CN106062079B - Thermoplastic resin composition comprising silsesquioxane composite polymer - Google Patents

Thermoplastic resin composition comprising silsesquioxane composite polymer Download PDF

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CN106062079B
CN106062079B CN201580012246.3A CN201580012246A CN106062079B CN 106062079 B CN106062079 B CN 106062079B CN 201580012246 A CN201580012246 A CN 201580012246A CN 106062079 B CN106062079 B CN 106062079B
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methyl
pomma
phenyl
eche
glyp
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CN106062079A (en
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崔胜皙
俞载元
南东镇
金斗植
黄钟源
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Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
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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

Thermoplastic resin composition comprising silsesquioxane composite high-molecular
Technical field
It the present invention relates to the use of the thermoplastic resin composition of silsesquioxane composite high-molecular, more specifically, related to And the sesquialter silicon by the inclusion of line style silsesquioxane chain and cage-type silsesquioxane containing specific structure in a macromolecule Oxygen alkane composite high-molecular is to which heat resistance, chemical resistance, soil resistance, gas are through preventing characteristic, permeability, coloring, wear-resisting The excellent thermoplastic resin composition such as property and surface hardness.
Background technique
Thermoplastic resin passes through molding, the film, fiber filament of injection or extrusion because of workability in various fields Equal variforms are applied and are applied flexibly, (poly- using PC (polycarbonate), PMMA as representative thermoplastic resin 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), PVCi (polyvinyl cinnamate), (triacetyl is fine by TAC Dimension element), polysilicon (Poly Silicone), polyurethane (Polyurethane) and epoxy resin (Epoxy Resin) etc..
Thermoplastic resin as described above due to heat resistance, chemical resistance, gas through prevent characteristic, water repellency, the transparency, Coloring, wearability and surface hardness etc. are low, therefore are meeting physical characteristic side required by the scene gone forward side by side with industry development Face Shortcomings carry out following effort to solve the shortcoming by persistence: various thermoplastic resins are mixed and It uses, or adds various functional additives to enhance physical property.
For example, 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 of vinyl copolymer 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 100 parts by weight of polycarbonate resin include silicon-type compound 0.01-10 parts by weight, The metal organic sulfonate 0.01-1.5 parts by weight and polyfluoroethylene resin 0.01-1 parts by weight that average grain diameter is 100-400 μm are 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 can not be solved through preventing characteristic, soil resistance, water repellency, coloring, wearability and surface hardness Deng.
Summary of the invention
Project to be solved
As described above in order to solve the problems, such as, the object of the present invention is to provide include by the inclusion of in a macromolecule There are the line style silsesquioxane chain of specific structure and the silsesquioxane composite high-molecular of cage-type silsesquioxane, thus heat-resisting Property, chemical resistance, soil resistance, gas is through the warm that prevents characteristic, permeability, coloring, wearability and surface hardness etc. excellent Thermoplastic resin composition.
It is further an object that provide by being manufactured by above-mentioned thermoplastic resin composition, thus heat resistance, Chemical resistance, soil resistance, gas are through the article for preventing characteristic, permeability, coloring, wearability and surface hardness etc. excellent.
The method to solve the problem
To achieve the goals above, the present invention provides a kind of thermoplastic resin composition, which is characterized in that includes followingization Silsesquioxane composite high-molecular represented by any of formula 1 to 9:
[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 group；Cyclohexyl ring oxygroup；(methyl) acryloyl group；Mercapto；Isocyanic acid Ester group；Itrile group；Nitro；Phenyl；By deuterium, halogen, amido, epoxy group, (methyl) acryloyl group, mercapto, isocyanate group, nitrile The substituted or non-substituted C of base, nitro, phenyl1~C40Alkyl；C2~C40Alkenyl；C1~C40Alkoxy；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 substituted or non-substituted C of base, itrile group, nitro, phenyl, cyclohexyl ring oxygroup1~C40Alkyl, C2~C40Alkenyl, amido, ring Oxygroup, cyclohexyl ring oxygroup, (methyl) acryloyl group, mercapto, phenyl or isocyanate group,
A and d is each independently 1 to 100,000 integer, and preferably a is that 3 to 1000, d is 1 to 500, and more preferable a is 5 It is 2 to 100 to 300, d,
B is each independently 1 to 500 integer,
E is each independently 1 or 2, preferably 1,
N is each independently integer of 1 to 20, preferably 3 to 10.
In addition, the present invention provides a kind of article, which is characterized in that manufactured by above-mentioned thermoplastic resin composition.
Invention effect
Thermoplastic resin composition of the invention is by the inclusion of the line style sesquialter in a macromolecule containing specific structure The silsesquioxane composite high-molecular of siloxane chain and cage-type silsesquioxane, thus heat resistance, chemical resistance, soil resistance, gas Body, which penetrates, prevents characteristic, permeability, coloring, wearability and surface hardness etc. excellent.
Specific embodiment
Hereinafter, the present invention will be described in detail.
Thermoplastic resin composition of the invention is characterized in that, comprising represented by any of following chemical formula 1 to 9 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 group；Cyclohexyl ring oxygroup；(methyl) acryloyl group；Mercapto；Isocyanic acid Ester group；Itrile group；Nitro；Phenyl；By deuterium, halogen, amido, epoxy group, (methyl) acryloyl group, mercapto, isocyanate group, nitrile The substituted or non-substituted C of base, nitro, phenyl1~C40Alkyl；C2~C40Alkenyl；C1~C40Alkoxy；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 substituted or non-substituted C of base, itrile group, nitro, phenyl, cyclohexyl ring oxygroup1~C40Alkyl, C2~C40Alkenyl, amido, ring Oxygroup, cyclohexyl ring oxygroup, (methyl) acryloyl group, mercapto, phenyl or isocyanate group,
A and d is each independently 1 to 100,000 integer, and preferably a is that 3 to 1000, d is 1 to 500, and more preferable a is 5 It is 2 to 100 to 300, d,
B is each independently 1 to 500 integer,
E is each independently 1 or 2, preferably 1,
N is each independently integer of 1 to 20, preferably 3 to 10.
Thermoplastic resin composition of the invention by the inclusion of in above-mentioned macromolecule there is above-mentioned [A] a and [D] d to repeat Unit, selectivity have the silsesquioxane of the specific structure of [B] b or [E] e repetitive unit, so as to make by thermoplastic resin Oil/fat composition manufacture article have heat resistance, chemical resistance, soil resistance, gas through prevent characteristic, permeability, coloring, Wearability and surface hardness.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 1 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation It closes object and is condensed, manufacture 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, acidic catalyst is added into reactor, reaction solution is adjusted to acidity, then adds organic-silylation and close Object simultaneously stirs；And third step adds basic catalyst into reactor after the second step described above, and reaction solution is changed For alkalinity, implement condensation reaction.
[chemical formula 10]
In above-mentioned formula, R1、R2、R16, D, a and d it is identical as the definition in above-mentioned chemical formula 1 to 9.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 2 of the invention can by carry out following steps come Manufacture: first step, in the reactor after mixed-alkali catalyst and organic solvent, addition organic silane compound is simultaneously 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, and acidic catalyst is added into reactor, reaction solution is adjusted to acidity, is then added Add excessive organic silane compound and stirs；Third step adds alkalinity into reactor and urges after the second step described above Reaction solution is changed into alkalinity, implements condensation reaction by agent；And purification step, by recrystallization removal as by third step Suddenly cage modle (cage) structure for the by-product being individually created.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 3 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation It closes object and is condensed, manufacture 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, acidic catalyst is added into reactor, reaction solution is adjusted to acidity, then adds organic-silylation and close Object simultaneously stirs；Third step adds basic catalyst into reactor after the second step described above, and reaction solution is changed into Alkalinity implements condensation reaction；And four steps, after above-mentioned third step, in order to by [E] eX2Structure imports compound high score The end of son, acidic catalyst is added into reactor, reaction solution is changed into acidic atmosphere, mixing organic silane compound is simultaneously Stirring.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 4 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation It closes object and adjusts condensation degree, manufacture 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, and acidic catalyst is added into reactor, reaction solution is adjusted to acidity, then Addition organic silane compound simultaneously stirs；And third step adds base catalysis into reactor after the second step described above Reaction solution is changed into alkalinity, implements condensation reaction by agent.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 5 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation It closes object and is condensed, manufacture 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, and acidic catalyst is added into reactor, reaction solution is adjusted to acidity, Then the organic silane compound of excessive addition and stirring；Third step is added into reactor after the second step described above Reaction solution is changed into alkalinity, implements condensation reaction by basic catalyst；And four steps, after the third step, by tying again Brilliant and filter process, removes the cagelike structure being individually created.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 6 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation It closes object and is condensed, manufacture 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, and acidic catalyst is added into reactor, reaction solution is adjusted to acidity, is then added with Organic silane compound simultaneously stirs；Third step adds basic catalyst into reactor after the second step described above, will be anti- It answers liquid to be changed into alkalinity, implements condensation reaction；And four steps, after the third step, in order to by [E] eX2Structure imports multiple High molecular end is closed, acidic catalyst is added into reactor, reaction solution is changed into acidic atmosphere, mixes organic-silylation It closes object and stirs.
