic atmosphere, is mixed with organic silane
Compound also stirs.
Preferably, in the method manufacturing above-mentioned chemical formula 1 to 6, the pH of the reactant liquor of the first step of the present invention is preferred
Being 9 to 11.5, the pH of the reactant liquor of second step is preferably 2 to 4, and the pH of the reactant liquor of third step is preferably 8 to 11.5, leads
The pH of the reactant liquor entering the 4th step of Ee is preferably 1.5 to 4.In the case of being in above-mentioned scope, manufactured sesquialter
The yield of siloxanes composite high-molecular is high, and can improve the mechanical properties of manufactured silsesquioxane composite high-molecular.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 7 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound, manufactures the above-mentioned chemical formula 10 of the two kinds of forms that have adjusted condensation degree；Second step, in order to by [B] b structure and [D] d
(OR12)2Structure imports the chemical formula 10 obtained in above-mentioned first step, adds acidic catalyst, by reactant liquor in reactor
It is adjusted to acidity, is then added with organic silane compound and stirs；Third step, after above-mentioned each second step reacts, to
Reactor adds base catalyst, reactant liquor is changed into alkalescence, implement condensation reaction；And the 4th step, will be by above-mentioned
The two or more material that third step obtains is condensed in the basic conditions and connects.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 8 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound, manufactures the above-mentioned chemical formula 10 of the two kinds of forms that have adjusted condensation degree；Second step, in order to by [B] b structure, [D] d
(OR14)2Structure imports the chemical formula 10 obtained in above-mentioned first step, adds acidic catalyst, by reactant liquor in reactor
It is adjusted to acidity, is then added with organic silane compound and stirs；Third step, after above-mentioned each second step reacts, to
Reactor adds base catalyst, reactant liquor is changed into alkalescence, implement condensation reaction；4th step, will be by above-mentioned
The two or more material that three steps obtain is condensed in the basic conditions and connects；5th step, after above-mentioned 4th step,
Import [D] d (OR to being used for13)2Reactor in add acidic catalyst, reactant liquor is adjusted to acidity, then adds organic
Silane compound also stirs；And the 6th step, after above-mentioned 5th step, in reactor, add base catalyst, will be anti-
Answer liquid to be changed into alkalescence, implement condensation reaction.
The silsesquioxane composite high-molecular represented by above-mentioned chemical formula 9 of the present invention can be made as follows
Making, described step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, is added with organic silane
Compound, manufactures the above-mentioned chemical formula 10 of the two kinds of forms that have adjusted condensation degree；Second step, in order to import above-mentioned by [B] b structure
The chemical formula 10 obtained in first step, adds acidic catalyst in reactor, reactant liquor is adjusted to acidity, then adds
Organic silane compound also stirs；Third step, after above-mentioned each second step reacts, adds base catalysis in reactor
Agent, is changed into alkalescence by reactant liquor, implements condensation reaction；4th step, two or more by obtained by above-mentioned third step
Material be condensed in the basic conditions and connect；5th step, after above-mentioned 4th step, imports [D] d (OR to being used for5)2
Reactor in add acidic catalyst, reactant liquor is adjusted to acidity, is then added with organic silane compound and stirs；6th
Step, after above-mentioned 5th step, adds base catalyst in reactor, reactant liquor is changed into alkalescence, implement condensation
Reaction；And the 7th step, after above-mentioned 6th step, in order to by [E] eX2Structure imports the end of composite high-molecular, to instead
Answer input acidic catalyst in device, reactant liquor is changed into acidic atmosphere, is mixed with organic silane compound and stirs.
Preferably, in the high molecular method manufacturing above-mentioned chemical formula 7 to 9, the pH of the reactant liquor of first step is preferred
Being 9 to 11.5, the pH of the reactant liquor of second step is preferably 2 to 4, and the pH of the reactant liquor of third step is preferably 8 to 11.5, the
The pH of the reactant liquor of four steps is preferably 9 to 11.5, and the pH of the reactant liquor of the 5th step is preferably 2 to 4, the reaction of the 6th step
The pH of liquid is preferably 8 to 11.5, and the pH of the reactant liquor importing the 7th step of Ee is preferably 1.5 to 4.In being in above-mentioned scope
In the case of, the yield of manufactured silsesquioxane composite high-molecular is high, and can improve manufactured silsesquioxane
The mechanical properties of composite high-molecular.
Additionally, if desired, in order to further by [B] b structure and [D] d (OR)2Structure imports each composite high-molecular, permissible
[B] b repetitive is comprised further: in reactor, add acidic catalyst in making composite high-molecular as follows, will
Reactant liquor is adjusted to acidity, is then added with organic silane compound the step stirred；And after the above step, to reactor
Middle interpolation base catalyst, is changed into alkalescence by reactant liquor, implements the step of condensation reaction.
Additionally, if desired, in order to further by [E] eX2Structure imports the end of each composite high-molecular, can be by as follows
Step makes the repetitive that the end of composite high-molecular comprises [E] e further: put into acidic catalyst in reactor, will be anti-
Answer liquid to be changed into acidic atmosphere, be mixed with organic silane compound and stir.
In the manufacture method of above-mentioned silsesquioxane composite high-molecular, as base catalyst, be preferably used two kinds with
The mixed catalyst of upper base catalyst, causes hydrolyze it with acidic catalyst neutralization and acidification, again with two
Plant the mixed catalyst of above base catalyst, be condensed with alkalescence such that it is able to continuously adjust in a reactor
Acidity and basicity.
Now, above-mentioned base catalyst can be by two kinds in metal system base catalyst and amine system base catalyst
Above material is appropriately combined to be manufactured, and described metal system base catalyst selects the group of free Li, Na, K, Ca and Ba composition.Excellent
Choosing and state amine system base catalyst can be Tetramethylammonium hydroxide (TMAH), and metal system base catalyst can be potassium hydroxide
Or sodium bicarbonate (NaHCO (KOH)3).About the content of each composition in above-mentioned mixed catalyst, preferably can be in amine system alkalescence
Catalyst arbitrarily regulates in the ratio that ratio is 10 to 90:10 to 90 weight portion of metal system base catalyst.On being in
In the case of in the range of stating, it is possible to the reactivity in hydrolysis Shi Shi functional group with catalyst minimizes, and thus makes Si-OH or Si-
The combination of the organo-functional groups such as alkoxyl substantially reduces, and has the advantage being free to regulate condensation degree.Additionally, as above-mentioned
Acidic catalyst, as long as acidic materials usually used in this field just can unrestrictedly use, such as, can use
HCl、H2SO4、HNO3、CH3The general acidic materials such as COOH, additionally can use lactic acid, tartaric acid, maleic acid, citric acid etc.
Organic system acidic materials.
In the manufacture method of the silsesquioxane composite high-molecular of the present invention, as long as logical in above-mentioned organic solvent this area
The organic solvent often used just can unrestrictedly use, such as, can use methanol, ethanol, isopropanol, butanol, cellosolve system
In the di-alcoholss such as the ketones such as alcohols, lactate system, acetone, methyl (isobutyl group) ethyl ketone, ethylene glycol, oxolane etc. furan
System, dimethylformamide, dimethyl acetylamide, METHYLPYRROLIDONE polar solvent, and hexane, ring can be used
Hexane, Ketohexamethylene, toluene, dimethylbenzene, cresol, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane,
The various solvents such as acrylonitrile, dichloromethane, 18-amine., aniline, dimethyl sulfoxide, benzylalcohol.
Additionally, as above-mentioned organosilan based compound, it is possible to use the silsesquioxane as the present invention is combined high score
Son chemical formula 1 to 9 comprise R, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、
R19、R20、R21、R22Organosilan, preferably can use have by increase silsesquioxane composite high-molecular chemical resistance
Thus improve comprising phenyl or the organic silane compound of amino or having by increasing compound height of the effect of non-swelling property
The cured density of molecule thus improve the mechanical strength of cured layer and the effect of hardness comprise epoxy radicals or (methyl) acryloyl
The organic silane compound of base.
As the concrete example of above-mentioned organosilan based compound, (3-epoxypropoxy) trimethoxy silicon can be enumerated
Alkane, (3-epoxypropoxy) triethoxysilane, (3-epoxypropoxy) methyl dimethoxysilane, (3-epoxy the third oxygen
Propyl group) dimethylethoxysilane, 3-(methacryloxy) propyl trimethoxy silicane, 3,4-epoxy radicals butyl trimethoxy
Base silane, 3,4-epoxy radicals butyl triethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-
Epoxycyclohexyl) ethyl triethoxysilane, aminopropyltriethoxywerene werene, VTES, vinyl three
Tert-butoxy silane, vinyl three isobutoxy silane, vinyl silane triisopropoxide, vinyltriphenoxysilane, benzene
Ethyl triethoxy silicane alkane, phenyltrimethoxysila,e, TSL 8330, N-phenyl-3-aminopropyl trimethoxy
Base silane, dimethyl tetramethoxy silica alkane, diphenyl tetramethoxy silica alkane etc., can be used alone one therein or
And with two or more.The physical property of the compositions in order to finally manufacture, is preferably use mixing two or more.
