CN106674451A - Fluorosilicone epoxy and polystyrene tetrablock polymer and preparation method thereof - Google Patents
Fluorosilicone epoxy and polystyrene tetrablock polymer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
Abstract
The invention relates to the field of materials and provides a fluorosilicone epoxy and polystyrene tetrablock polymer which is polydimethylsiloxane-epoxy-b-polystyrene-b-polymethyl methacrylate. A preparation method of the fluorosilicone epoxy and polystyrene tetrablock polymer comprises the following steps: step one, preparing a polydimethylsiloxane-epoxy diblock copolymer; step two, preparing a halogen atom terminated polydimethylsiloxane chain initiator; step three, preparing a polydimethylsiloxane-epoxy-b-polystyrene triblock copolymer; step four, preparing a polydimethylsiloxane-epoxy-b-polystyrene-b-hexafluorobutyl polymethacrylate tetrablock polymer. Epoxy chain segments introduced in the reaction have high adhesion, so that the adhesion to the target substrate surfaces is greatly improved, and the firm adhesion to various substrate surfaces can be achieved.
Description
Technical field
The present invention relates to Material Field, and in particular to polymer.
Background technology
Fluorine material has excellent physico-chemical property and mechanical performance, is widely used in each neck of the national economic development
Domain, has especially become irreplaceable raw material in space flight and aviation, defence and military and high-technology field.In national oil chemical industry
Be fluorinated in " 12 " development plan work be one it is special a piece is single-row is planned, and listed in by State Economic and Trade Commission, the Department of Science and Technology ought
One of front state key encouragement, the high-technology field given priority to, work office of national defence section is also listed in " 12 " emphasis and is sent out
The high end materials of exhibition.Fluorocarbon resin coating material receives much concern because of its excellent physical and chemical performance, and China is after the U.S., day
The 3rd possesses fluorocarbon coating synthetic technology and realizes the country of industrialization after this.At present China has become fluorine the biggest in the world
Chemical industry primary producing country and exported country, but apply research and development deficiency, technical merit to fall behind and allow domestic fluorine chemical industry to be difficult to
Break away from the passive situation that low-end product is superfluous, high-end product is not enough.High-technology field, such as photovoltaic industry, communication electronics are produced
Industry, the appearance and development of New Energy Industry, the coating material of its critical component to traditional fluorocarbon resin retain high-weatherability and
Chemicals, in the performance basis such as water and oil-resistant, easy to clean, it is proposed that new requirement：Such as high-flexibility, high rub resistance
Property, self-cleaning property and is produced on a large scale.
At the same time, (referring mainly to skin surface) and ocean (referring mainly to oceanographic equipment outer surface) two kinds of rows are built
Coating used in industry is although numerous, but antifouling automatic cleaning coating species is simultaneously few.Current nonpolluting coating is limited primarily to propylene
Acid esters coating, the coating of silicon third and the class of Fluorocarbon resin coating three.Because the coating performance of single base material compounding is difficult in adapt to again
Miscellaneous external environment, also appears in the newspapers repeatly to above-mentioned three kinds of coating modified products.It is to adopt modified propylene than more typical two class
Acid esters coating, organic silicon-acrylate composite coating.Wherein acrylate type coating is preferable in terms of weather resistance, antifouling effect
It is really undesirable.Organic silicon-acrylate composite coating is mainly in the ageing-resistant of acrylate coatings, UV resistant irradiation, resistance to
In corrosion and the performance basis such as water-fast, alkaline-resisting, using organosilicon coating performance is improved, make coating have preferably it is heat-resisting, antifouling,
The characteristic such as do not after-tack under high temperature, thus relative acrylate coatings, the Technological Economy good combination property of the type coating, anti-fouling effect
Also have some improvement.Compared with improving coating more than, there is longer durability, more preferably without improved Fluorocarbon resin coating
Antifouling property, but production cost is high, application is limited to.Even if in addition, outstanding Fluorocarbon resin coating still cannot be realized
It is antifouling from source, also, the weatherability of these materials, drug-resistant aspect of performance remain a need for improving to adapt to external working environment
Require.In a word, comprehensive various aspects of performance, especially at antifouling aspect, fluor resin coating show at present it is most with prospects, and
Because its low-surface-energy also has good potential in terms of friction resistant.For actual demand, domestic or even two kinds of the whole world
All there is antifouling automatically cleaning in industry " object " (such as in-service ship).Market existing procucts single function, although temporarily
Certain aspect functional requirement can be met, but generally existing life of product is short, consumption big, or even there is secondary pollution defect.