Preferably, in the method for manufacturing above-mentioned chemical formula 1 to 6, the pH of the reaction solution of first step of the invention is preferred It is 9 to 11.5, the pH of the reaction solution of second step is preferably 2 to 4, and the pH of the reaction solution of third step is preferably 8 to 11.5, is led The pH for entering the reaction solution of the four steps of Ee is preferably 1.5 to 4.In the case where within the above range, manufactured sesquialter The high income of siloxanes composite high-molecular, and can be improved the mechanical properties of manufactured silsesquioxane composite high-molecular.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 7 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation Object is closed, manufacture has adjusted the above-mentioned chemical formula 10 of two kinds of forms of condensation degree；Second step, in order to by [B] b structure and [D] d (OR12)2Structure imports chemical formula 10 obtained in above-mentioned first step, acidic catalyst is added into reactor, by reaction solution It is adjusted to acidity, then add organic silane compound and is stirred；Third step, after above-mentioned each second step reaction, to Basic catalyst is added in reactor, and reaction solution is changed into alkalinity, implements condensation reaction；And four steps, it will be by above-mentioned The two or more substances that third step obtains are condensed under alkaline condition and connect.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 8 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation Object is closed, manufacture has adjusted the above-mentioned chemical formula 10 of two kinds of forms of condensation degree；Second step, in order to by [B] b structure, [D] d (OR14)2Structure imports chemical formula 10 obtained in above-mentioned first step, acidic catalyst is added into reactor, by reaction solution It is adjusted to acidity, then add organic silane compound and is stirred；Third step, after above-mentioned each second step reaction, to Basic catalyst is added in reactor, and reaction solution is changed into alkalinity, implements condensation reaction；Four steps will pass through above-mentioned The two or more substances that three steps obtain are condensed under alkaline condition and connect；5th step, after above-mentioned four steps, To for importing [D] d (OR13)2Reactor in add acidic catalyst, reaction solution is adjusted to acidity, is then added organic Silane compound simultaneously stirs；And the 6th step basic catalyst is added into reactor after above-mentioned 5th step, will be anti- It answers liquid to be changed into alkalinity, implements condensation reaction.
Silsesquioxane composite high-molecular represented by above-mentioned chemical formula 9 of the invention can be made as follows It makes, the step includes: first step, in the reactor after mixed-alkali catalyst and organic solvent, adds organic-silylation Object is closed, manufacture has adjusted the above-mentioned chemical formula 10 of two kinds of forms of condensation degree；Second step, it is above-mentioned in order to import [B] b structure Chemical formula 10 obtained in first step, acidic catalyst is added into reactor, and reaction solution is adjusted to acidity, is then added Organic silane compound simultaneously stirs；Third step adds base catalysis into reactor after above-mentioned each second step reaction Reaction solution is changed into alkalinity, implements condensation reaction by agent；Four steps will be obtained two or more by above-mentioned third step Substance be condensed and connect under alkaline condition；5th step, after above-mentioned four steps, to for importing [D] d (OR5)2 Reactor in add acidic catalyst, reaction solution is adjusted to acidity, then adds and organic silane compound and stirs；6th Step adds basic catalyst into reactor after above-mentioned 5th step, and reaction solution is changed into alkalinity, implements 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 anti- It answers and puts into acidic catalyst in device, reaction solution is changed into acidic atmosphere, mix organic silane compound and stir.
Preferably, in the high molecular method for manufacturing above-mentioned chemical formula 7 to 9, the pH of the reaction solution of first step is preferred It is 9 to 11.5, the pH of the reaction solution of second step is preferably 2 to 4, and the pH of the reaction solution of third step is preferably 8 to 11.5, the The pH of the reaction solution of four steps is preferably 9 to 11.5, and the pH of the reaction solution 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 for importing the reaction solution of the 7th step of Ee is preferably 1.5 to 4.Within the above range In the case where, the high income of manufactured silsesquioxane composite high-molecular, and can be improved manufactured silsesquioxane The mechanical properties of composite high-molecular.
In addition, when necessary, in order to further by [B] b structure and [D] d (OR)2Structure imports each composite high-molecular, can be with Make to further include [B] b repetitive unit in composite high-molecular as follows: adding acidic catalyst into reactor, it will The step of reaction solution is adjusted to acidity, then adds organic silane compound and stirs；And after the above step, to reactor Middle addition basic catalyst, the step of being changed into alkalinity by reaction solution, implement condensation reaction.
In addition, when necessary, in order to further by [E] eX2Structure imports the end of each composite high-molecular, can be by as follows Step makes the end of composite high-molecular further include the repetitive unit of [E] e: acidic catalyst is put into reactor, it will be anti- It answers liquid to be changed into acidic atmosphere, mix organic silane compound and stirs.
In the manufacturing method of above-mentioned silsesquioxane composite high-molecular, as basic catalyst, it is preferable to use two kinds with It is caused and is hydrolyzed again with acidic catalyst neutralization and acidification, utilizes two again by the mixed catalyst of upper basic catalyst Kind or more basic catalyst mixed catalyst, be condensed with alkalinity, so as to be continuously adjusted in a reactor Acidity and basicity.
At this point, above-mentioned basic catalyst can be by two kinds in metal system basic catalyst and amine system basic catalyst Above substance is appropriately combined to be manufactured, and the metal system basic catalyst is selected from the group being made of Li, Na, K, Ca and Ba.It is excellent Choosing and stating amine system basic catalyst to be tetramethylammonium hydroxide (TMAH), and metal system basic catalyst can be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO3).It, preferably can be in amine system alkalinity about the content of each ingredient in above-mentioned mixed catalyst The ratio of catalyst and metal system basic catalyst is arbitrarily adjusted for 10 to 90:10 into the ratio of 90 parts by weight.In upper In the case where stating in range, the reactivity of functional group and catalyst can be made to minimize in hydrolysis, thus make Si-OH or Si- The combination of the organo-functional groups such as alkoxy substantially reduces, and has the advantages that be free to adjust condensation degree.In addition, as above-mentioned Acidic catalyst can be used for example as long as acidic materials usually used in this field can be used unlimitedly HCl、H2SO4、HNO3、CH3The general acidic materials such as COOH, additionally can be used lactic acid, tartaric acid, maleic acid, citric acid etc. Organic system acidic materials.
In the manufacturing method of silsesquioxane composite high-molecular of the invention, as long as lead in above-mentioned organic solvent this field The organic solvent being often used can be used unlimitedly, and methanol, ethyl alcohol, isopropanol, butanol, cellosolve system can be used for example Equal alcohols, lactate system, the ketones such as acetone, methyl (isobutyl group) ethyl ketone, the di-alcohols such as ethylene glycol, the furans such as tetrahydrofuran System, dimethylformamide, dimethyl acetamide, n-methyl-2-pyrrolidone isopolarity solvent, and hexane, ring can be used Hexane, cyclohexanone, toluene, dimethylbenzene, cresols, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane, The various solvents such as acrylonitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzylalcohol.