In the present invention, import to the [(SiO of repetitive [D] d of above-mentioned chemical formula3/2R)4+2nO] n of structure can generation
Enter the integer of 1 to 20, preferably 3 to 10, the meansigma methods of more preferably n is 4 to 5, such as, when above-mentioned n is 4, the knot being substituted into
Being expressed as follows of structure is stated shown in chemical formula 11:
[chemical formula 11]
In above-mentioned formula, R is as defined above.
In the present invention, import to repetitive [B] b or the [(SiO of [E] e of above-mentioned chemical formula3/2R)4+2nR] n of structure
Can substitute into the integer of 1 to 20, preferably 3 to 10, the meansigma methods of more preferably n is 4 to 5, such as, when above-mentioned n is 4, by generation
Being expressed as follows of the structure entered is stated shown in chemical formula 12:
[chemical formula 12]
In above-mentioned formula, R is as defined above.
As concrete example, can be table 1 below to the macromolecule in 18 according to the silsesquioxane macromolecule of the present invention.Under
Stating in table 1 to 9, ECHE refers to that (epoxycyclohexyl) ethyl, GlyP refer to that epoxypropoxy, POMMA refer to (methacryl
Epoxide) propyl group, when recording two or more, it is meant that be used in mixed way.N is each independently 1 to 8.
The silsesquioxane composite high-molecular of above-mentioned chemical formula 1 can macromolecule described in table 1 below or 2.
[table 1]
| No | R1 | R2 | R16 | R19 | The R of Y |
| 1-1 | OH, methoxyl group | H, methyl | ECHE | ECHE | ECHE |
| 1-2 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | Phenyl |
| 1-3 | OH, methoxyl group | H, methyl | Methyl | Methyl | Methyl |
| 1-4 | OH, methoxyl group | H, methyl | GlyP | GlyP | GlyP |
| 1-5 | OH, methoxyl group | H, methyl | POMMA | POMMA | POMMA |
| 1-6 | OH, methoxyl group | H, methyl | ECHE | Phenyl | Phenyl |
| 1-7 | OH, methoxyl group | H, methyl | ECHE | Methyl | Methyl |
| 1-8 | OH, methoxyl group | H, methyl | ECHE | GlyP | GlyP |
| 1-9 | OH, methoxyl group | H, methyl | ECHE | POMMA | POMMA |
| 1-10 | OH, methoxyl group | H, methyl | Phenyl | ECHE | ECHE |
| 1-11 | OH, methoxyl group | H, methyl | Phenyl | Methyl | Methyl |
| 1-12 | OH, methoxyl group | H, methyl | Phenyl | GlyP | GlyP |
| 1-13 | OH, methoxyl group | H, methyl | Phenyl | POMMA | POMMA |
| 1-14 | OH, methoxyl group | H, methyl | Methyl | ECHE | ECHE |
| 1-15 | OH, methoxyl group | H, methyl | Methyl | Phenyl | Phenyl |
| 1-16 | OH, methoxyl group | H, methyl | Methyl | GlyP | GlyP |
| 1-17 | OH, methoxyl group | H, methyl | Methyl | POMMA | POMMA |
| 1-18 | OH, methoxyl group | H, methyl | GlyP | ECHE | ECHE |
| 1-19 | OH, methoxyl group | H, methyl | GlyP | Phenyl | Phenyl |
| 1-20 | OH, methoxyl group | H, methyl | GlyP | Methyl | Methyl |
| 1-21 | OH, methoxyl group | H, methyl | GlyP | POMMA | POMMA |
| 1-22 | OH, methoxyl group | H, methyl | POMMA | ECHE | ECHE |
| 1-23 | OH, methoxyl group | H, methyl | POMMA | Phenyl | Phenyl |
| 1-24 | OH, methoxyl group | H, methyl | POMMA | Methyl | Methyl |
| 1-25 | OH, methoxyl group | H, methyl | POMMA | GlyP | GlyP |
[table 2]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 2 can be described in Table 3 below and 4
Macromolecule.
[table 3]
| No | R3 | R4 | R16 | R19 | The R of Y |
| 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 |
[table 4]
| No | R3 | R4 | R16 | R19 | The R of Y |
| 4-1 | OH, methoxyl group | H, methyl | ECHE | Alkyl sulfide alcohol radical | ECHE |
| 4-2 | OH、CF3 | H, ethyl | Phenyl | Phenyl | Phenyl |
| 4-3 | OH, methoxyl group | H, acetyl group | Alkyl sulfide alcohol radical | Methyl | Methyl |
| 4-4 | CF3, methoxyl group | Vinyl, methyl | POMMA | Dodecyl | GlyP |
| 4-5 | OH, acryloyl group | H, methyl | POMMA | Alkyl sulfide alcohol radical | Octyl group |
| 4-6 | Vinyl, methoxyl group | H、F | ECHE | Phenyl | POMMA |
| 4-7 | Alkylamine | CF3, methyl | ECHE | Octyl group | Methyl |
| 4-8 | OH, ethyl, methyl | H, methyl | F | Aminopropyl | GlyP |
| 4-9 | Acetate, methoxyl group | H、CF3 | Aminopropyl | POMMA | Hexyl |
| 4-10 | Propoxyl group, methoxyl group | H, methyl | Phenyl | Alkyl sulfide alcohol radical | ECHE |
| 4-11 | OH、C8F13 | Aryl, methyl | Alkyl sulfide alcohol radical | Methyl | Hexyl |
| 4-12 | OH, methoxyl group | H, methylacryloyl | Phenyl | GlyP | GlyP |
| 4-13 | CF3, methoxyl group | H, methyl | Octyl group | POMMA | POMMA |
| 4-14 | OH, acryloyl group | H, octyl group | Methyl | ECHE | Aminopropyl |
| 4-15 | Vinyl, methoxyl group | H, methyl | Octyl group | Alkyl sulfide alcohol radical | Phenyl |
| 4-16 | Alkylamine | H, methyl | Octyl group | GlyP | GlyP |
| 4-17 | OH, methoxyl group | Alkyl sulfide alcohol radical, methyl | Methyl | POMMA | POMMA |
| 4-18 | Acetate, methoxyl group | H, methyl | GlyP | ECHE | Aminopropyl |
| 4-19 | Propoxyl group, methoxyl group | H、CF3 | GlyP | Aminopropyl | Phenyl |
| 4-20 | OH, methoxyl group | H, methyl | Aminopropyl | Methyl | Octyl group |
| 4-21 | Propoxyl group, methoxyl group | C8F13, methyl | GlyP | POMMA | POMMA |
| 4-22 | OH, methoxyl group | H, propyl group | POMMA | Propyl group | ECHE |
| 4-23 | C8F13, methoxyl group | F, methyl | POMMA | Phenyl | Phenyl |
| 4-24 | OH, aryl | H, methyl | GlyP | Methyl | GlyP |
| 4-25 | OH, methoxyl group | H, ethyl | Aminopropyl | GlyP | GlyP |
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 3 can be described in table 5 below and 6
Macromolecule.
[table 5]
| No | R5 | R16 | R19 | R20 | The R of Y | The R of X |
| 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 |
[table 6]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 4 can be described in table 7 below and 8
Macromolecule.