Currently there are some researchs in fluorosilicic block copolymer forward position, such as positive letter of sieve etc. is adopted in CN101215364A
Polydimethylsiloxane-b-polymethyl methacrylate-b-poly- seven fluorine butyl methyl third is prepared for atom transfer polymerization
Olefin(e) acid ester.This kind of product remains the characteristic of fluorine silicon, and reduces cost by PMMA, but due to the rigidity of segment itself, nothing
Method is used in the larger occasion of basic unit's STRESS VARIATION, is easily caused cracking phenomena；In CN103435764A big vast outstanding person et al. in sieve just
The concentration of catalyst is improved on the basis of letter, but target product is basically identical；Cheng Xitao et al. is adopted in CN104193923A
The method of micro- heating equally adopts atom transfer radical polymerization, prepares the triblock polymer of hydrophobic/oleophobic fluorine silicon.
CN101983976A Li Hui et al. prepare the block copolymerization of dimethyl siloxane-polyacrylic acid fluoroalkyl fat using RAFT techniques
Thing；Li Hui et al. is prepared for fluorosilicone-POSS acrylate block copolymers and leads for biomedical in CN103524752A
Domain；Liu Yue great waves et al. are prepared for the copolymer of organic fluorinated silicone-polyurethane blocks and generate in field of textiles in CN105646828A
Effect.
These researchs focus mostly on adopting silicone backbone, fluorine-containing functional group pendant to reach the fundamental characteristics of fluorine silicon,
Some researchs take into account cost, and some researchs take into account pliability.But research is there is no for building and marine anti-pollution two
Market development targetedly product.
The content of the invention
The present invention for produced problem at present research, novelty propose it is a kind of can be with the target of industrialization production
Polymer, i.e. polydimethylsiloxane-epoxy-b-polystyrene-b-block polymerization of polymethylacrylic acid hexafluoro butyl ester four
Thing, abbreviation fluorine silicon epoxy and the block polymer of polystyrene four.
The present invention also aims to provide the preparation method of a kind of fluorine silicon epoxy and the block polymer of polystyrene four.
Technical problem solved by the invention can employ the following technical solutions to realize：
Fluorine silicon epoxy and the block polymer of polystyrene four, it is characterised in that for polydimethylsiloxane-epoxy-b-
Polystyrene-b-polymethylacrylic acid hexafluoro butyl ester, structural formula is
Wherein R is bisphenol-A group：
Wherein m, n, j, x, y are each segment degree of polymerization.
This polymer due to introducing polystyrene chain segment inexpensively, by the molecular weight for controlling the segment, can be with
The cost of control targe product, reaches the surface characteristic for both possessing F-Si hydrophobic oleophobic, is provided simultaneously with higher adhesive force and strong
Degree, it is also possible to which cost is cheap, reaches the purpose of industrial volume production.
The preparation method of fluorine silicon epoxy and the block polymer of polystyrene four, it is characterised in that
Step one, prepares polydimethylsiloxane-epoxy di-block copolymer：Under nitrogen protection, by bisphenol-A epoxy
Resin and both-end hydroxyl-polydimethylsiloxane are according to mol ratio 1：1.1 ratio is added in reaction bulb, is reacted under 80 degrees Celsius
2-6 hour, obtains polydimethylsiloxane-epoxy di-block copolymer；
Step 2, prepares polydimethylsiloxane-epoxy di-block copolymer：Under nitrogen protection, step one is obtained
Polydimethylsiloxane-epoxy di-block copolymer and 2- chlorine isobutyryl chloride and triethylamine be sufficiently stirred for 10- at room temperature
15 hours, wherein reaction mol ratio is polydimethylsiloxane-epoxy di-block copolymer：2- chlorine isobutyryl chlorides：Three second
Amine=1:1.4~3.8:3.8~7.2, after reaction terminates, filter, it is dissolved in after separation in dichloromethane, sodium bicarbonate is used successively
Saturated solution and dilute hydrochloric acid are washed at least one times, are filtered again, and purified product chlorine atom end-blocking is obtained after filtrate decompression is distilled
Polydimethylsiloxane-polyurethane copolymer；
Step 3, prepares polydimethylsiloxane-epoxy-b-polystyrene triblock copolymer：In nitrogen protection
Under, using the polydimethylsiloxane-epoxy di-block copolymer of chlorine atom end-blocking as initiator, with Cu-lyt. as catalysis
Agent, with diethylenetriamine as part, according to mol ratio styrene：Catalyst：Macromole evocating agent：Part=10-5000:1:1:
2 carry out atom transfer radical polymerization in dimethylbenzene, and temperature is between 50-80 degree, plus 10-24 hour of thermal polymerization, cooling
Dchloromethane is used afterwards, and is precipitated, obtain polydimethylsiloxane-epoxy-b-polystyrene three after at least three times repeatedly
Block copolymer；
Step 4, prepares polydimethylsiloxane-epoxy-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester
Four block polymers：Under nitrogen protection, it is embedding with the polydimethylsiloxane-epoxy-b-polystyrene three of step 3 acquisition
Section copolymer as macromole evocating agent, with Cu-lyt. as catalyst, with diethylenetriamine as part, according to the poly- first of mol ratio
Base hexafluorobutyl acrylate：Catalyst：Macromole evocating agent：Part=10-100:1:1:2 carry out atom transfer in dimethylbenzene
Radical polymerization, temperature is between 50-80 degree, plus 10-24 hour of thermal polymerization, and dchloromethane is used after cooling, and precipitates,
Repeatedly polydimethylsiloxane-epoxy-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester is obtained after at least three times
Four block polymers.
