CN106699998A - Fluorine-silicon epoxy and polyacrylate tetra-block polymer and preparation method for same - Google Patents
Fluorine-silicon epoxy and polyacrylate tetra-block polymer and preparation method for same Download PDFInfo
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- CN106699998A CN106699998A CN201611128550.7A CN201611128550A CN106699998A CN 106699998 A CN106699998 A CN 106699998A CN 201611128550 A CN201611128550 A CN 201611128550A CN 106699998 A CN106699998 A CN 106699998A
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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
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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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- 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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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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Abstract
The invention relates to the field of materials, and discloses a fluorine-silicon epoxy and polyacrylate tetra-block polymer, which is polydimethylsiloxane-epoxy-b-polymethyl methacrylate-b-polyhexafluorobutyl methacrylate. A method for preparing the fluorine-silicon epoxy and polyacrylate tetra-block polymer comprises the following steps: 1, preparing a polydimethylsiloxane-epoxy di-block copolymer; 2, preparing a halogen atom-terminated polydimethylsiloxane chain initiator; 3, preparing a polydimethylsiloxane-epoxy-b-polystyrene methyl methacrylate polymethyl methacrylate triblock copolymer; 4, preparing a polydimethylsiloxane-epoxy-b-polymethyl methacrylate-b-polyhexafluorobutyl methacrylate tetra-block polymer. An epoxy chain segment introduced in reaction has relatively strong adhesive force, so that the adhesion performance with a target basic surface is greatly improved, and the effect of firm adhesion to various basic 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 turned into 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 preceding state key encouragement, the high-technology field given priority to, " 12 " emphasis hair is also listed in by work office of national defence section
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.Current China has turned into 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, rub resistance high
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
The 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 use 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 ageing-resistant, the UV resistant irradiation, resistance in acrylate coatings
In corrosion and the performance basis such as water-fast, alkaline-resisting, coating performance is improved using organosilicon, make coating have preferably it is heat-resisting, antifouling,
Characteristic, thus the relative acrylate coatings, the Technological Economy good combination property of the type coating, anti-fouling effect such as do not after-tack under high temperature
Also have some improvement.More than improve coating compared with, without improved Fluorocarbon resin coating have longer durability, more preferably
Antifouling property, but production cost it is high, using being 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 still need to improve to adapt to external working environment
It is required that.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 unitary 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
Dimethyl silicone polymer-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 used in CN104193923A
The method of micro- heating equally uses ATRP, 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 for biomedical neck in CN103524752A
Domain；Liu Yue great waves et al. are prepared for the copolymer of organic fluorinated silicone-polyurethane blocks and are generated in field of textiles in CN105646828A
Effect.
These researchs focus mostly on and are using silicone backbone, and fluorine-containing functional group pendant has reached 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
The market development targetedly product.This patent is to have considered construction market for cost and the demand of adhesive force.
The content of the invention
The present invention at present research in produced problem, novelty propose it is a kind of can be with the target of industrialization production
Polymer, i.e. dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-polymethylacrylic acid hexafluoro butyl ester four are embedding
Section polymer, abbreviation fluorine silicon epoxy and the block polymer of polyacrylate four.
A kind of preparation method the present invention also aims to provide fluorine silicon epoxy and the block polymer of polyacrylate four.
Technical problem solved by the invention can be realized using following technical scheme：
Fluorine silicon epoxy and the block polymer of polyacrylate four, it is characterised in that for dimethyl silicone polymer-epoxy-
B-poly-methyl acrylate-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.