In addition, can be used as above-mentioned organosilan based compound as the compound high score of silsesquioxane of the invention The chemical formula 1 to 9 of son includes 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 be used with by increase silsesquioxane composite high-molecular chemical resistance To improve the organic silane compound comprising phenyl or amino of the effect of non-swelling property or have by increasing compound height The cured density of molecule to improve the mechanical strength of cured layer and the effect of hardness comprising epoxy group 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, (the third oxygen of 3- epoxy Propyl) dimethylethoxysilane, 3- (methacryloxy) propyl trimethoxy silicane, 3,4- epoxy group butyl trimethoxy Base silane, 3,4- epoxy group butyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- Epoxycyclohexyl) ethyl triethoxysilane, aminopropyltriethoxywerene werene, vinyltriethoxysilane, vinyl three Tert-butoxy silane, three isobutoxy silane of vinyl, vinyl silane triisopropoxide, vinyltriphenoxysilane, benzene Ethyl triethoxy silicane alkane, phenyltrimethoxysila,e, TSL 8330, N- phenyl -3- aminopropyl trimethoxy Base silane, dimethyl tetramethoxy siloxanes, diphenyl tetramethoxy siloxanes etc., can be used alone it is one such or And with two or more.For the physical property of the composition finally manufactured, preferably it is use mixing two or more.
In the present invention, it imported into the [(SiO of repetitive unit [D] d of above-mentioned chemical formula3/2R)4+2nO] n of structure can generation Entering integer of 1 to 20, preferably 3 to 10, the average value of more preferable n is 4 to 5, for example, when above-mentioned n is 4, the knot that is substituted into Being expressed as follows for structure is stated shown in chemical formula 11:
[chemical formula 11]
In above-mentioned formula, R is as defined above.
In the present invention, it imported into the [(SiO of repetitive unit [B] b or [E] e of above-mentioned chemical formula3/2R)4+2nR] structure n Integer of 1 to 20, preferably 3 to 10 can be substituted into, the average value of more preferable n is 4 to 5, for example, when above-mentioned n is 4, by generation Being expressed as follows for 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, silsesquioxane macromolecule according to the present invention can be the macromolecule in following table 1 to 18.Under It states in table 1 to 9, ECHE refers to that (epoxycyclohexyl) ethyl, GlyP refer to that epoxypropoxy, POMMA refer to (methacryl Oxygroup) propyl, when recording more than two, 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 be the macromolecule recorded in following table 1 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 to record in following Table 3 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
4-6 Vinyl, methoxyl group H、F ECHE Phenyl POMMA
4-7 Alkylamine CF3, methyl ECHE Octyl 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 POMMA POMMA
4-14 OH, acryloyl group H, octyl Methyl ECHE Aminopropyl
4-15 Vinyl, methoxyl group H, methyl Octyl Alkyl sulfide alcohol radical Phenyl
4-16 Alkylamine H, methyl Octyl 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
4-21 Propoxyl group, methoxyl group C8F13, methyl GlyP POMMA POMMA
4-22 OH, methoxyl group H, propyl POMMA Propyl 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 to record in following table 5 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 to record in following table 7 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 to record in following table 9 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 to record in following table 11 and 12 Macromolecule.
[table 11]
[table 12]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 7 can be to record in following table 13 and 14 Macromolecule.
[table 13]
[table 14]
As concrete example, the silsesquioxane composite high-molecular of above-mentioned chemical formula 8 can be to record in following table 15 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 to record in following table 17 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 above-mentioned silsesquioxane composite high-molecular of the invention, obtained in order to ensure excellent keeping stability wide Condensation degree can be adjusted to 1 to 99.9% by general application.I.e., it is possible to be adjusted to be incorporated into the alkane of the Si of end and center The content of oxygroup is 50% to 0.01% relative to all high molecular conjugated groups.
In addition, the weight average molecular weight of silsesquioxane composite high-molecular can be 1,000 to 1,000,000 in the present invention, Preferably 5,000 to 100,000, more preferably 7,000 to 50,000.In this case, silsesquioxane can be improved simultaneously Processability and physical characteristic.
Silsesquioxane composite high-molecular represented by any of above-mentioned chemical formula 1 to 9 has 50 to 250 DEG C of glass Change transition temperature (Tg), the content of repetitive unit [A] a is more, and Tg is lower, and the content of repetitive unit [B] b, [D] d and [E] e are got over More, Tg is higher, therefore can suitably adjust the content of repetitive unit according to used purposes to have Tg.
Thermoplastic resin composition of the invention can be only by the silsesquioxane represented by any of above-mentioned chemical formula 1 to 9 Alkane composite high-molecular is constituted, and can also be mixed and be used with macromolecule used in previous thermoplastic resin composition.As upper The macromolecule that can be used in mixed way is stated, is not particularly limited, for example, can be used selected from by PC (polycarbonate), PMMA (poly- methyl-prop E pioic acid methyl ester), PES (polyether sulfone), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), 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 of polysilicon (Poly Silicone), polyurethane (Polyurethane) and epoxy resin (Epoxy Resin) composition More than one macromolecule resins.The compound high score of silsesquioxane represented by any of above-mentioned chemical formula 1 to 9 when being used in mixed way The content of son can arbitrarily be selected in 0.1 to 99 weight % and be used, it is preferable that, can using 1 weight % or more Further increase the physical property such as the chemical resistance of thermoplastic resin.
In addition, thermoplastic resin composition of the invention can also be with the silsesquioxane represented by any of chemical formula 1 to 9 Alkane composite high-molecular is used in mixed way the inorfils such as glass fibre or carbon fiber together.In above-mentioned chemical formula 1 to 9 when being used in mixed way The content of silsesquioxane composite high-molecular represented by any one can arbitrarily be selected in 1 to 90 weight % and be used, preferably Ground can further improve the physical property such as the waterproofness of thermoplastic resin using 5 weight % or more.
It is multiple for silsesquioxane represented by any of chemical formula 1 to 9 in thermoplastic resin composition of the invention 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, pass through the macromolecule resin or inorfil for selecting to use be used in mixed way in silsesquioxane composite high-molecular Functional group excellent in compatibility steadily can persistently keep anti-flammability, prevent so as to improve the stability of thermoplastic resin The physical property such as aqueous, soil resistance, the transparency.
In addition, above-mentioned resin combination can further include pigment.Any of above-mentioned chemical formula 1 to 9 of the invention institute The silsesquioxane composite high-molecular of expression improves the dispersibility of pigment, excellent in compatibility with pigment, in thermoplastic resin group Object is closed comprising that there can be excellent coloring effect in the case where pigment.Well known pigment undoubtedly can be used in above-mentioned pigment, about The content of pigment, those skilled in the art can select to use within the appropriate range.
In the present invention, above-mentioned thermoplastic resin composition can further include increasing usually used in this field as needed Mould agent, ultraviolet screener, ultraviolet absorbing agent, antioxidant, defoaming agent, levelling agent, water repellent, fire retardant, bonding improver, The additives such as other function additive improve physical property.Such additive is not particularly limited when in use, can not damage It is suitable for addition in the range of the physical property of evil thermoplastic resin, as concrete example, above-mentioned additive is relative to composition total weight 100 Parts by weight may include 0.01-10 parts by weight each independently.
As additive workable in the present invention, polyether-modified dimethyl polysiloxane system can be enumerated (Polyether-modified polydimethylsiloxane, for example, 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, for example, BYK-308, BYK-373 etc.), methylalkylpolysiloxanes system (Methylalkylpolysiloxane, for example, BYK-077, BYK-085 etc.), polyether-modified methylalkylpolysiloxanes system (Polyether modified methylalkylpolysiloxane, for example, BYK-320, BYK-325 etc.), polyester modification Methylalkylpolysiloxanes system (Polyester modified poly-methyl-alkyl-siloxane, for example, BYK-315 Deng), aralkyl modified methylalkylpolysiloxanes system (Aralkyl modified methylalkyl polysiloxane, example Such as, BYK-322, BYK-323 etc.), polyester modification hydroxy-functional polydimethylsiloxanes system (Polyester modified Hydroxy functional polydimethylsiloxane, for example, BYK-370 etc.), polyester modification acrylic acid function it is poly- 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, for example, BYK-375 etc.), it is poly- Ether modified dimethyl polysiloxane system (Polyether modified dimethylpolysiloxane, for example, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337 etc.), nonionic acrylic copolymer system (Non- Ionic acrylic copolymer, for example, BYK-380 etc.), ionic acrylic copolymer system (Ionic acrylic Copolymer, for example, BYK-381 etc.), polyacrylate system (Polyacrylate, for example, BYK-353, BYK-356, BYK- 354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 etc.), polymethacrylates system (Polymethacrylate, for example, BYK-390 etc.), polyether-modified acrylic acid functional polydimethylsiloxanes system (Polyether modified acryl functional polydimethylsiloxane, for example, BYK-UV3500, BYK-UV3530 etc.), polyether modified siloxane system (Polyether modified siloxane, for example, BYK-347 etc.), alcohol Alcoxylates system (Alcohol alkoxylates, for example, BYK-DYNWET 800 etc.), acrylic ester (Acrylate, For example, BYK-392 etc.), hydroxyl-functional silicone-modified polyacrylate system (Silicone modified polyacrylate (OH-functional), for example, BYK-Silclean 3700 etc.) etc..