In step one, both-end hydroxyl-polydimethylsiloxane can be with '-diphenylmethane diisocyanate or different fluorine that
The monomer containing two isocyanate groups such as ketone diisocyanate is substituted, and bisphenol A type epoxy resin can use bisphenol F type epoxy
Resin is substituted.
In step 2,2- chlorine isobutyryl chlorides, but poly- the two of the as bromine atoms end-blocking for obtaining can be replaced with bromo-derivative
Methylsiloxane-b-polyurethane copolymer, for the polydimethylsiloxane-polyurethane copolymer for replacing chlorine atom to block.
In step 3, catalyst can replace Cu-lyt. with cuprous bromide, and part can be with three (2- pyridines) methyl amines
Replace diethylenetriamine.The styrene of selection is a kind of monomer inexpensively, while the step also can be cheap using other
Styrene or benzyl ethylene monomer such as p-methylstyrene, 2,5- dimethyl styrenes etc.；If will to end of the chain pliability
Ask higher, substituted ethylene can be selected or replace the third vinyl monomer.
In step 4, catalyst can replace Cu-lyt. with cuprous bromide, and part can be with three (2- pyridines) methyl amines
Replace diethylenetriamine.Fluorochemical monomer can equally select other kinds, such as the fluorine butyl ester of methacrylic acid seven or other
The alkyl chain of all or part of fluoro.
Beneficial effect：Compared with the silicon-fluorine polymer thing in existing document patent, the present invention is with special effect：
1. atom transfer radical polymerization is adopted, and reaction is gentle, product yield high, narrow molecular weight distribution；
2. in reacting city can be reached by controlling cheap styrene monomer molal quantity come the cost of control targe product
The demand of field, to meet the purpose of industrialization；
3. the epoxy segment introduced in reacting possesses higher adhesive force, greatly improves the tack with target basal plane
Can so that it can realize the function of firm attachment on various basal planes.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, enter below
One step illustrates the present invention.
Subject polymer polydimethylsiloxane-epoxy-b-poly-methyl acrylate-b-of the present invention gathers
Hexafluorobutyl mathacrylate, structural formula is as follows：
Wherein R is bisphenol-A group：
Wherein m, n, j, x, y are each segment degree of polymerization
The preparation method of four above-mentioned block polymers is：
Step one, prepare polydimethylsiloxane-epoxy di-block copolymer macromolecular chain initiator
Under nitrogen protection, by bisphenol A epoxide resin and both-end hydroxyl-polydimethylsiloxane according to mol ratio 1：1.1
Ratio add reaction bulb in, under 80 degrees Celsius react 2-6 hour, obtain the block copolymerization of polydimethylsiloxane-epoxy two
Thing.Wherein isocyanates can also select other species, such as '-diphenylmethane diisocyanate, PPDI or different
The monomers containing two isocyanate groups such as fluorine that ketone diisocyanate, epoxy also may be selected other types epoxy resin, such as
Bisphenol F.
Step 2, the PolydimethylsiloxaneChain Chain initiator for preparing halogen atom end-blocking
Under nitrogen protection, di-block copolymer macromole obtained above and 2- chlorine isobutyryl chloride and triethylamine are existed
10-15 hour is sufficiently stirred under room temperature, after reaction terminates, is filtered, be dissolved in after separation in dichloromethane, bicarbonate is used successively
Sodium saturated solution and dilute hydrochloric acid are washed at least one times.Filter again, purified product chlorine atom envelope is obtained after filtrate decompression is distilled
The polydimethylsiloxane at end-polyurethane copolymer macromole evocating agent.Also can be different using bromo-derivative such as 2- bromines in this reaction
Butyl acylbromide, but the polydimethylsiloxane-b-polyurethane macromolecular initiator for being bromine atoms end-blocking for obtaining.