The preparation method of fluorine silicon epoxy and the block polymer of polyacrylate four, it is characterised in that
Step one, prepares dimethyl silicone polymer-epoxy di-block copolymer：Under nitrogen protection, by bisphenol-A epoxy
Resin and both-end hydroxyl-dimethyl silicone polymer are according to mol ratio 1：1.1 ratio is added in reaction bulb, is reacted under 80 degrees Celsius
2-6 hour, obtain dimethyl silicone polymer-epoxy di-block copolymer；
Step 2, prepares dimethyl silicone polymer-epoxy di-block copolymer：Under nitrogen protection, step one is obtained
Dimethyl silicone polymer-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 dimethyl silicone polymer-epoxy di-block copolymer：2- chlorine isobutyryl chlorides：Three second
Amine=1:1.4~3.8:3.8~7.2, after reaction terminates, filtering is dissolved in dichloromethane after separation, and sodium acid carbonate is used successively
Saturated solution and watery hydrochloric acid washing at least one times, are filtered again, and purified product chlorine atom end-blocking is obtained after filtrate decompression is distilled
Dimethyl silicone polymer-polyurethane copolymer；
Step 3, prepares dimethyl silicone polymer-epoxy-b-polymethyl methacrylate triblock copolymer：In nitrogen
Under gas shielded, using chlorine atom end-blocking dimethyl silicone polymer-epoxy di-block copolymer as initiator, with stannous chloride
It is catalyst, with diethylenetriamine as part, according to mol ratio methyl methacrylate：Catalyst：Macromole evocating agent：Part
=10-5000:1:1:2 carry out ATRP in dimethylbenzene, and temperature heats polymerization 10- between 50-80 degree
24 hours, dchloromethane is used after cooling, and precipitated, obtain after at least three times repeatedly dimethyl silicone polymer-epoxy-
B-polymethyl methacrylate triblock copolymer；
Step 4, prepares dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-polymethylacrylic acid six
The block polymer of fluorine butyl ester four：Under nitrogen protection, the dimethyl silicone polymer-epoxy-b-poly- methyl for being obtained with step 3
Methyl acrylate triblock copolymer as macromole evocating agent, with stannous chloride as catalyst, with diethylenetriamine as part,
According to mol ratio polymethylacrylic acid hexafluoro butyl ester：Catalyst：Macromole evocating agent：Part=10-100:1:1:2 in dimethylbenzene
In carry out ATRP, temperature between 50-80 degree, heating polymerization 10-24 hour, dichloromethane is used after cooling
Alkane dilutes, and precipitates, obtain after at least three times repeatedly dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-
The block polymer of polymethylacrylic acid hexafluoro butyl ester four.
In step one, both-end hydroxyl-dimethyl silicone polymer can use '-diphenylmethane diisocyanate or different fluorine that
Ketone diisocyanate etc. is substituted containing two monomers of isocyanate groups, and bisphenol A type epoxy resin can use bisphenol F type epoxy
Resin is substituted.
In step 2,2- chlorine isobutyryl chlorides, but be bromine atoms end-blocking poly- two for obtaining can be replaced with bromo-derivative
Methylsiloxane-b-polyurethane copolymer, for replacing the dimethyl silicone polymer-polyurethane copolymer of chlorine atom end-blocking.
In step 3, catalyst can replace the stannous chloride, part can to use three (2- pyridines) methyl amines with cuprous bromide
Instead of diethylenetriamine.The methyl methacrylate of selection is a kind of monomer inexpensively, while the step also can be used it
His cheap lipid monomer such as EMA, butyl methacrylate etc..
In step 4, catalyst can replace the stannous chloride, part can to use three (2- pyridines) methyl amines with cuprous bromide
Instead of 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. ATRP is used, and reaction is gentle, product yield high, narrow molecular weight distribution；
2. react in can by control cheap methyl methacrylate monomer molal quantity come control targe product into
This, reaches the demand in market, to meet the purpose of industrialization；
3. the epoxy segment introduced in reacting possesses adhesive force higher, greatly improves the tack with target basal plane
Can so that its function that firm attachment can be realized 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 dimethyl silicone polymer-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, prepares dimethyl silicone polymer-epoxy di-block copolymer macromolecular chain initiator
Under nitrogen protection, by bisphenol A epoxide resin and both-end hydroxyl-dimethyl silicone polymer 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 dimethyl silicone polymer-epoxy two
Thing.Wherein isocyanates can also select other species, such as '-diphenylmethane diisocyanate, PPDI or different
Containing two monomers of isocyanate groups, epoxy also may be selected other types epoxy resin to fluorine that ketone diisocyanate etc., such as
Bisphenol F.
Step 2, prepares the PolydimethylsiloxaneChain Chain initiator of halogen atom end-blocking
Under nitrogen protection, di-block copolymer macromolecular obtained above and 2- chlorine isobutyryl chloride and triethylamine are existed
10-15 hour is sufficiently stirred at room temperature, and after reaction terminates, filtering is dissolved in dichloromethane after separation, and bicarbonate is used successively
Sodium saturated solution and watery hydrochloric acid washing are at least one times.Filter again, purified product chlorine atom envelope is obtained after filtrate decompression is distilled
The dimethyl silicone polymer at end-polyurethane copolymer macromole evocating agent.Also can be used bromo-derivative such as 2- bromines different in this reaction
Butyl acylbromide, but the dimethyl silicone polymer-b-polyurethane macromolecular initiator for being bromine atoms end-blocking for obtaining.