In addition, the present invention provides the article that manufactures using above-mentioned thermoplastic resin composition, if above-mentioned article use it is upper It states thermoplastic resin composition's manufacture to be just not particularly limited, it may for example comprise film, the molding by injecting or squeezing out, foaming Object, fiber filament.About above-mentioned film, molding, foamed or filametntary method is manufactured, undoubtedly using the heat of aforementioned present invention Thermoplastic resin composition is simultaneously manufactured using well known each manufacture film, molding, foamed or filametntary process.As upper The concrete example of article is stated, the cover including the shell of various electronic products can be enumerated, the plastic living including ornaments is used Product, illumination, head protector, automobile interior exterior ornament materials, fishing rod, golf club, yacht, Discussion on architecture ornament materials, piping, family Tool, film, functional fiber, functional garment etc..
Hereinafter, providing preferred embodiment, but following embodiments only illustrate this to facilitate understanding of the invention Invention, the scope of the present invention are not limited to following embodiments.In following the embodiment of the present invention, ECHETMS refers to 2- (3,4- rings Oxygen cyclohexyl) ethyl trimethoxy silane, GPTMS refers to glycidoxypropyltrime,hoxysilane, and MAPTMS refers to (methyl Acryloyl-oxy) propyl trimethoxy silicane, PTMS refers to phenyltrimethoxysila,e, and MTMS refers to methyltrimethoxysilane, ECHETMDS refers to that two (epoxycyclohexylethyl) tetramethoxy disiloxane, GPTMDS refer to two (glycidoxypropyl groups) four Methoxyl group disiloxane, MAPTMDS refer to that two (methacryloxy) propyl tetramethoxy disiloxane, PTMDS refer to two (phenyl) tetramethoxy disiloxane, MTMDS refer to two (methyl) tetramethoxy disiloxane.
The manufacture of [embodiment 1] comprising copolymer 1 and 9 coating composition
It is following to carry out continuous hydrolysis and condensation by step about synthesis step.
The manufacture of [embodiment 1-a] catalyst
In order to adjust basicity, 10 weight % hydroxides are mixed in 25 weight % aqueous solution of tetramethylammonium hydroxide (TMAH) Potassium (KOH) aqueous solution and prepare catalyst 1a.
The synthesis of [embodiment 1-b] line style silsesquioxane structure
In the drying flask for having condenser pipe and blender, be added dropwise 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 2- (3,4- epoxycyclohexyl) second is added dropwise after stirring at normal temperature 1 hour in 1 parts by weight of catalyst manufactured in above-described embodiment 1-a 15 parts by weight of tetrahydrofuran are added dropwise again and futher stir 5 hours for 20 parts by weight of base trimethoxy silane.It takes in stirring Mixed solution after removing catalyst and impurity and cleaning twice and filtering, is confirmed by IR analysis in end group SI-OH functional group (the 3200cm of generation-1), measure molecular weight as a result, confirming the line style knot as 4 structure of chemical formula The silsesquioxane of structure has 8,000 styrene conversion molecular weight.
[embodiment 1-c] cagelike structure continuously generates
In above-described embodiment 1-b mixed solution, 5 parts by weight of HCL aqueous solution of 0.36 weight % are very slowly added dropwise, Be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, it is added at one time two silicon oxygen of diphenyl tetramethoxy 5 parts by weight of alkane realize that stable hydrolysis adds 7 parts by weight of catalyst manufactured in embodiment 1-a after stirring 1 hour again, The pH of mixed solution is adjusted to alkaline state.At this point, independently forming the D structure that alkoxy opens with linear macromolecule Precursor.A small amount of sample is acquired, is analyzed by H-NMR and IR, after the survival rate for confirming methoxyl group, when survival rate is 20% When, 10 parts by weight of HCL aqueous solution of 0.36 weight % are slowly added dropwise, pH is adjusted to acidity.Later, it is added at one time phenyl three 1 parts by weight of methoxy silane simultaneously stir 15 minutes, then add 20 parts by weight of catalyst manufactured in 1-a.In mixing in 4 hours It is confirming after stirring as a result, confirming the macromolecule for generating cage modle in macromolecule.Later, so that temperature is become room temperature, lead to The tetrahydrofuran being removed in vacuo in mixed solution is crossed, the whole is made to be changed into water solution mixture.Mixing at 4 hours is stirred After mixing, a part is taken, is passed through29It is that Si-NMR is analyzed as a result, confirm using phenyl import structure analysis Peak shows two sharp forms, has not manufactured A-D high as 50% or more chemical formula 1 to other remaining by-products Molecule.In addition, the average value that the styrene conversion molecular weight of measurement is 11,000, n is 4.6.29Si-NMR(CDCl3)δ
[embodiment 1-D]
With opposite under the molten condition of raw material fragment polyethylene terephthalate (Di Ren company, TR-8550T1) It is that 10 weight % cooperate the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C in total weight, manufacture is poly- to benzene two The compound fragment of formic acid glycol ester.
[embodiment 1-E]
Raw material fragment polycarbonate (Di Ren company,) molten condition under with relative to total weight be 5 weights Amount % cooperates the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C, manufactures the compound fragment of polycarbonate.
[embodiment 1-F]
Raw material fragment polyethylene naphthalate (Di Ren company,TN8065S under molten condition) To be that 5 weight % cooperate the silsesquioxane composite high-molecular manufactured in above-described embodiment 1-C relative to total weight, poly- naphthalene is manufactured The compound fragment of naphthalate.
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 19.This When, manufacturing method has used the method with the equity of method used 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, using following embodiments, using with recorded in above-described embodiment 1 Method equity method, manufactured compound fragment.About the manufacture of catalyst and linear structure, use and embodiment 1-a Method identical with the method for 1-b in order to continuously generate D-A-D structure, is manufactured later using following methods.
The generation of [embodiment 2-a] excessive continuous cagelike structure
In above-described embodiment 1-b mixed solution, 5 parts by weight of HCL aqueous solution of 0.36 weight % are very slowly added dropwise, Be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, the 5 of the usage amount of embodiment 1-b are added at one time I.e. 25 parts by weight diphenyl tetramethoxy disiloxane again realize that stable hydrolysis adds embodiment after stirring 1 hour again 7 parts by weight of catalyst manufactured in 1-a, are adjusted to alkaline state for the pH of mixed solution.At this point, independently with linear macromolecule Form the precursor for the D structure that alkoxy opens.A small amount of sample is acquired, is analyzed by H-NMR and IR, confirms methoxyl group Survival rate after, when survival rate be 20% when, 10 parts by weight of HCL aqueous solution of 0.36 weight % are slowly added dropwise, pH is adjusted to It is acid.Later, 1 parts by weight of phenyltrimethoxysila,e are added at one time and are stirred 15 minutes, what is then manufactured in addition 1-a urges 20 parts by weight of agent.It is confirming after mixing in 4 hours as a result, confirming the high score for generating cage modle in macromolecule Son.Later, so that temperature is become room temperature, by the way that the tetrahydrofuran in mixed solution is removed in vacuo, the whole is made to be changed into water Solution mixture.After mixing in 4 hours, a part is taken, is passed through29It is that Si-NMR is analyzed as a result, can confirm Two sharp forms are shown to the analysis peak of the structure imported using phenyl, are not manufactured other remaining by-products A-D macromolecule as chemical formula 1.In addition, it is 4.6 that the styrene conversion molecular weight of measurement, which is 14,000, n value,.In addition, by Si-NMR analysis confirms, different from A-D structure, and the peak near the visible -68ppm in the 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 (width), -81.1 (points), - 80.8 (points), -82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 20.This When, manufacturing method has used the method with the equity of method used 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, using following embodiments, using with recorded in above-described embodiment 1 Method equity method, manufactured compound fragment.About the manufacture of catalyst and linear structure, use and embodiment 1 The identical method of method in order to generate E-A-D structure, is manufactured later using following methods.