[table 7]
| No | R6 | R7 | R16 | R17 | R18 | R19 | The R of X | The R of Y |
| 7-1 | OH, methoxyl group | H, methyl | ECHE | ECHE | H, methyl | ECHE | ECHE | ECHE |
| 7-2 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | H, methyl | Phenyl | Phenyl | Phenyl |
| 7-3 | OH, methoxyl group | H, methyl | Methyl | Methyl | H, methyl | Methyl | Methyl | Methyl |
| 7-4 | OH, methoxyl group | H, methyl | GlyP | GlyP | H, methyl | GlyP | GlyP | GlyP |
| 7-5 | OH, methoxyl group | H, methyl | POMMA | POMMA | H, methyl | POMMA | POMMA | POMMA |
| 7-6 | OH, methoxyl group | H, methyl | ECHE | ECHE | H, methyl | Phenyl | ECHE | Phenyl |
| 7-7 | OH, methoxyl group | H, methyl | ECHE | ECHE | H, methyl | Methyl | ECHE | Methyl |
| 7-8 | OH, methoxyl group | H, methyl | ECHE | ECHE | H, methyl | GlyP | ECHE | GlyP |
| 7-9 | OH, methoxyl group | H, methyl | ECHE | ECHE | H, methyl | POMMA | ECHE | POMMA |
| 7-10 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | H, methyl | ECHE | Phenyl | ECHE |
| 7-11 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | H, methyl | Methyl | Phenyl | Methyl |
| 7-12 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | H, methyl | GlyP | Phenyl | GlyP |
| 7-13 | OH, methoxyl group | H, methyl | Phenyl | Phenyl | H, methyl | POMMA | Phenyl | POMMA |
| 7-14 | OH, methoxyl group | H, methyl | Methyl | Methyl | H, methyl | ECHE | Methyl | ECHE |
| 7-15 | OH, methoxyl group | H, methyl | Methyl | Methyl | H, methyl | Phenyl | Methyl | Phenyl |
| 7-16 | OH, methoxyl group | H, methyl | Methyl | Methyl | H, methyl | GlyP | Methyl | GlyP |
| 7-17 | OH, methoxyl group | H, methyl | Methyl | Methyl | H, methyl | POMMA | Methyl | POMMA |
| 7-18 | OH, methoxyl group | H, methyl | GlyP | GlyP | H, methyl | ECHE | GlyP | ECHE |
| 7-19 | OH, methoxyl group | H, methyl | GlyP | GlyP | H, methyl | Phenyl | GlyP | Phenyl |
| 7-20 | OH, methoxyl group | H, methyl | GlyP | GlyP | H, methyl | Methyl | GlyP | Methyl |
| 7-21 | OH, methoxyl group | H, methyl | GlyP | GlyP | H, methyl | POMMA | GlyP | POMMA |
| 7-22 | OH, methoxyl group | H, methyl | POMMA | POMMA | H, methyl | ECHE | POMMA | ECHE |
| 7-23 | OH, methoxyl group | H, methyl | POMMA | POMMA | H, methyl | Phenyl | POMMA | Phenyl |
| 7-24 | OH, methoxyl group | H, methyl | POMMA | POMMA | H, methyl | Methyl | POMMA | Methyl |
| 7-25 | OH, methoxyl group | H, methyl | POMMA | POMMA | H, methyl | GlyP | POMMA | GlyP |
[table 8]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 5 can be described in table 9 below and 10
Macromolecule.
[table 9]
| No | R8 | R9 | R16 | R17 | R18 | R19 | The R of X | The R of Y |
| 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 |
[table 10]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 6 can be described in table 1 below 1 and 12
Macromolecule.
[table 11]
[table 12]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 7 can be described in table 1 below 3 and 14
Macromolecule.
[table 13]
[table 14]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 8 can be described in table 1 below 5 and 16
Macromolecule.
[table 15]
| No | R13 | R14 | R16 | R17 | R18 | R19 | The R of X | The R of Y |
| 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 |
[table 16]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 9 can be described in table 1 below 7 and 18
Macromolecule.
[table 17]
| No | R16 | R17 | R18 | R19 | R20 | The R of X | The R of Y | The end 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 |
[table 18]
About the above-mentioned silsesquioxane composite high-molecular of the present invention, obtain wide in order to ensure excellent keeping stability
General application, can be adjusted to 1 to 99.9% by condensation degree.I.e., it is possible to be adjusted to be incorporated into the alkane of the Si of end and central authorities
The content of epoxide is 50% to 0.01% relative to whole high molecular conjugated groups.
Additionally, in the present invention, the weight average molecular weight of silsesquioxane composite high-molecular can be 1,000 to 1,000,000,
It is preferably 5,000 to 100,000, more preferably 7,000 to 50,000.In the case of Gai, it is possible to improve silsesquioxane simultaneously
Processability and physical characteristic.
In above-mentioned chemical formula 1 to 9, any one represented silsesquioxane composite high-molecular has the glass of 50 to 250 DEG C
Changing transition temperature (Tg), the content of repetitive [A] a is the most, and Tg is the lowest, and the content of repetitive [B] b, [D] d and [E] e is more
Many, Tg is the highest, therefore can regulate the content of repetitive aptly according to the purposes used and have Tg.
The thermoplastic resin composition of the present invention can be only by the silsesquioxane that in above-mentioned chemical formula 1 to 9, any one is represented
Alkane composite high-molecular is constituted, it is possible to mixes with the macromolecule used in conventional thermoplastic resin composition and uses.As upper
State the macromolecule that can be used in mixed way, be not particularly limited, such as, the free PC of choosing (Merlon), PMMA (poly-methyl-prop can be used
E pioic acid methyl ester), PES (polyether sulfone), PET (polyethylene terephthalate), PEN (PEN), COC
(cyclic olefine copolymer), PAc (polyacrylate), PE (polyethylene), PEEK (polyether-ether-ketone), PEI (Polyetherimide), PI
(polyimides), PSF (polysulfones), PVA (polyvinyl alcohol), PVCi (polyvinyl cinnamate), TAC (triacetyl cellulose),
In the group that polysilicon (Poly Silicone), polyurethane (Polyurethane) and epoxy resin (Epoxy Resin) form
More than one macromolecule resins.Above-mentioned when being used in mixed way in chemical formula 1 to 9 any one represented silsesquioxane be combined high score
The content of son arbitrarily can select and use in 0.1 to 99 weight %, it is preferable that in the case of using more than 1 weight %, can
The physical property such as the further chemical resistance improving thermoplastic resin.
Additionally, the thermoplastic resin composition of the present invention also can be with the silsesquioxane that in chemical formula 1 to 9, any one is represented
Alkane composite high-molecular is together used in mixed way the inorfil such as glass fibre or carbon fiber.Above-mentioned when being used in mixed way in chemical formula 1 to 9
The content of any one represented silsesquioxane composite high-molecular arbitrarily can select and use, preferably in 1 to 90 weight %
Ground, in the case of using more than 5 weight %, can further improve the physical property such as water proofing property of thermoplastic resin.
In the thermoplastic resin composition of the present invention, multiple for the silsesquioxane that in chemical formula 1 to 9, any one is represented
Close high molecular functional group i.e. R, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、
R20、R21、R22, by selecting the macromolecule resin or the inorfil that use and be used in mixed way in silsesquioxane composite high-molecular
The functional group of excellent compatibility such that it is able to improve the stability of thermoplastic resin, it is possible to the most persistently keep anti-flammability, prevent
The physical property such as aqueous, soil resistance, the transparency.
Additionally, above-mentioned resin combination can further include pigment.Any one institute in the above-mentioned chemical formula 1 to 9 of the present invention
The silsesquioxane composite high-molecular represented improves the dispersibility of pigment, and the excellent compatibility of pigment, in thermoplastic resin group
In the case of compound comprises pigment, it is possible to there is the coloring effect of excellence.Above-mentioned pigment can use known pigment undoubtedly, about
The content of pigment, those skilled in the art can select to use in suitable scope.
In the present invention, above-mentioned thermoplastic resin composition can further include increasing usually used in this field as required
Mould agent, ultraviolet screening agent, UV absorbent, antioxidant, defoamer, levelling agent, water repellent, fire retardant, bonding improving agent,
The additives such as other functional additives improve physical property.Such additive is not particularly limited in use, can not damage
Suitably adding in the range of the physical property of evil thermoplastic resin, as concrete example, above-mentioned additive is relative to composition total weight 100
Weight portion can comprise 0.01-10 weight portion independently of one another.
As additive spendable in the present invention, polyether-modified dimethyl polysiloxane system can be enumerated
(Polyether-modified polydimethylsiloxane, such as, BYK-300, BYK-301, BYK-of BYK company
302、BYK-331、BYK-335、BYK-306、BYK-330、BYK-341、BYK-344、BYK-307、BYK-333、BYK-310
Deng), polyether-modified hydroxy-functional polydimethylsiloxanes system (Polyether modified hydroxyfunctional
Poly-dimethyl-siloxane, such as, BYK-308, BYK-373 etc.), methylalkylpolysiloxanes system
(Methylalkylpolysiloxane, such as, BYK-077, BYK-085 etc.), polyether-modified methylalkylpolysiloxanes system
(Polyether modified methylalkylpolysiloxane, such as, BYK-320, BYK-325 etc.), polyester modification
Methylalkylpolysiloxanes system (Polyester modified poly-methyl-alkyl-siloxane, such as, BYK-315
Deng), aralkyl modified methylalkylpolysiloxanes system (Aralkyl modified methylalkyl polysiloxane, example
As, BYK-322, BYK-323 etc.), polyester modification hydroxy-functional polydimethylsiloxanes system (Polyester modified
Hydroxy functional polydimethylsiloxane, such as, BYK-370 etc.), polyester modification acrylic acid official can gather
Dimethyl silica methane series (Acrylic functional polyester modified polydimethylsiloxane, example
Such as, BYK-371, BYK-UV 3570 etc.), polyether-polyester modified hydroxyl functional polydimethylsiloxanes system (Polyeher-
Polyester modified hydroxy functional polydimethylsiloxane, such as, BYK-375 etc.), poly-
Ether modified dimethyl polysiloxane system (Polyether modified dimethylpolysiloxane, such as, BYK-345,
BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337 etc.), nonionic acrylic copolymerization system (Non-
Ionic acrylic copolymer, such as, BYK-380 etc.), ionic acrylic copolymerization system (Ionic acrylic
Copolymer, such as, BYK-381 etc.), polyacrylate system (Polyacrylate, such as, BYK-353, BYK-356, BYK-
354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 etc.), polymethacrylates system
(Polymethacrylate, such as, BYK-390 etc.), polyether-modified acrylic acid functional polydimethylsiloxanes system
(Polyether modified acryl functional polydimethylsiloxane, such as, BYK-UV3500,
BYK-UV3530 etc.), polyether modified siloxane system (Polyether modified siloxane, such as, BYK-347 etc.), alcohol
Alkoxylate system (Alcohol alkoxylates, such as, BYK-DYNWET 800 etc.), acrylic ester (Acrylate,
Such as, BYK-392 etc.), hydroxyl-functional silicone-modified polyacrylate system (Silicone modified polyacrylate
(OH-functional), such as, BYK-Silclean 3700 etc.) etc..