It is polydimethylsiloxane-polyurethane wherein to react mol ratio：2- chlorine isobutyryl chlorides：Triethylamine=1:1.4~
3.8:3.8~7.2, further preferably, 1:1.5~3.0:4~6, still more preferably, 1:1.7:5.
Step 3, prepare polydimethylsiloxane-epoxy-b-polystyrene triblock copolymer macromolecular chain and cause
Agent
The atom transfer radical polymerization is carried out under nitrogen protection, with polydimethylsiloxane-ring that chlorine atom is blocked
Oxygen macromole as initiator, with Cu-lyt. as catalyst, with diethylenetriamine as part, according to mol ratio styrene：Urge
Agent：Macromole evocating agent：Part=10-5000:1:1:2, further preferably, 1000-5000:1:1:2, still further preferably
4000:1:1:2.Atom transfer radical polymerization is carried out in dimethylbenzene, temperature is between 50-80 degree, plus thermal polymerization 10-24 individual
Hour, dchloromethane is used after cooling, and precipitate.Obtain after at least three times repeatedly polydimethylsiloxane-epoxy-b-
Polystyrene triblock copolymer macromolecular chain initiator.Wherein catalyst is alternatively cuprous bromide, and part also may be selected three (2-
Pyridine) methyl amine.
Styrene is a kind of monomer inexpensively, and the step also can be using other cheap styrene or benzyl ethylene
Monomer such as p-methylstyrene, 2,5- dimethyl styrenes etc.；If higher to end of the chain flexibility requirements, can select to replace
Ethylene replaces the third vinyl monomer.
Step 4, prepare target product polydimethylsiloxane-epoxy-b-polystyrene-b-polymethylacrylic acid
Hexafluoro butyl ester
Preparing target product is equally carried out under nitrogen protection, is drawn as macromole using the target product in above-mentioned step 3
Agent is sent out, with Cu-lyt. as catalyst, with diethylenetriamine as part, according to mol ratio polymethylacrylic acid hexafluoro butyl ester：Urge
Agent：Macromole evocating agent：Part=10-100:1:1:2, further preferred 80-100:1:1:2, still further preferably 90:1:
1:2.Atom transfer radical polymerization is carried out in dimethylbenzene, temperature is between 50-80 degree, plus 10-24 hour of thermal polymerization, cold
But dchloromethane is used afterwards, and is precipitated.Repeatedly polydimethylsiloxane-polyurethane-b-polyphenyl second is obtained after at least three times
Alkene-b-polymethylacrylic acid hexafluoro butyl ester Tetrablock copolymer macromolecular chain initiator.Wherein catalyst is alternatively protobromide
Copper, part also may be selected three (2- pyridines) methyl amines.
In this step, fluorochemical monomer can equally select other kinds, such as the fluorine fourth of methacrylic acid seven in target product
The alkyl chain of base ester or other all or part of fluoro.
In above steps, the proportioning of substitute, those skilled in the art can be calculated with oneself, therefore not in this sieve
Row, after substitute, reaction environment, course of reaction are constant.
Compared with the silicon-fluorine polymer thing in existing document patent, the present invention is with special effect：
1st, atom transfer radical polymerization is adopted, reaction is gentle, product yield high, narrow molecular weight distribution；
2nd, city can be reached by controlling cheap styrene monomer molal quantity come the cost of control targe product in reacting
The demand of field, to meet the purpose of industrialization；
3rd, the epoxy segment introduced in reacting possesses higher adhesive force, greatly improves the tack with target basal plane
Can so that it can realize the function of firm attachment on various basal planes.
The ultimate principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement is both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (10)
1. fluorine silicon epoxy and the block polymer of polystyrene four, it is characterised in that for polydimethylsiloxane-epoxy-b-poly-
Styrene-b-polymethylacrylic acid hexafluoro butyl ester, structural formula is
Wherein R is bisphenol-A group：
Wherein m, n, j, x, y are each segment degree of polymerization.