The generation of [embodiment 3-a] chain end E structure
20 parts by weight of methylene chloride, drop are added dropwise in the A-D mixture obtained in the embodiment 1-c of not additional purification 5 parts by weight of HCL aqueous solution for adding 0.36 weight %, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, It is added at one time 1 parts by weight of dimethyl tetramethoxy-silicane.At this point, not yet hydrolyzed and existing part exists in the molecular structure It is easy to be changed into hydrolysate in the acidic aqueous solution layer separated with solvent, the other reactant with generation is in organic solvent layer It is condensed and imports E in terminal units.After stirring in 5 hours, stops the stirring of reaction, the temperature of reactor is adjusted to often Temperature.
[embodiment 3-b] imports cagelike structure in the E structure of end
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 3-a, then utilizes trifunctional Monomer makes end be changed into cagelike structure.In the embodiment 3-a mixed solution just reacted, it is added at one time methyl trimethoxy 3 parts by weight of oxysilane realize that stable hydrolysis adds the catalyst 3 manufactured in embodiment 1-a after stirring 24 hours again The pH of mixed solution is adjusted to alkaline state by parts by weight.At this point, the macromolecule of cage modle can be imported in E structure end, reacting It is continuously reacted in device, forms macromolecule as chemical formula 3.But due to being obtained together with other by-products, Need additional purification.Later, so that temperature is become room temperature, prepare essence and the tetrahydrofuran in mixed solution is removed in vacuo System.
[embodiment 3-c] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
After reacting the mixture of end in obtaining above-described embodiment 3-b, benefit is washed with distilled water, as the pH of distillation water layer When being in neutrality, solvent is completely removed by vacuum decompression.Later, it precipitates 2 times in methyl alcohol, unreacted monomer is removed, in tetrahydro In the solvent that furans and aqueous solution are mixed with 9.5:0.5 weight ratio with 30 parts by weight dissolution after -20 DEG C at a temperature of protect Pipe 2 days.This is in order to recrystallize the substance for not importeding into macromolecule and being closed by cagelike structure, thus purification easy to accomplish.
The solid matter obtained after recrystallization process filtering will be completed, is confirmed together with a variety of by-products after vacuum decompression Obtain the macromolecule of chemical formula 3.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight is calculated as 17,000, n value with styrene scaled value as 4-66, the result of especially chemical formula 3 is as follows.
29Si-NMR(CDCl3) δ -68.2, -71.8 (points), -72.3 (width), -81.1 (points), -80.8 (points), -82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 21.This When, manufacturing method has used the method with the equity of method used in above-described embodiment 3.
[table 21]
Embodiment 4: the high molecular synthesis of A-B-D structure composite silsesquioxane
It is following to carry out continuous hydrolysis and condensation by step about synthesis step, the composite high-molecular of E-A-D structure has been manufactured, Using method corresponding with the method recorded in above-described embodiment 1, compound fragment has been manufactured.
[embodiment 4-a] is used to hydrolyze and the manufacture of the catalyst of condensation reaction
In order to adjust basicity, 10 weight % hydroxides are mixed in 25 weight % aqueous solution of tetramethylammonium hydroxide (TMAH) Potassium (KOH) aqueous solution and prepare catalyst 1a.
The synthesis (synthesis of A-B precursor) of [embodiment 4-b] line style silsesquioxane structure
In the drying flask for having condenser pipe and blender, be added dropwise 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of catalyst manufactured in above-described embodiment 4-a are added dropwise 2- (3,4- epoxycyclohexyl) after stirring at normal temperature 1 hour 20 parts by weight of tetrahydrofuran are added dropwise again and futher stir 2 hours for 10 parts by weight of ethyl trimethoxy silane.It takes in stirring Mixed solution, removed and cleaning twice catalyst and impurity and filter after, passed through1The alkane of H-NMR analysis remaining Oxygroup is 0.1mmol/g line style silsesquioxane below, this is sharp when importing cagelike structure by successive reaction later Part.About the morphological analysis of linear structure, by XRD analysis, confirming overall structure is linear structure.Measurement point Son amount as a result, confirm linear structure silsesquioxane have 6,000 styrene convert molecular weight.
1H-NMR(CDCl3) δ 3.7,3.4,3.3 (width), 3.1,2.8,2.6,1.5 (width), 0.6.
[embodiment 4-c] in chain for generating the pH reacting condition (importing of B, D structure) of cagelike structure
In the embodiment 4-b mixed solution just reacted, the aqueous solution 5 of 0.36wt%HCl is very slowly added dropwise Parts by weight, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, it is added at one time diphenyl tetramethoxy 5 parts by weight of disiloxane add 5 parts by weight of catalyst manufactured in embodiment 4-a, by mixed solution after stirring 1 hour again PH be adjusted to alkaline state.At this point, confirming the structural body for independently generating cage modle with linear structure and importeding into height Strand makes temperature become room temperature, by the way that the tetrahydrofuran in mixed solution is removed in vacuo, is changed into the whole water-soluble Liquid mixture.After mixing in 4 hours, a part is taken, is passed through29Si-NMR and1It is that H-NMR is analyzed as a result, The quantitative change for confirming the alkoxy present in B structure is 0.025mmol/g, and the repetition list of B and D is imported with 5:5 ratio Member.In addition, the styrene conversion molecular weight of measurement is 10,000.In addition, even if having imported cagelike structure, in high molecular GPC The molecular weight distribution of individual cage modle substance can not be seen in form, therefore can confirm that cagelike structure is good by successive reaction Ground imported into macromolecular chain.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (width), 3.1,2.8,2.6,1.5 (width), 0.6.29Si-NMR (CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -82.5 (width)
[embodiment 4-d] imports X (importing of B, D structure) in B structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 4-c, then utilizes trifunctional Monomer makes end be changed into cagelike structure.100 parts by weight of substance obtained in embodiment 4-c are dissolved in the tetrahydro of 50 parts by weight Then furans is added the distilled water of 5 parts by weight and manufactures mixed solution.Later, it is added in manufactured mixed solution 10 parts by weight of HCl of 0.36wt% simultaneously stir 10 minutes, are then added at one time 3 parts by weight of methyltrimethoxysilane, realize Stable hydrolysis.After stirring 24 hours, 3 parts by weight of catalyst manufactured in embodiment 4-a are added again, by the pH of mixed solution It is adjusted to alkaline state.At this point, the macromolecule of cage modle can imported into the X section of B structure, continuously carry out in the reactor anti- It answers, forms macromolecule as chemical formula 4.But due to being obtained together with other by-products, it is therefore desirable to additional purification. Later, so that temperature is become room temperature, prepare to refine and the tetrahydrofuran in mixed solution is removed in vacuo.
[embodiment 4-e] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
In the mixture for reacting end in above-described embodiment 4-d, 200 parts by weight of methylene chloride are added, with distilled water one Classification washing is played, when the pH for distilling water layer is in neutrality, solvent is completely removed by vacuum decompression.Later, 2 are precipitated in methyl alcohol It is secondary, unreacted monomer is removed, with 30 parts by weight in the solvent that tetrahydrofuran and aqueous solution are mixed with 9.5:0.5 weight ratio After dissolution -20 DEG C at a temperature of take care of 2 days.This be in order to make not imported into macromolecule and the substance closed by cagelike structure again Crystallization, thus purification easy to accomplish.
It will complete the solid matter obtained after recrystallization process to filter, after vacuum decompression with confirming no a variety of by-products Obtain the macromolecule of chemical formula 4.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight can in terms of styrene scaled value acquisition 12,000 value, the n value of X is 4-6, and the n value of Y is 4-6, especially The result of chemical formula 4 is as follows.
29Si-NMR(CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -81.5 (points), - 82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 22.This When, manufacturing method has used the method with the equity of method used 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, using following methods, and by reciprocity with above-described embodiment 1 Method, manufactured compound fragment.