Additionally, the present invention provides the article using above-mentioned thermoplastic resin composition to manufacture, as long as above-mentioned article use
State thermoplastic resin composition's manufacture to be just not particularly limited, it may for example comprise film, the article shaped by injection or extruded, foaming
Thing, cellosilk.About manufacturing above-mentioned film, article shaped, foamed or filametntary method, may utilize the heat of the invention described above undoubtedly
Thermoplastic resin composition also utilizes each manufacture film known, article shaped, foamed or filametntary operation to manufacture.As upper
State the concrete example of article, the cover including the shell of various electronic products can be enumerated, plastic living including ornaments is used
Product, illumination, head protector, automobile interior exterior ornament materials, fishing rod, golf clubs, yacht, Discussion on architecture ornament materials, pipe arrangement, family
Tool, film, functional fiber, functional garment etc..
Hereinafter, in order to contribute to the understanding of the present invention, it is provided that preferred embodiment, but following embodiment simply illustrates this
Invention, the scope of the present invention is not limited to following embodiment.In following embodiments of the invention, ECHETMS refers to 2-(3,4-rings
Oxygen cyclohexyl) ethyl trimethoxy silane, GPTMS refers to that glycidoxypropyltrime,hoxysilane, MAPTMS refer to (methyl
Acryloyl-oxy) propyl trimethoxy silicane, PTMS refers to that phenyltrimethoxysila,e, MTMS refer to MTMS,
ECHETMDS refers to two (epoxycyclohexylethyl) tetramethoxy disiloxane, and GPTMDS refers to two (glycidoxypropyl group) four
Methoxyl group disiloxane, MAPTMDS refers to two (methacryloxy) propyl group tetramethoxy disiloxane, and PTMDS refers to two
(phenyl) tetramethoxy disiloxane, MTMDS refers to two (methyl) tetramethoxy disiloxane.
[embodiment 1] comprises the manufacture of coating composition of copolymer 1 and 9
About synthesis step, carry out continuous hydrolysis and condensation by step as follows.
The manufacture of [embodiment 1-a] catalyst
In order to regulate basicity, in Tetramethylammonium hydroxide (TMAH) 25 weight % aqueous solution, mix 10 weight % hydroxides
Potassium (KOH) aqueous solution and prepare catalyst 1a.
The synthesis of [embodiment 1-b] line style silsesquioxane alkyl structure
In possessing the dry flask of condensing tube and agitator, dropping distilled water 5 weight portion, oxolane 15 weight portion,
Catalyst 1 weight portion manufactured in above-described embodiment 1-a, after stirring at normal temperature 1 hour, drips 2-(3,4-epoxycyclohexyl) second
Base trimethoxy silane 20 weight portion, dropping oxolane 15 weight portion further stirring 5 hours again.Take in stirring
Mixed solution, after being removed catalyst and impurity by twice cleaning and filtering, is analyzed by IR and can confirm that at end group
SI-OH functional group (the 3200cm generated-1), measure the result of molecular weight, can confirm that line style knot as chemical formula 4 structure
The silsesquioxane of structure has 8,000 styrene conversion molecular weight.
Continuously generating of [embodiment 1-c] cagelike structure
In above-described embodiment 1-b mixed solution, very slowly drip HCl/water solution 5 weight portion of 0.36 weight %,
Being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, disposable addition diphenyl tetramethoxy two silica
Alkane 5 weight portion, it is achieved stable hydrolysis, after stirring 1 hour, adds catalyst 7 weight portion manufactured in embodiment 1-a again,
It is alkaline state by the pH regulator of mixed solution.Now, the D structure that alkoxyl opens independently is formed with linear macromolecule
Precursor.Gather a small amount of sample, be analyzed by H-NMR and IR, after confirming the survival rate of methoxyl group, when survival rate is 20%
Time, it is slowly added dropwise HCl/water solution 10 weight portion of 0.36 weight %, is acid by pH regulator.Afterwards, disposable addition phenyl three
Methoxy silane 1 weight portion also stirs 15 minutes, then adds catalyst 20 weight portion manufactured in 1-a.The mixing of 4 hours
The result confirmed after stirring, can confirm that the macromolecule generating cage modle in macromolecule.Afterwards, temperature is made to become room temperature, logical
Cross vacuum and remove the oxolane in mixed solution, make the whole be changed into water solution mixture.Mixing at 4 hours is stirred
After mixing, take a part, pass through29The result that Si-NMR is analyzed, can confirm that the analysis of the structure utilizing phenyl to import
Peak demonstrates two sharp-pointed forms, has manufactured A-D as more than 50% chemical formula 1 with not having other remaining by-products high
Molecule.Additionally, the meansigma methods that styrene conversion molecular weight is 11,000, n measured is 4.6.29Si-NMR(CDCl3)δ
[embodiment 1-D]
With relatively under the molten condition of raw material fragment polyethylene terephthalate (Di Ren company, TR-8550T1)
It is that 10 weight % coordinate the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C in gross weight, manufactures poly-to benzene two
Formic acid glycol ester is combined fragment.
[embodiment 1-E]
Raw material fragment Merlon (Di Ren company,) molten condition under being 5 weights relative to gross weight
Amount % coordinates the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C, manufactures Merlon and is combined fragment.
[embodiment 1-F]
Raw material fragment PEN (Di Ren company,TN8065S) under molten condition with
It is that 5 weight % coordinate the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C relative to gross weight, manufactures poly-naphthalene two
Formic acid glycol ester is combined fragment.
Additionally, use the monomer described in table 1 below 9, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 1-b, 1-c, 1-d, 1-e and 1-f.
[table 19]
Embodiment 2:The high molecular synthesis of silsesquioxane D-A-D structure composite
In order to manufacture the composite high-molecular of D-A-D structure, use following embodiment, utilize and described in above-described embodiment 1
Method equity method, manufactured compound fragment.About catalyst and the manufacture of linear structure, employ and embodiment 1-a
The method identical with the method for 1-b, afterwards, in order to continuously generate D-A-D structure, utilizes following method to manufacture.
The generation of the continuous print cagelike structure of [embodiment 2-a] excess
In above-described embodiment 1-b mixed solution, very slowly drip HCl/water solution 5 weight portion of 0.36 weight %,
Being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, the 5 of the disposable usage amount adding embodiment 1-b
The most i.e. 25 weight portion diphenyl tetramethoxy disiloxane, it is achieved stable hydrolysis, after stirring 1 hour, add embodiment again
Catalyst 7 weight portion manufactured in 1-a, is alkaline state by the pH regulator of mixed solution.Now, with linear macromolecule independently
Form the precursor of the D structure that alkoxyl opens.Gather a small amount of sample, be analyzed by H-NMR and IR, confirm methoxyl group
Survival rate after, when survival rate is 20%, is slowly added dropwise HCl/water solution 10 weight portion of 0.36 weight %, by pH regulator is
Acid.Afterwards, disposable addition phenyltrimethoxysila,e 1 weight portion also stirs 15 minutes, and then manufacture in interpolation 1-a urges
Agent 20 weight portion.The result confirmed after the mix and blend of 4 hours, can confirm that the high score generating cage modle in macromolecule
Son.Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum, make the whole be changed into water
Solution mixture.After the mix and blend of 4 hours, take a part, pass through29The result that Si-NMR is analyzed, can confirm that
Peak of analyzing to the structure utilizing phenyl to import demonstrates two sharp-pointed forms, does not manufactures with having other remaining by-products
A-D macromolecule as chemical formula 1.Additionally, the styrene conversion molecular weight measured is 14,000, n value is 4.6.Additionally, by
Si-NMR analyzes and can confirm that, different from A-D structure, and the peak near the visible-68ppm of end of A structure disappears, A structure
End be completely reformed into D structure and generate D-A-D structure.29Si-NMR(CDCl3) δ-72.3 (wide) ,-81.1 (sharp) ,-
80.8 (sharp) ,-82.5 (wide)
Additionally, use the monomer described in table 2 below 0, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 2.