2. the preparation method of fluorine silicon epoxy and the block polymer of polystyrene four, it is characterised in that
Step one, prepares polydimethylsiloxane-epoxy di-block copolymer：Under nitrogen protection, by bisphenol A epoxide resin
With both-end hydroxyl-polydimethylsiloxane according to mol ratio 1：1.1 ratio is added in reaction bulb, and under 80 degrees Celsius 2-6 is reacted
Individual hour, obtains polydimethylsiloxane-epoxy di-block copolymer；
Step 2, prepares polydimethylsiloxane-epoxy di-block copolymer：Under nitrogen protection, will gather obtained in step one
Dimethyl siloxane-epoxy di-block copolymer is sufficiently stirred at room temperature 10-15 with 2- chlorine isobutyryl chloride and triethylamine
Hour, wherein reaction mol ratio is polydimethylsiloxane-epoxy di-block copolymer：2- chlorine isobutyryl chlorides：Triethylamine=
1:1.4~3.8:3.8~7.2, after reaction terminates, filter, it is dissolved in after separation in dichloromethane, sodium bicarbonate saturation is used successively
Solution and dilute hydrochloric acid are washed at least one times, are filtered again, and the poly- of purified product chlorine atom end-blocking is obtained after filtrate decompression is distilled
Dimethyl siloxane-polyurethane copolymer；
Step 3, prepares polydimethylsiloxane-epoxy-b-polystyrene triblock copolymer：Under nitrogen protection, with
Chlorine atom end-blocking polydimethylsiloxane-epoxy di-block copolymer as initiator, with Cu-lyt. as catalyst, with
Diethylenetriamine is part, according to mol ratio styrene：Catalyst：Macromole evocating agent：Part=10-5000:1:1:2,
Atom transfer radical polymerization is carried out in dimethylbenzene, temperature is between 50-80 degree, plus 10-24 hour of thermal polymerization, uses after cooling
Dchloromethane, and precipitating, obtains polydimethylsiloxane-epoxy-b-polystyrene three block after at least three times repeatedly
Copolymer；
Step 4, prepares polydimethylsiloxane-epoxy-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester four embedding
Section polymer：Under nitrogen protection, the polydimethylsiloxane-epoxy-b-polystyrene three block for being obtained with step 3 is total to
Polymers as macromole evocating agent, with Cu-lyt. as catalyst, with diethylenetriamine as part, according to the poly- methyl-prop of mol ratio
Olefin(e) acid hexafluoro butyl ester：Catalyst：Macromole evocating agent：Part=10-100:1:1:2, atom transfer is carried out in dimethylbenzene certainly
It is polymerized by base, temperature is between 50-80 degree, plus 10-24 hour of thermal polymerization, dchloromethane is used after cooling, and precipitated, instead
Polydimethylsiloxane-epoxy-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester four is obtained after multiple at least three times
Block polymer.
3. the preparation method of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, it is characterised in that
In step one, both-end hydroxyl-polydimethylsiloxane is substituted with the monomer containing two isocyanate groups.
4. the preparation method of a kind of fluorine silicon epoxy according to claim 3 and the block polymer of polystyrene four, its feature
It is, in step one, both-end hydroxyl-polydimethylsiloxane '-diphenylmethane diisocyanate or the Carbimide. of isophorone two
Ester replaces.
5. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, its feature
It is that in step one, bisphenol A type epoxy resin is substituted with bisphenol f type epoxy resin.
6. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, its feature
It is in step 2,2- chlorine isobutyryl chlorides, but the polydimethylsiloxanes for being bromine atoms end-blocking for obtaining to be replaced with bromo-derivative
Alkane-b-polyurethane copolymer, for the polydimethylsiloxane-polyurethane copolymer for replacing chlorine atom to block.
7. the preparation method of a kind of fluorine silicon epoxy according to claim 6 and the block polymer of polystyrene four, its feature
It is that bromo-derivative is 2- bromine isobutyl group acylbromides.
8. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, its feature
It is that in step 3 and/or step 4, catalyst cuprous bromide replaces Cu-lyt., or, part is with three (2- pyridines) first
Base amine replaces diethylenetriamine.
9. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, its feature
It is, in step 3, any one generation of styrene methyl styrene, 2,5- dimethyl styrenes, ethylene or propylene apoplexy due to endogenous wind
Replace.
10. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polystyrene four, its feature
It is that in step 4, polymethylacrylic acid hexafluoro butyl ester is with the fluorine butyl ester of methacrylic acid seven or other are all or part of
The alkyl chain of fluoro replaces.
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| CN112175503A (en) * | 2020-10-09 | 2021-01-05 | 赵玮 | Super-smooth coating |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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