[embodiment 5-a] is used to generate the pH reacting condition (importing of B, D structure) of excessive D structure
In the embodiment 4-b mixed solution just reacted, the HCL aqueous solution 5 of 0.36wt% is very slowly added dropwise Parts by weight, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, 5 times of the amount of preparation embodiment 4-b is The diphenyl tetramethoxy disiloxane of 25 parts by weight, and be added at one time, after stirring 1 hour, embodiment is added again 5 parts by weight of catalyst manufactured in 1-a, are adjusted to alkaline state for the pH of mixed solution.After reaction, temperature is made to become normal Temperature makes the whole be changed into water solution mixture by the way that the tetrahydrofuran in mixed solution is removed in vacuo.At 4 hours After mixing, a part is taken, is passed through29Si-NMR and1It is that H-NMR is analyzed to be deposited in B structure as a result, confirming Alkoxy quantitative change be 0.012mmol/g, the repetitive unit of B and D are imported with about 1:9 ratio.In addition, the benzene second of measurement Alkene conversion molecular weight is 24,000.In addition, can not see list in high molecular GPC form even if having imported cagelike structure The molecular weight distribution of only cage modle substance, therefore can confirm that cagelike structure imported into macromolecular chain by successive reaction well.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (width), 3.1,2.8,2.6,1.5 (width), 0.6.29Si-NMR (CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -82.5 (width)
[embodiment 5-b] imports X (importing of B, D structure) in B structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 5-a, then utilizes trifunctional Monomer makes end be changed into cagelike structure.100 parts by weight of substance obtained in embodiment 5-a are dissolved in the tetrahydro of 50 parts by weight Then furans is added the distilled water of 5 parts by weight and manufactures mixed solution.Later, it is added in manufactured mixed solution 10 parts by weight of HCl of 0.36wt% simultaneously stir 10 minutes, are then added at one time 3 parts by weight of methyltrimethoxysilane, realize Stable hydrolysis.After stirring 24 hours, 3 parts by weight of catalyst manufactured in embodiment 4-a are added again, by the pH of mixed solution It is adjusted to alkaline state.At this point, the macromolecule of cage modle can imported into the X section of B structure, continuously carry out in the reactor anti- It answers, forms macromolecule as chemical formula 5.But due to being obtained together with other by-products, it is therefore desirable to additional purification. Later, so that temperature is become room temperature, prepare to refine and the tetrahydrofuran in mixed solution is removed in vacuo.
[embodiment 5-c] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
In the mixture for reacting end in above-described embodiment 5-b, 200 parts by weight of methylene chloride are added, with distilled water one Classification washing is played, when the pH for distilling water layer is in neutrality, solvent is completely removed by vacuum decompression.Later, 2 are precipitated in methyl alcohol It is secondary, unreacted monomer is removed, with 30 parts by weight in the solvent that tetrahydrofuran and aqueous solution are mixed with 9.5:0.5 weight ratio After dissolution -20 DEG C at a temperature of take care of 2 days.This be in order to make not imported into macromolecule and the substance closed by cagelike structure again Crystallization, thus purification easy to accomplish.
It will complete the solid matter obtained after recrystallization process to filter, after vacuum decompression with confirming no a variety of by-products Obtain the macromolecule of chemical formula 5.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight can in terms of styrene scaled value acquisition 16,000 value, the n value of X is 4-6, and the n value of Y is 4-6, especially The result of chemical formula 5 is as follows.
29Si-NMR(CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -81.5 (points), - 82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 23.This When, manufacturing method has used the method with the equity of method used 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, using following methods, and by reciprocity with above-described embodiment 1 Method, manufactured compound fragment.
The generation of [embodiment 6-a] chain end E structure
20 parts by weight of methylene chloride are added dropwise in the mixture obtained in the embodiment 4-c of not additional purification, are added dropwise 5 parts by weight of HCL aqueous solution of 0.36 weight %, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, one 1 parts by weight of dimethyl tetramethoxy-silicane are added in secondary property.At this point, in the molecular structure not yet hydrolyzed and existing part with It is easy to be changed into hydrolysate in the acidic aqueous solution layer of solvent separation, the other reactant with generation contracts in organic solvent layer It closes and imports E in terminal units.After stirring in 5 hours, stops the stirring of reaction, the temperature of reactor is adjusted to room temperature.
[embodiment 6-b] imports cagelike structure in B structure and the X of end E structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 6-a, then utilizes trifunctional Monomer makes end be changed into cagelike structure.In the embodiment 6-a mixed solution just reacted, it is added at one time methyl trimethoxy 3 parts by weight of oxysilane realize that stable hydrolysis adds the catalyst 3 manufactured in embodiment 1-a after stirring 24 hours again The pH of mixed solution is adjusted to alkaline state by parts by weight.At this point, the macromolecule of cage modle can be imported in E structure end, reacting It is continuously reacted in device, forms macromolecule as chemical formula 6.But due to being obtained together with other by-products, Need additional purification.Later, so that temperature is become room temperature, prepare essence and the tetrahydrofuran in mixed solution is removed in vacuo System.
[embodiment 6-c] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
After obtaining the mixture that reaction terminates in above-described embodiment 6-b, benefit is washed with distilled water, when the pH of distillation water layer is in When neutral, solvent is completely removed by vacuum decompression.Later, it precipitates 2 times in methyl alcohol, unreacted monomer is removed, in tetrahydro furan Mutter and solvent that aqueous solution is mixed with 9.5:0.5 weight ratio in after the dissolution of 30 parts by weight -20 DEG C at a temperature of take care of 2 It.This is in order to recrystallize the substance for not importeding into macromolecule and being closed by cagelike structure, thus purification easy to accomplish.
The solid matter obtained after recrystallization process filtering will be completed, is confirmed together with a variety of by-products after vacuum decompression Obtain the macromolecule of chemical formula 6.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight obtains 21,000 value in terms of styrene scaled value, the n value of X is 4-6, and the n value of Y is 4-6, especially chemical The result of formula 6 is as follows.
29Si-NMR(CDCl3) δ -68.2, -71.8 (points), -72.3 (width), -81.1 (points), -80.8 (points), -82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 24.This When, manufacturing method has used the method with the equity of method used in above-described embodiment 6.
[table 24]
Embodiment 7: the high molecular synthesis of silsesquioxane A-B-A-D structure composite
It is following to carry out continuous hydrolysis and condensation by step about synthesis step, using identical with the method for above-described embodiment 1 Method has manufactured compound fragment.
The manufacture of [embodiment 7-a] catalyst
In order to adjust basicity, 10 weight % hydroxides are mixed in 25 weight % aqueous solution of tetramethylammonium hydroxide (TMAH) Potassium (KOH) aqueous solution and prepare catalyst 1a.
[embodiment 7-b] line style silsesquioxane synthesizes (A precursor)
In the drying flask for having condenser pipe and blender, be added dropwise 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 2- (3,4- epoxycyclohexyl) second is added dropwise after stirring at normal temperature 1 hour in 1 parts by weight of catalyst manufactured in above-described embodiment 7-a 15 parts by weight of tetrahydrofuran are added dropwise again and futher stir 5 hours for 20 parts by weight of base trimethoxy silane.It takes in stirring Mixed solution after removing catalyst and impurity and cleaning twice and filtering, is confirmed by IR analysis in end group SI-OH functional group (the 3200cm of generation-1), measure molecular weight as a result, confirming 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 structure
In the drying flask for having condenser pipe and blender, be added dropwise 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of catalyst manufactured in above-described embodiment 7-a are added dropwise 2- (3,4- epoxycyclohexyl) after stirring at normal temperature 1 hour 20 parts by weight of tetrahydrofuran are added dropwise again and futher stir 2 hours for 10 parts by weight of ethyl trimethoxy silane.It takes in stirring Mixed solution, removed and cleaning twice catalyst and impurity and filter after, passed through1The alkane of H-NMR analysis remaining Oxygroup is 0.1mmol/g line style silsesquioxane below, this is sharp when importing cagelike structure by successive reaction later Part.About the morphological analysis of linear structure, by XRD analysis, confirming overall structure is linear structure.Measurement point Son amount as a result, confirm linear structure silsesquioxane have 8,000 styrene convert molecular weight.