[table 20]
Embodiment 3: the high molecular synthesis of silsesquioxane E-A-D structure composite
In order to manufacture the composite high-molecular of E-A-D structure, use following embodiment, utilize and described in above-described embodiment 1
Method equity method, manufactured compound fragment.About catalyst and the manufacture of linear structure, employ and embodiment 1
The method that method is identical, afterwards, in order to generate E-A-D structure, utilizes following method to manufacture.
The generation of [embodiment 3-a] chain end E structure
The A-D mixture obtained in not having extra refined embodiment 1-c drips dichloromethane 20 weight portion, drips
Adding HCl/water solution 5 weight portion of 0.36 weight %, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards,
Disposable addition dimethyl tetramethoxy-silicane 1 weight portion.Now, the part being the most not yet hydrolyzed and exist exists
The acidic aqueous solution layer separated with solvent is easily changed into hydrolysate, with the other reactant generated in organic solvent layer
It is condensed and imports E in terminal units.After the stirring of 5 hours, the stirring of stopped reaction, the temperature of reactor is adjusted to often
Temperature.
[embodiment 3-b] imports cagelike structure in end E structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 3-a refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.In just carrying out the embodiment 3-a mixed solution reacted, disposably add methyl trimethoxy
TMOS 3 weight portion, it is achieved stable hydrolysis, after stirring 24 hours, adds the catalyst 3 manufactured in embodiment 1-a again
Weight portion, is alkaline state by the pH regulator of mixed solution.Now, the macromolecule of cage modle can be imported at E structure end, in reaction
Device reacts continuously, forms macromolecule as chemical formula 3.But, owing to obtaining together with other by-products, therefore
Need extra refining.Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare essence
System.
[embodiment 3-c] is removed by the by-product of precipitation and recrystallization, the acquirement of product
After reacting the mixture of end in obtaining above-described embodiment 3-b, utilize distilled water wash, as the pH of distillation water layer
During in neutrality, removed solvent completely by vacuum decompression.Afterwards, precipitate 2 times in methanol, remove unreacted monomer, at tetrahydrochysene
Protect at a temperature of-20 DEG C after the solvent that furan and aqueous solution mix with 9.5:0.5 weight ratio dissolves with 30 weight portions
Pipe 2 days.This is the material recrystallization closed by cagelike structure to make not import to macromolecule, thus easily realizes refined.
The solid matter obtained after completing recrystallization process filters, and confirms after vacuum decompression together with multiple by-product
Obtain the macromolecule of chemical formula 3.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight is calculated as 17 with styrene scaled value, and 000, n value is 4-66, and the especially result of chemical formula 3 is as follows.
29Si-NMR(CDCl3) δ-68.2 ,-71.8 (sharp) ,-72.3 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-82.5
(wide)
Additionally, use the monomer described in table 2 below 1, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 3.
[table 21]
Embodiment 4: the high molecular synthesis of A-B-D structure composite silsesquioxane
About synthesis step, carry out continuous hydrolysis and condensation by step as follows, manufacture the composite high-molecular of E-A-D structure,
Utilize the method corresponding with the method described in above-described embodiment 1, manufacture compound fragment.
[embodiment 4-a] is for hydrolysis and the manufacture of the catalyst of condensation reaction
In order to regulate basicity, in Tetramethylammonium hydroxide (TMAH) 25 weight % aqueous solution, mix 10 weight % hydroxides
Potassium (KOH) aqueous solution and prepare catalyst 1a.
The synthesis (synthesis of A-B precursor) of [embodiment 4-b] line style silsesquioxane alkyl structure
In possessing the dry flask of condensing tube and agitator, dropping distilled water 5 weight portion, oxolane 40 weight portion,
Catalyst 0.5 weight portion manufactured in above-described embodiment 4-a, after stirring at normal temperature 1 hour, dropping 2-(3,4-epoxycyclohexyl)
Ethyl trimethoxy silane 10 weight portion, dropping oxolane 20 weight portion further stirring 2 hours again.Take in stirring
Mixed solution, removed by twice cleaning catalyst and impurity and filter after, it is thus achieved that pass through1H-NMR analyzes the alkane of remaining
Epoxide is the line style silsesquioxane of below 0.1mmol/g, and this is later by sharp during successive reaction importing cagelike structure
Part.About the morphological analysis of linear structure, by XRD analysis, confirming overall structure is linear structure.Measure and divide
The result of son amount, can confirm that the silsesquioxane of linear structure has 6,000 styrene conversion molecular weight.
1H-NMR(CDCl3) δ 3.7,3.4,3.3 (wide), 3.1,2.8,2.6,1.5 (wide), 0.6.
[embodiment 4-c] is for generating the pH reacting condition (importing of B, D structure) of cagelike structure in chain
In just carrying out the embodiment 4-b mixed solution reacted, very slowly drip the aqueous solution 5 of 0.36wt%HCl
Weight portion, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, disposable addition diphenyl tetramethoxy
Disiloxane 5 weight portion, after stirring 1 hour, adds catalyst 5 weight portion manufactured in embodiment 4-a, again by mixed solution
PH regulator be alkaline state.Now, can confirm that and independently generate the structure of cage modle with linear structure and import to height
Strand, makes temperature become room temperature, removes the oxolane in mixed solution by vacuum, makes the whole be changed into water-soluble
Liquid mixture.After the mix and blend of 4 hours, take a part, pass through29Si-NMR and1The result that H-NMR is analyzed,
Can confirm that the quantitative change of alkoxyl is 0.025mmol/g present in the B structure, is imported with the repetition list of B Yu D with 5:5 ratio
Unit.Additionally, the styrene conversion molecular weight measured is 10,000.Even if additionally, imported cagelike structure, at high molecular GPC
Form can not be seen the molecular weight distribution of single cage modle material, therefore can confirm that cagelike structure passes through successive reaction good
Import to macromolecular chain.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (wide), 3.1,2.8,2.6,1.5 (wide), 0.6.29Si-NMR
(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-82.5 (wide)
[embodiment 4-d] imports X (importing of B, D structure) in B structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 4-c refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.Material 100 weight portion obtained in embodiment 4-c is dissolved in the tetrahydrochysene of 50 weight portions
Furan, is subsequently adding the distilled water of 5 weight portions and manufactures mixed solution.Afterwards, add in manufactured mixed solution
HCl 10 weight portion of 0.36wt% also stirs 10 minutes, the most disposably adds MTMS 3 weight portion, it is achieved
Stable hydrolysis.After stirring 24 hours, again add catalyst 3 weight portion manufactured in embodiment 4-a, by the pH of mixed solution
It is adjusted to alkaline state.Now, the macromolecule of cage modle can import to the X section of B structure, carries out anti-the most continuously
Should, form macromolecule as chemical formula 4.But, owing to obtaining together with other by-products, it is therefore desirable to extra is refined.
Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare to refine.
[embodiment 4-e] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 4-d reacts in the mixture of end, add dichloromethane 200 weight portion, with distilled water one
Play classification washing, when the pH distilling water layer is neutrality, removed solvent completely by vacuum decompression.Afterwards, in methanol, precipitate 2
Secondary, remove unreacted monomer, with 30 weight portions in the solvent that oxolane and aqueous solution mix with 9.5:0.5 weight ratio
Take care of 2 days at a temperature of-20 DEG C after dissolving.This be the material closed by cagelike structure to make not import to macromolecule again
Crystallization, thus easily realize refined.
The solid matter obtained after completing recrystallization process filters, and confirms and do not have multiple by-product ground after vacuum decompression
Obtain the macromolecule of chemical formula 4.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight can in terms of styrene scaled value the value of acquisition 12,000, the n value that n value is 4-6, Y of X is 4-6, especially
The result of chemical formula 4 is as follows.
29Si-NMR(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-81.5 (sharp) ,-
82.5 (wide)
Additionally, use the monomer described in table 2 below 2, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 4.
[table 22]
Embodiment 5: the high molecular synthesis of D-A-B-D structure composite silsesquioxane
In order to manufacture the composite high-molecular of D-A-B-D structure, utilize following method, and by reciprocity with above-described embodiment 1
Method, manufactured compound fragment.
[embodiment 5-a] is for generating the pH reacting condition (importing of B, D structure) of the D structure of excess
In just carrying out the embodiment 4-b mixed solution reacted, very slowly drip the HCl/water solution 5 of 0.36wt%
Weight portion, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, the amount of 5 times of embodiment 4-b is prepared i.e.
The diphenyl tetramethoxy disiloxane of 25 weight portions, and it is disposably added, after stirring 1 hour, again add embodiment
Catalyst 5 weight portion manufactured in 1-a, is alkaline state by the pH regulator of mixed solution.After reaction terminates, temperature is made to become normal
Temperature, removes the oxolane in mixed solution by vacuum, makes the whole be changed into water solution mixture.At 4 hours
After mix and blend, take a part, pass through29Si-NMR and1The result that H-NMR is analyzed, can confirm that and deposit in B structure
The quantitative change of alkoxyl be 0.012mmol/g, be imported with the repetitive of B Yu D with about 1:9 ratio.Additionally, the benzene second measured
Alkene conversion molecular weight is 24,000.Even if additionally, imported cagelike structure, list can not be seen in high molecular GPC form
The molecular weight distribution of only cage modle material, therefore can confirm that cagelike structure is passed through successive reaction and imported to macromolecular chain well.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (wide), 3.1,2.8,2.6,1.5 (wide), 0.6.29Si-NMR
(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-82.5 (wide)
[embodiment 5-b] imports X (importing of B, D structure) in B structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 5-a refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.Material 100 weight portion obtained in embodiment 5-a is dissolved in the tetrahydrochysene of 50 weight portions
Furan, is subsequently adding the distilled water of 5 weight portions and manufactures mixed solution.Afterwards, add in manufactured mixed solution
HCl 10 weight portion of 0.36wt% also stirs 10 minutes, the most disposably adds MTMS 3 weight portion, it is achieved
Stable hydrolysis.After stirring 24 hours, again add catalyst 3 weight portion manufactured in embodiment 4-a, by the pH of mixed solution
It is adjusted to alkaline state.Now, the macromolecule of cage modle can import to the X section of B structure, carries out anti-the most continuously
Should, form macromolecule as chemical formula 5.But, owing to obtaining together with other by-products, it is therefore desirable to extra is refined.
Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare to refine.
[embodiment 5-c] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 5-b reacts in the mixture of end, add dichloromethane 200 weight portion, with distilled water one
Play classification washing, when the pH distilling water layer is neutrality, removed solvent completely by vacuum decompression.Afterwards, in methanol, precipitate 2
Secondary, remove unreacted monomer, with 30 weight portions in the solvent that oxolane and aqueous solution mix with 9.5:0.5 weight ratio
Take care of 2 days at a temperature of-20 DEG C after dissolving.This be the material closed by cagelike structure to make not import to macromolecule again
Crystallization, thus easily realize refined.
The solid matter obtained after completing recrystallization process filters, and confirms and do not have multiple by-product ground after vacuum decompression
Obtain the macromolecule of chemical formula 5.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight can in terms of styrene scaled value the value of acquisition 16,000, the n value that n value is 4-6, Y of X is 4-6, especially
The result of chemical formula 5 is as follows.
29Si-NMR(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-81.5 (sharp) ,-
82.5 (wide)
Additionally, use the monomer described in table 2 below 3, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 5.
[table 23]
Embodiment 6: the high molecular synthesis of silsesquioxane E-A-B-D structure composite
In order to manufacture the composite high-molecular of E-A-B-D structure, utilize following method, and by reciprocity with above-described embodiment 1
Method, manufactured compound fragment.
The generation of [embodiment 6-a] chain end E structure
The mixture obtained in not having extra refined embodiment 4-c drips dichloromethane 20 weight portion, dropping
HCl/water solution 5 weight portion of 0.36 weight %, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, one
Secondary property adds dimethyl tetramethoxy-silicane 1 weight portion.Now, the part being the most not yet hydrolyzed and exist with
The acidic aqueous solution layer that solvent separates easily is changed into hydrolysate, contracts in organic solvent layer with the other reactant generated
Close and import E in terminal units.After the stirring of 5 hours, the stirring of stopped reaction, the temperature of reactor is adjusted to room temperature.
[embodiment 6-b] imports cagelike structure in the X of B structure and end E structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 6-a refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.In just carrying out the embodiment 6-a mixed solution reacted, disposably add methyl trimethoxy
TMOS 3 weight portion, it is achieved stable hydrolysis, after stirring 24 hours, adds the catalyst 3 manufactured in embodiment 1-a again
Weight portion, is alkaline state by the pH regulator of mixed solution.Now, the macromolecule of cage modle can be imported at E structure end, in reaction
Device reacts continuously, forms macromolecule as chemical formula 6.But, owing to obtaining together with other by-products, therefore
Need extra refining.Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare essence
System.
[embodiment 6-c] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 6-b obtains reaction terminate mixture after, utilize distilled water wash, when distillation water layer pH in
Time neutral, removed solvent completely by vacuum decompression.Afterwards, precipitate 2 times in methanol, remove unreacted monomer, at tetrahydrochysene furan
Mutter keeping 2 at a temperature of-20 DEG C after dissolving with 30 weight portions in the solvent mixed with 9.5:0.5 weight ratio with aqueous solution
My god.This is the material recrystallization closed by cagelike structure to make not import to macromolecule, thus easily realizes refined.
The solid matter obtained after completing recrystallization process filters, and confirms after vacuum decompression together with multiple by-product
Obtain the macromolecule of chemical formula 6.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight obtains 21 in terms of styrene scaled value, the value of 000, and the n value that n value is 4-6, Y of X is 4-6, especially chemistry
The result of formula 6 is as follows.
29Si-NMR(CDCl3) δ-68.2 ,-71.8 (sharp) ,-72.3 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-82.5
(wide)
Additionally, use the monomer described in table 2 below 4, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 6.
[table 24]
Embodiment 7: the high molecular synthesis of silsesquioxane A-B-A-D structure composite
About synthesis step, carry out continuous hydrolysis and condensation by step as follows, utilize identical with the method for above-described embodiment 1
Method, has manufactured compound fragment.
The manufacture of [embodiment 7-a] catalyst
In order to regulate basicity, in Tetramethylammonium hydroxide (TMAH) 25 weight % aqueous solution, mix 10 weight % hydroxides
Potassium (KOH) aqueous solution and prepare catalyst 1a.
[embodiment 7-b] line style silsesquioxane synthesis (A precursor)
In possessing the dry flask of condensing tube and agitator, dropping distilled water 5 weight portion, oxolane 15 weight portion,
Catalyst 1 weight portion manufactured in above-described embodiment 7-a, after stirring at normal temperature 1 hour, drips 2-(3,4-epoxycyclohexyl) second
Base trimethoxy silane 20 weight portion, dropping oxolane 15 weight portion further stirring 5 hours again.Take in stirring
Mixed solution, after being removed catalyst and impurity by twice cleaning and filtering, is analyzed by IR and can confirm that at end group
SI-OH functional group (the 3200cm generated-1), measure the result of molecular weight, can confirm that the silsesquioxane of linear structure has
6,000 styrene conversion molecular weight.
The synthesis (synthesis of A-B precursor) of [embodiment 7-c] line style silsesquioxane alkyl structure
In possessing the dry flask of condensing tube and agitator, dropping distilled water 5 weight portion, oxolane 40 weight portion,
Catalyst 0.5 weight portion manufactured in above-described embodiment 7-a, after stirring at normal temperature 1 hour, dropping 2-(3,4-epoxycyclohexyl)
Ethyl trimethoxy silane 10 weight portion, dropping oxolane 20 weight portion further stirring 2 hours again.Take in stirring
Mixed solution, removed by twice cleaning catalyst and impurity and filter after, it is thus achieved that pass through1H-NMR analyzes the alkane of remaining
Epoxide is the line style silsesquioxane of below 0.1mmol/g, and this is later by sharp during successive reaction importing cagelike structure
Part.About the morphological analysis of linear structure, by XRD analysis, confirming overall structure is linear structure.Measure and divide
The result of son amount, can confirm that the silsesquioxane of linear structure has 8,000 styrene conversion molecular weight.
The synthesis (synthesis of A-B-A precursor) of [embodiment 7-d] line style silsesquioxane alkyl structure
In possessing the dry flask of condensing tube and agitator, drip distilled water 5 weight portion, oxolane 5 weight portion, institute
Embodiment 7-a catalyst 10 weight portion manufactured, after stirring at normal temperature 1 hour, dropping embodiment 7-b precursor and 7-c precursor are each
20 weight portions, dropping oxolane 10 weight portion further stirring 24 hours again.Take the mixed solution in stirring, pass through
Twice cleaning and remove catalyst and impurity and filter after, by IR analyze can confirm that end group generate SI-OH official
Can group (3200cm-1), measuring the result of molecular weight, can confirm that the silsesquioxane of linear structure has 15,000 styrene changes
Calculate molecular weight.