The synthesis (synthesis of A-B-A precursor) of [embodiment 7-d] line style silsesquioxane structure
In the drying flask for having condenser pipe and blender, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, institute are added dropwise 10 parts by weight of embodiment 7-a catalyst of manufacture are added dropwise embodiment 7-b precursor and 7-c precursor are each after stirring at normal temperature 1 hour 10 parts by weight of tetrahydrofuran are added dropwise again and futher stir 24 hours for 20 parts by weight.The mixed solution in stirring is taken, is passed through Clean twice and remove catalyst and impurity and filter after, by IR analysis confirm end group generate SI-OH official It can group (3200cm-1), measure molecular weight as a result, confirming the silsesquioxane of linear structure there is 15,000 styrene to change Calculate molecular weight.
1H-NMR(CDCl3) δ 3.7,3.4,3.3 (width), 3.1,2.8,2.6,1.5 (width), 0.6.
[embodiment 7-e] cagelike structure continuously generates (importing of D structure)
In above-described embodiment 7-d mixed solution, 5 parts by weight of HCL aqueous solution of 0.36 weight % are very slowly added dropwise, Be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, it is added at one time two silicon oxygen of diphenyl tetramethoxy 5 parts by weight of alkane realize that stable hydrolysis adds 7 parts by weight of catalyst manufactured in embodiment 7-a after stirring 1 hour again, The pH of mixed solution is adjusted to alkaline state.At this point, independently forming the D structure that alkoxy opens with linear macromolecule Precursor.A small amount of sample is acquired, is analyzed by H-NMR and IR, after the survival rate for confirming methoxyl group, when survival rate is 10% When, 10 parts by weight of HCL aqueous solution of 0.36 weight % are slowly added dropwise, pH is adjusted to acidity.Later, it is added at one time phenyl three 1 parts by weight of methoxy silane simultaneously stir 15 minutes, then add 20 parts by weight of catalyst manufactured in 1-a.In mixing in 4 hours It is confirming after stirring as a result, confirming the macromolecule for generating cage modle in macromolecule.Later, so that temperature is become room temperature, lead to The tetrahydrofuran being removed in vacuo in mixed solution is crossed, the whole is made to be changed into water solution mixture.Mixing at 4 hours is stirred After mixing, a part is taken, is passed through29It is that Si-NMR is analyzed as a result, confirm using phenyl import structure analysis Peak shows two sharp forms, has not manufactured macromolecule as chemical formula 7 to other remaining by-products.In addition, The styrene conversion molecular weight of measurement is 18,000.
29Si-NMR(CDCl3) δ -68.2, -72.3 (width), -81.1 (points), -80.8 (points), -82.5 (width)
[embodiment 7-f] imports X (completion of A-B-A-D structure) in B structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 7-e, then utilizes trifunctional Monomer makes end be changed into cagelike structure.100 parts by weight of substance obtained in embodiment 7-e are dissolved in the tetrahydro of 50 parts by weight Then furans is added the distilled water of 5 parts by weight and manufactures mixed solution.Later, it is added in manufactured mixed solution 10 parts by weight of HCl of 0.36wt% simultaneously stir 10 minutes, are then added at one time 3 parts by weight of methyltrimethoxysilane, realize Stable hydrolysis.After stirring 24 hours, 3 parts by weight of catalyst manufactured in embodiment 7-a are added again, by the pH of mixed solution It is adjusted to alkaline state.At this point, the macromolecule of cage modle can imported into the X section of B structure, continuously carry out in the reactor anti- It answers, forms macromolecule as chemical formula 7.But due to being obtained together with other by-products, it is therefore desirable to additional purification. Later, so that temperature is become room temperature, prepare to refine and the tetrahydrofuran in mixed solution is removed in vacuo.
[embodiment 7-g] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
In the mixture for reacting end in above-described embodiment 7-f, 200 parts by weight of methylene chloride are added, with distilled water one Classification washing is played, when the pH for distilling water layer is in neutrality, solvent is completely removed by vacuum decompression.Later, 2 are precipitated in methyl alcohol It is secondary, unreacted monomer is removed, with 30 parts by weight in the solvent that tetrahydrofuran and aqueous solution are mixed with 9.5:0.5 weight ratio After dissolution -20 DEG C at a temperature of take care of 2 days.This be in order to make not imported into macromolecule and the substance closed by cagelike structure again Crystallization, thus purification easy to accomplish.
It will complete the solid matter obtained after recrystallization process to filter, after vacuum decompression with confirming no a variety of by-products Obtain the macromolecule of chemical formula 7.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight can in terms of styrene scaled value acquisition 24,000 value, the n value of X is 4-6, and the n value of Y is 4-6.
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 25.This When, manufacturing method has used the method with the equity of method used 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, using following embodiments, and by with 1 phase of above-described embodiment Same method, has manufactured compound fragment.
[embodiment 8-a] is used to generate the pH reacting condition of excessive D structure
In the embodiment 7-d mixed solution just reacted, the HCL aqueous solution 15 of 0.36wt% is very slowly added dropwise Parts by weight, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, 5 times of the amount of preparation embodiment 7-e is The diphenyl tetramethoxy disiloxane of 25 parts by weight, and be added at one time, after stirring 1 hour, embodiment is added again 20 parts by weight of catalyst manufactured in 7-a, are adjusted to alkaline state for the pH of mixed solution.After reaction, become temperature Room temperature makes the whole be changed into water solution mixture by the way that the tetrahydrofuran in mixed solution is removed in vacuo.At 4 hours Mixing after, take a part, pass through29Si-NMR and1It is that H-NMR is analyzed as a result, confirming in B structure The quantitative change of existing alkoxy is 0.006mmol/g, and the repetitive unit of B and D are imported with about 5:5 ratio.In addition, the benzene of measurement Ethylene conversion molecular weight is 32,000.In addition, can not see in high molecular GPC form even if having imported cagelike structure The molecular weight distribution of individual cage modle substance, therefore can confirm that cagelike structure imported into macromolecule by successive reaction well Chain.
1H-NMR(CDCl3) δ 7.5,7.2,3.7,3.4,3.3 (width), 3.1,2.8,2.6,1.5 (width), 0.6.29Si-NMR (CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -82.5 (width)
[embodiment 8-b] imports X in B structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 8-a, then utilizes trifunctional Monomer makes end be changed into cagelike structure.100 parts by weight of substance obtained in embodiment 8-a are dissolved in the tetrahydro of 50 parts by weight Then furans is added the distilled water of 5 parts by weight and manufactures mixed solution.Later, it is added in manufactured mixed solution 10 parts by weight of HCl of 0.36wt% simultaneously stir 10 minutes, are then added at one time 3 parts by weight of methyltrimethoxysilane, realize Stable hydrolysis.After stirring 24 hours, 3 parts by weight of catalyst manufactured in embodiment 7-a are added again, by the pH of mixed solution It is adjusted to alkaline state.At this point, the macromolecule of cage modle can imported into the X section of B structure, continuously carry out in the reactor anti- It answers, forms macromolecule as chemical formula 8.But due to being obtained together with other by-products, it is therefore desirable to additional purification. Later, so that temperature is become room temperature, prepare to refine and the tetrahydrofuran in mixed solution is removed in vacuo.
[embodiment 8-c] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
In the mixture for reacting end in above-described embodiment 8-b, 200 parts by weight of methylene chloride are added, with distilled water one Classification washing is played, when the pH for distilling water layer is in neutrality, solvent is completely removed by vacuum decompression.Later, 2 are precipitated in methyl alcohol It is secondary, unreacted monomer is removed, with 30 parts by weight in the solvent that tetrahydrofuran and aqueous solution are mixed with 9.5:0.5 weight ratio After dissolution -20 DEG C at a temperature of take care of 2 days.This be in order to make not imported into macromolecule and the substance closed by cagelike structure again Crystallization, thus purification easy to accomplish.
It will complete the solid matter obtained after recrystallization process to filter, after vacuum decompression with confirming no a variety of by-products Obtain the macromolecule of chemical formula 1.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight can in terms of styrene scaled value acquisition 36,000 value, the n value of X is 4-6, and the n value of Y is 4-6, especially The result of chemical formula 8 is as follows.