1H-NMR(CDCl3) δ 3.7,3.4,3.3 (wide), 3.1,2.8,2.6,1.5 (wide), 0.6.
[embodiment 7-e] cagelike structure continuously generate (importing of D structure)
In above-described embodiment 7-d mixed solution, very slowly drip HCl/water solution 5 weight portion of 0.36 weight %,
Being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, disposable addition diphenyl tetramethoxy two silica
Alkane 5 weight portion, it is achieved stable hydrolysis, after stirring 1 hour, adds catalyst 7 weight portion manufactured in embodiment 7-a again,
It is alkaline state by the pH regulator of mixed solution.Now, the D structure that alkoxyl opens independently is formed with linear macromolecule
Precursor.Gather a small amount of sample, be analyzed by H-NMR and IR, after confirming the survival rate of methoxyl group, when survival rate is 10%
Time, it is slowly added dropwise HCl/water solution 10 weight portion of 0.36 weight %, is acid by pH regulator.Afterwards, disposable addition phenyl three
Methoxy silane 1 weight portion also stirs 15 minutes, then adds catalyst 20 weight portion manufactured in 1-a.The mixing of 4 hours
The result confirmed after stirring, can confirm that the macromolecule generating cage modle in macromolecule.Afterwards, temperature is made to become room temperature, logical
Cross vacuum and remove the oxolane in mixed solution, make the whole be changed into water solution mixture.Mixing at 4 hours is stirred
After mixing, take a part, pass through29The result that Si-NMR is analyzed, can confirm that the analysis of the structure utilizing phenyl to import
Peak demonstrates two sharp-pointed forms, has manufactured macromolecule as chemical formula 7 with not having other remaining by-products.Additionally,
The styrene conversion molecular weight measured is 18,000.
29Si-NMR(CDCl3) δ-68.2 ,-72.3 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-82.5 (wide)
[embodiment 7-f] imports X (completing of A-B-A-D structure) in B structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 7-e refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.Material 100 weight portion obtained in embodiment 7-e is dissolved in the tetrahydrochysene of 50 weight portions
Furan, is subsequently adding the distilled water of 5 weight portions and manufactures mixed solution.Afterwards, add in manufactured mixed solution
HCl 10 weight portion of 0.36wt% also stirs 10 minutes, the most disposably adds MTMS 3 weight portion, it is achieved
Stable hydrolysis.After stirring 24 hours, again add catalyst 3 weight portion manufactured in embodiment 7-a, by the pH of mixed solution
It is adjusted to alkaline state.Now, the macromolecule of cage modle can import to the X section of B structure, carries out anti-the most continuously
Should, form macromolecule as chemical formula 7.But, owing to obtaining together with other by-products, it is therefore desirable to extra is refined.
Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare to refine.
[embodiment 7-g] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 7-f reacts in the mixture of end, add dichloromethane 200 weight portion, with distilled water one
Play classification washing, when the pH distilling water layer is neutrality, removed solvent completely by vacuum decompression.Afterwards, in methanol, precipitate 2
Secondary, remove unreacted monomer, with 30 weight portions in the solvent that oxolane and aqueous solution mix with 9.5:0.5 weight ratio
Take care of 2 days at a temperature of-20 DEG C after dissolving.This be the material closed by cagelike structure to make not import to macromolecule again
Crystallization, thus easily realize refined.
The solid matter obtained after completing recrystallization process filters, and confirms and do not have multiple by-product ground after vacuum decompression
Obtain the macromolecule of chemical formula 7.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight can in terms of styrene scaled value the value of acquisition 24,000, the n value that n value is 4-6, Y of X is 4-6.
Additionally, use the monomer described in table 2 below 5, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 7.
[table 25]
Embodiment 8: the high molecular synthesis of D-A-B-A-D structure composite silsesquioxane
In order to manufacture the composite high-molecular of D-A-B-D structure, use following embodiment, and by with above-described embodiment 1 phase
Same method, has manufactured compound fragment.
[embodiment 8-a] is for generating the pH reacting condition of the D structure of excess
In just carrying out the embodiment 7-d mixed solution reacted, very slowly drip the HCl/water solution 15 of 0.36wt%
Weight portion, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, the amount of 5 times of embodiment 7-e is prepared i.e.
The diphenyl tetramethoxy disiloxane of 25 weight portions, and it is disposably added, after stirring 1 hour, again add embodiment
Catalyst 20 weight portion manufactured in 7-a, is alkaline state by the pH regulator of mixed solution.After reaction terminates, temperature is made to become
Room temperature, removes the oxolane in mixed solution by vacuum, makes the whole be changed into water solution mixture.At 4 hours
Mix and blend after, take a part, pass through29Si-NMR and1The result that H-NMR is analyzed, can confirm that in B structure
The quantitative change of the alkoxyl existed is 0.006mmol/g, is imported with the repetitive of B Yu D with about 5:5 ratio.Additionally, the benzene measured
Ethylene conversion molecular weight is 32,000.Even if additionally, imported cagelike structure, can not see in high molecular GPC form
Individually the molecular weight distribution of cage modle material, therefore can confirm that cagelike structure is passed through successive reaction and imported to macromolecule well
Chain.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (wide), 3.1,2.8,2.6,1.5 (wide), 0.6.29Si-NMR
(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-82.5 (wide)
[embodiment 8-b] imports X in B structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 8-a refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.Material 100 weight portion obtained in embodiment 8-a is dissolved in the tetrahydrochysene of 50 weight portions
Furan, is subsequently adding the distilled water of 5 weight portions and manufactures mixed solution.Afterwards, add in manufactured mixed solution
HCl 10 weight portion of 0.36wt% also stirs 10 minutes, the most disposably adds MTMS 3 weight portion, it is achieved
Stable hydrolysis.After stirring 24 hours, again add catalyst 3 weight portion manufactured in embodiment 7-a, by the pH of mixed solution
It is adjusted to alkaline state.Now, the macromolecule of cage modle can import to the X section of B structure, carries out anti-the most continuously
Should, form macromolecule as chemical formula 8.But, owing to obtaining together with other by-products, it is therefore desirable to extra is refined.
Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare to refine.
[embodiment 8-c] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 8-b reacts in the mixture of end, add dichloromethane 200 weight portion, with distilled water one
Play classification washing, when the pH distilling water layer is neutrality, removed solvent completely by vacuum decompression.Afterwards, in methanol, precipitate 2
Secondary, remove unreacted monomer, with 30 weight portions in the solvent that oxolane and aqueous solution mix with 9.5:0.5 weight ratio
Take care of 2 days at a temperature of-20 DEG C after dissolving.This be the material closed by cagelike structure to make not import to macromolecule again
Crystallization, thus easily realize refined.
The solid matter obtained after completing recrystallization process filters, and confirms and do not have multiple by-product ground after vacuum decompression
Obtain the macromolecule of chemical formula 1.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight can in terms of styrene scaled value the value of acquisition 36,000, the n value that n value is 4-6, Y of X is 4-6, especially
The result of chemical formula 8 is as follows.
29Si-NMR(CDCl3) δ-72.5 (wide) ,-81.1 (sharp) ,-80.8 (sharp) ,-79.9 (sharp) ,-81.5 (sharp) ,-
82.5 (wide)
Additionally, use the monomer described in table 2 below 6, silsesquioxane composite high-molecular and compound fragment are manufactured.This
Time, manufacture method employs the method for the method equity with use in above-described embodiment 8.
[table 26]
Embodiment 9: the high molecular synthesis of silsesquioxane E-A-B-A-D structure composite
In order to manufacture the composite high-molecular of E-A-B-A-D structure, use following embodiment, and by with above-described embodiment 1
The method of equity, has manufactured compound fragment.
The generation of [embodiment 9-a] chain end E structure
The mixture obtained in not having extra refined embodiment 7-g drips dichloromethane 20 weight portion, dropping
HCl/water solution 5 weight portion of 0.36 weight %, being adjusted to pH is acidity, and stirs 30 minutes at a temperature of 4 DEG C.Afterwards, one
Secondary property adds dimethyl tetramethoxy-silicane 1 weight portion.Now, the part being the most not yet hydrolyzed and exist with
The acidic aqueous solution layer that solvent separates easily is changed into hydrolysate, contracts in organic solvent layer with the other reactant generated
Close and import E in terminal units.After the stirring of 5 hours, the stirring of stopped reaction, the temperature of reactor is adjusted to room temperature.
[embodiment 9-b] imports cagelike structure in the X of B structure and end E structure
There is no the organic layer of the extra product preparing to obtain in above-described embodiment 9-a refinedly, then utilize trifunctional
Monomer makes end be changed into cagelike structure.In just carrying out the embodiment 9-a mixed solution reacted, disposably add methyl trimethoxy
TMOS 3 weight portion, it is achieved stable hydrolysis, after stirring 24 hours, adds the catalyst 3 manufactured in embodiment 7-a again
Weight portion, is alkaline state by the pH regulator of mixed solution.Now, the macromolecule of cage modle can be imported at E structure end, in reaction
Device reacts continuously, forms macromolecule as chemical formula 9.But, owing to obtaining together with other by-products, therefore
Need extra refining.Afterwards, make temperature become room temperature, remove the oxolane in mixed solution by vacuum and prepare essence
System.
[embodiment 9-c] is removed by the by-product of precipitation and recrystallization, the acquirement of product
Above-described embodiment 9-b obtains reaction terminate mixture after, utilize distilled water wash, when distillation water layer pH in
Time neutral, removed solvent completely by vacuum decompression.Afterwards, precipitate 2 times in methanol, remove unreacted monomer, at tetrahydrochysene furan
Mutter keeping 2 at a temperature of-20 DEG C after dissolving with 30 weight portions in the solvent mixed with 9.5:0.5 weight ratio with aqueous solution
My god.This is the material recrystallization closed by cagelike structure to make not import to macromolecule, thus easily realizes refined.
The solid matter obtained after completing recrystallization process filters, and confirms after vacuum decompression together with multiple by-product
Obtain the macromolecule of chemical formula 9.Additionally, during by GPC result and NMR results contrast, the macromolecule in each stage does not has in growing
Derive the cage modle of sharp-pointed form the low molecule individually obtained, can confirm that from this result and can successfully obtain compound high score
Son.Now, molecular weight obtains 28 in terms of styrene scaled value, the value of 000, and the n value that n value is 4-6, Y of X is 4-6.
Additionally, use the monomer described in table 2 below 7, manufacture silsesquioxane composite high-molecular.Now, manufacturer
Method employs the method for the method equity with use in above-described embodiment 9.
[table 27]
[experiment]
The thin slice (Sheet) utilizing the compound fragment manufactured in above-described embodiment 1 to 9 to manufacture is measured physics, optics spy
Property.
-glass transition temperature evaluation (IPC-TM-650): become 2X20mm big the shearing of thin disc made with 0.3mm thickness
Little, it is placed in the geometry tonometer (Tension geometry) of dynamic viscoelastic analyser (DMA-8000) and is measured.This
Time, about condition determination, it is measured with the speed of 2 DEG C per minute under normally used 1Hz frequency.
-case hardness measures: generally, about pencil hardness method (JIS 5600-5-4), typically comment by 750g load
Valency, but with than this condition more exacting terms, i.e. 1kgf load, on coated face with the angle of 45 degree by pencil with per second
The speed of 0.5mm moves horizontally 10mm and scratches film, and is evaluated with cut.If do not had for more than 2 times in 5 experiments
Confirm the cut of more than 3mm, then select the pencil of a degree of hardness to be evaluated, if it is confirmed that to cut be 2 times with
On, then select the pencil of the next grade of this pencil hardness and be evaluated as pencil hardness.
-scratch test (Scratch test) measures: about utilizing the abrasion assessment method of steel wool, in about 1kg weight
Iron hammer front end be wound around #0000 steel wool (Steel wool), reciprocating friction test film 15 times, measure its haze value, but
In this evaluation, with than that is 400 times friction test sheets of this condition more exacting terms, and measure mist degree and carry out meat with microscope
Eye is evaluated.About result, it is judged as failure when mist degree increases by more than 0.05%.
-permeability (ASTM D1746): utilize ultraviolet-visible absorption spectroscopy (UV/vis spectroscopy) measure for
The total light transmittance of the light that the thin slice made is incident.
-yellow chromaticity (ASTM D1925): utilize color difference meter (CM-3700A) to measure the thin slice relative to standard light source (CIE)
Chromaticity coordinates value.
[table 28]
As shown in above-mentioned table 28, when blending with each macromolecule, show the rising effect of the glass transition temperature of excellence
Really, and can confirm that optical characteristics and case hardness, cut characteristic etc. are improved simultaneously.
INDUSTRIAL APPLICABILITY
The thermoplastic resin composition of the present invention is contained within the line style sesquialter silicon of ad hoc structure by comprising a macromolecule
Oxygen alkane chain and the silsesquioxane composite high-molecular of cage-type silsesquioxane, thus thermostability, chemical resistance, soil resistance, gas
Through preventing the excellences such as characteristic, permeability, coloring, wearability and case hardness.
Claims (13)
1. a thermoplastic resin composition, it is characterised in that comprise any one in following chemical formula 1 to 9 represented times
Half siloxanes composite high-molecular,
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
In above-mentioned chemical formula 1 to 9,
A isB isD is
Y is each independently O, NR21Or [(SiO3/2R)4+2nO], and at least one is [(SiO3/2R)4+2nO], X is independently of one another
For R22Or [(SiO3/2R)4+2nR], and at least one is [(SiO3/2R)4+2nR],
R、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22Each
Independently be hydrogen；Deuterium；Halogen；Amido；Epoxy radicals；Cyclohexyl ring epoxide；(methyl) acryloyl group；Mercapto；NCO；
Itrile group；Nitro；Phenyl；By deuterium, halogen, amido, epoxy radicals, (methyl) acryloyl group, mercapto, NCO, itrile group, nitre
The C that base, phenyl are substituted or non-substituted1～C40Alkyl；C2～C40Thiazolinyl；C1～C40Alkoxyl；C3～C40Cycloalkyl；
C3～C40Heterocyclylalkyl；C6～C40Aryl；C3～C40Heteroaryl；C3～C40Aralkyl；C3～C40Aryloxy group；Or
C3～C40Aryl mercaptan base,
A and d is each independently 1 to 100, the integer of 000,
B is each independently the integer of 1 to 500,
E is each independently 1 or 2,
N is each independently the integer of 1 to 20.
Thermoplastic resin composition the most according to claim 1, it is characterised in that a is 3 to 1000, b is 1 to 500, and d is
1 to 500.
Thermoplastic resin composition the most according to claim 1, it is characterised in that the meansigma methods of n is 4 to 5.
Thermoplastic resin composition the most according to claim 1, it is characterised in that described silsesquioxane composite high-molecular
Weight average molecular weight be 1,000 to 1,000,000.
Thermoplastic resin composition the most according to claim 1, it is characterised in that described thermoplastic resin composition comprises
Any one represented silsesquioxane composite high-molecular and macromolecule resin in described chemical formula 1 to 9.
Thermoplastic resin composition the most according to claim 4, it is characterised in that described macromolecule resin is to select free PC
(Merlon), PMMA (polymethyl methacrylate), PES (polyether sulfone), PET (polyethylene terephthalate), PEN
(PEN), COC (cyclic olefine copolymer), PAc (polyacrylate), PE (polyethylene), PEEK (polyethers ether
Ketone), PEI (Polyetherimide), PI (polyimides), PSF (polysulfones), PVA (polyvinyl alcohol), PVCi (polyvinyl alcohol cinnamic acid
Ester), TAC (triacetyl cellulose), polysilicon, polyurethane and epoxy resin composition group in more than one macromolecule resins.
Thermoplastic resin composition the most according to claim 1, it is characterised in that described thermoplastic resin composition comprises
Any one represented silsesquioxane composite high-molecular and inorfil in described chemical formula 1 to 9.
Thermoplastic resin composition the most according to claim 1, it is characterised in that described silsesquioxane composite high-molecular
Content be at least 1 weight %.
Thermoplastic resin composition the most according to claim 1, it is characterised in that described compositions comprises face further
Material.
10. the article manufactured by the thermoplastic resin composition described in claim 1.
11. article according to claim 10, it is characterised in that described article are the shells of electronic products.
12. article according to claim 10, it is characterised in that described article are functional fiber or functional garment.
13. article according to claim 10, it is characterised in that described article are plastic living articles for use, illuminate, protect
Cap, automobile interior exterior ornament materials, fishing rod, golf clubs, yacht, Discussion on architecture ornament materials, pipe arrangement, furniture or film.
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| KR10-2015-0031279 | 2015-03-05 | ||
| KR1020150031279A KR102325278B1 (en) | 2014-03-07 | 2015-03-05 | A thermoplastic resin composion comprising silsesquioxane composite polymer |
| PCT/KR2015/002193 WO2015133864A1 (en) | 2014-03-07 | 2015-03-06 | Thermoplastic resin composition comprising silsesquioxane composite polymer |
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| CN109400903A (en) * | 2018-11-08 | 2019-03-01 | 山东大学 | A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI668272B (en) | 2019-08-11 |
| JP2017512236A (en) | 2017-05-18 |
| KR20150105603A (en) | 2015-09-17 |
| KR102325278B1 (en) | 2021-11-16 |
| CN106062079B (en) | 2019-09-17 |
| JP7122083B2 (en) | 2022-08-19 |
| TW201546191A (en) | 2015-12-16 |
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