29Si-NMR(CDCl3) δ -72.5 (width), -81.1 (points), -80.8 (points), -79.9 (points), -81.5 (points), - 82.5 (width)
In addition, having manufactured silsesquioxane composite high-molecular and compound fragment using the monomer recorded in following table 26.This When, manufacturing method has used the method with the equity of method used 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, using following embodiments, 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
20 parts by weight of methylene chloride are added dropwise in the mixture obtained in the embodiment 7-g of not additional purification, are added dropwise 5 parts by weight of HCL aqueous solution of 0.36 weight %, be adjusted to pH in acidity, and 4 DEG C at a temperature of stir 30 minutes.Later, one 1 parts by weight of dimethyl tetramethoxy-silicane are added in secondary property.At this point, in the molecular structure not yet hydrolyzed and existing part with It is easy to be changed into hydrolysate in the acidic aqueous solution layer of solvent separation, the other reactant with generation contracts in organic solvent layer It closes and imports E in terminal units.After stirring in 5 hours, stops the stirring of reaction, the temperature of reactor is adjusted to room temperature.
[embodiment 9-b] imports cagelike structure in B structure and the X of end E structure
Not additional purification ground prepares the organic layer of product obtained in above-described embodiment 9-a, then utilizes trifunctional Monomer makes end be changed into cagelike structure.In the embodiment 9-a mixed solution just reacted, it is added at one time methyl trimethoxy 3 parts by weight of oxysilane realize that stable hydrolysis adds the catalyst 3 manufactured in embodiment 7-a after stirring 24 hours again The pH of mixed solution is adjusted to alkaline state by parts by weight.At this point, the macromolecule of cage modle can be imported in E structure end, reacting It is continuously reacted in device, forms macromolecule as chemical formula 9.But due to being obtained together with other by-products, Need additional purification.Later, so that temperature is become room temperature, prepare essence and the tetrahydrofuran in mixed solution is removed in vacuo System.
[embodiment 9-c] passes through the removal of the by-product of precipitating and recrystallization, the acquirement of product
After obtaining the mixture that reaction terminates in above-described embodiment 9-b, benefit is washed with distilled water, when the pH of distillation water layer is in When neutral, solvent is completely removed by vacuum decompression.Later, it precipitates 2 times in methyl alcohol, unreacted monomer is removed, in tetrahydro furan Mutter and solvent that aqueous solution is mixed with 9.5:0.5 weight ratio in after the dissolution of 30 parts by weight -20 DEG C at a temperature of take care of 2 It.This is in order to recrystallize the substance for not importeding into macromolecule and being closed by cagelike structure, thus purification easy to accomplish.
The solid matter obtained after recrystallization process filtering will be completed, is confirmed together with a variety of by-products after vacuum decompression Obtain the macromolecule of chemical formula 9.In addition, by GPC result compared with NMR result when, in each stage macromolecule growth in do not have The cage modle for exporting to the low molecule individually obtained sharp form, compound high score can successfully be obtained by confirming from the result Son.At this point, molecular weight obtains 28,000 value in terms of styrene scaled value, the n value of X is 4-6, and the n value of Y is 4-6.
In addition, having manufactured silsesquioxane composite high-molecular using the monomer recorded in following table 27.At this point, manufacturer Method has used the method with the equity of method used in above-described embodiment 9.
[table 27]
[experiment]
To special using thin slice (Sheet) measurement physics, the optics of the compound fragment manufacture manufactured in above-described embodiment 1 to 9 Property.
Glass transition temperature evaluates (IPC-TM-650): the shearing of thin disc made with 0.3mm thickness is big at 2X20mm It is small, it is placed in the geometry tensometer (Tension geometry) of dynamic viscoelastic analyzer (DMA-8000) and is measured.This When, about determination condition, it is measured under usually used 1Hz frequency with 2 DEG C of speed per minute.
Surface hardness measurement: it in general, about pencil hardness method (JIS 5600-5-4), is generally commented with 750g load Valence, but with the more exacting terms than the condition, i.e. 1kgf load, on coated face with 45 degree of angle by pencil with per second The speed of 0.5mm moves horizontally 10mm and scratches film, and is evaluated with scratch.If do not had for 2 times or more in 5 experiments Confirm the scratch of 3mm or more, then the pencil of a degree of hardness selected to be evaluated, if it is confirmed that scratch be 2 times with On, then it selects the pencil of next grade of the pencil hardness and is evaluated as pencil hardness.
Scratch test (Scratch test) measurement: about the abrasion evaluation assessment using steel wool, in 1kg or so weight Iron hammer front end winding #0000 steel wool (Steel wool), reciprocating friction test film 15 times, measure its haze value, but In this evaluation, with the more exacting terms i.e. 400 time friction test piece than the condition, and measures mist degree and carry out meat with microscope Eye evaluation.About as a result, being judged as failure when mist degree increases by 0.05% or more.
Permeability (ASTM D1746): using ultraviolet-visible absorption spectroscopy (UV/vis spectroscopy) measurement for The total light transmittance of the light of the thin slice incidence of production.
Yellow chromaticity (ASTM D1925): the thin slice relative to standard sources (CIE) is measured using color difference meter (CM-3700A) Chromaticity coordinates value.
[table 28]
As shown in above-mentioned table 28, when blending with each macromolecule, the rising effect of excellent glass transition temperature is shown Fruit, and confirm optical characteristics and surface hardness, scratch characteristic etc. while being improved.
INDUSTRIAL APPLICABILITY
Thermoplastic resin composition of the invention is by the inclusion of the line style sesquialter silicon in a macromolecule containing specific structure The silsesquioxane composite high-molecular of oxygen alkane chain and cage-type silsesquioxane, thus heat resistance, chemical resistance, soil resistance, gas Through preventing characteristic, permeability, coloring, wearability and surface hardness etc. excellent.

Claims (13)

1. a kind of thermoplastic resin composition, which is characterized in that include represented by any of following chemical formula 1 to 9 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 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、R22Respectively It independently is hydrogen；Deuterium；Halogen；Amido；Epoxy group；Cyclohexyl ring oxygroup；(methyl) acryloyl group；Mercapto；Isocyanate group； Itrile group；Nitro；By deuterium, halogen, amido, epoxy group, (methyl) acryloyl group, mercapto, isocyanate group, itrile group, nitro, benzene The substituted or non-substituted C of base1~C40Alkyl；C2~C40Alkenyl；C1~C40Alkoxy；C3~C40Naphthenic base；C3~ C40Heterocyclylalkyl；C6~C40Aryl；C3~C40Heteroaryl；C3~C40Aralkyl；C3~C40Aryloxy group；Or C3~ C40Aryl mercaptan base,
A and d is each independently 1 to 100,000 integer,
B is each independently 1 to 500 integer,
E is each independently 1 or 2,
N is each independently integer of 1 to 20.
2. thermoplastic resin composition according to claim 1, which is characterized in that a be 3 to 1000 integer, b be 1 to 500 integer, the integer that d is 1 to 500.
3. thermoplastic resin composition according to claim 1, which is characterized in that the average value of n is 4 to 5.
4. thermoplastic resin composition according to claim 1, which is characterized in that the silsesquioxane composite high-molecular Weight average molecular weight be 1,000 to 1,000,000.
5. thermoplastic resin composition according to claim 1, which is characterized in that the thermoplastic resin composition includes Silsesquioxane composite high-molecular and macromolecule resin represented by any of described chemical formula 1 to 9.
6. thermoplastic resin composition according to claim 5, which is characterized in that the macromolecule resin is selected from by PC (polycarbonate), PMMA (polymethyl methacrylate), PES (polyether sulfone), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), 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), polyurethane and epoxy resin composition one or more of group macromolecule resin.
7. thermoplastic resin composition according to claim 1, which is characterized in that the thermoplastic resin composition includes Silsesquioxane composite high-molecular and inorfil represented by any of described chemical formula 1 to 9.
8. thermoplastic resin composition according to claim 1, which is characterized in that the silsesquioxane composite high-molecular Content be at least 1 weight %.
9. thermoplastic resin composition according to claim 1, which is characterized in that the composition further includes face Material.
10. the article manufactured by thermoplastic resin composition described in claim 1.
11. article according to claim 10, which is characterized in that the article is the shell of electronic products.
12. article according to claim 10, which is characterized in that the article is functional fiber or functional garment.
13. article according to claim 10, which is characterized in that the article is plastic living articles, illumination, protection Cap, automobile interior exterior ornament materials, fishing rod, golf club, yacht, Discussion on architecture ornament materials, piping, furniture or film.
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