Wherein reaction mol ratio is dimethyl silicone polymer-polyurethane：2- chlorine isobutyryl chlorides：Triethylamine=1:1.4~
3.8:3.8~7.2, further preferred 1:1.7~3.5:4~6, still further preferably 1:2:5,
Step 3, prepares dimethyl silicone polymer-epoxy-b-polymethyl methacrylate triblock copolymer and divides greatly
Subchain initiator
The ATRP is carried out under nitrogen protection, with dimethyl silicone polymer-ring that chlorine atom is blocked
Oxygen macromolecular as initiator, with stannous chloride as catalyst, with diethylenetriamine as part, according to mol ratio methacrylic acid
Methyl esters：Catalyst：Macromole evocating agent：Part=10-5000:1:1:2, further preferred 10-20:1:1:2, it is further excellent
Select 15:1:1:2.ATRP is carried out in dimethylbenzene, between 50-80 degree, 10-24 is individual for heating polymerization for temperature
Hour, dchloromethane is used after cooling, and precipitate.Obtain after at least three times repeatedly dimethyl silicone polymer-epoxy-b-
Polymethyl methacrylate triblock copolymer macromolecular chain initiator.Wherein catalyst is alternatively cuprous bromide, and part also may be used
Three (2- pyridines) methyl amines of selection.
Step 4, prepares target product dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-poly- methyl
Hexafluorobutyl acrylate
Prepare target product is equally carried out under nitrogen protection, is drawn as macromolecular using the target product in above-mentioned step 3
Hair agent, with stannous chloride 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 50-60:1:1:2, still further preferably 55:1:
1:2.ATRP is carried out in dimethylbenzene, temperature is heating 10-24 hour of polymerization, cold between 50-80 degree
But dchloromethane is used afterwards, and is precipitated.Dimethyl silicone polymer-polyurethane-b-poly- methyl is obtained after at least three times repeatedly
Acrylate-b-polymethylacrylic acid hexafluoro butyl ester Tetrablock copolymer macromolecular chain initiator.Wherein catalyst is alternatively
Cuprous bromide, part also may be selected three (2- pyridines) methyl amines.
It is big in the dimethyl silicone polymer-epoxy-b-polymethyl methacrylate triblock copolymer described in step 3
The preparation method of molecule chain initiator, the methyl methacrylate that it is selected is a kind of monomer inexpensively, while the step
Also other cheap lipid monomer such as EMAs, butyl methacrylate etc. can be used；
Fluorochemical monomer can equally select other kinds, such as methacrylic acid seven in the target product described in step 4
The alkyl chain of fluorine butyl ester or other all or part of fluoro.
Compared with the silicon-fluorine polymer thing in existing document patent, the present invention is with special effect：Turned using atom
Radical polymerization is moved, reaction is gentle, product yield high, narrow molecular weight distribution；Can be by controlling cheap acrylic acid in reaction
Ester monomer molal quantity carrys out the cost of control targe product, reaches the demand in market, to meet the purpose of industrialization.
It should be understood by those skilled in the art that, the present invention is not limited to the above embodiments, above-described embodiment and explanation
Merely illustrating the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also has
Various changes and modifications, these changes and improvements all fall within the protetion 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 polyacrylate four, it is characterised in that for dimethyl silicone polymer-epoxy-b-
Poly-methyl acrylate-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 polyacrylate four, it is characterised in that
Step one, prepares dimethyl silicone polymer-epoxy di-block copolymer：Under nitrogen protection, by bisphenol A epoxide resin
With both-end hydroxyl-dimethyl silicone polymer according to mol ratio 1：1.1 ratio is added in reaction bulb, and 2-6 is reacted under 80 degrees Celsius
Individual hour, obtain dimethyl silicone polymer-epoxy di-block copolymer；
Step 2, prepares dimethyl siloxane-epoxy di-block copolymer：Under nitrogen protection, by obtained in step one poly- two
It is individual small that methylsiloxane-epoxy di-block copolymer is sufficiently stirred for 10-15 at room temperature with 2- chlorine isobutyryl chloride and triethylamine
When, wherein reaction mol ratio is dimethyl silicone polymer-epoxy di-block copolymer：2- chlorine isobutyryl chlorides：Triethylamine=1:
1.4~3.8:3.8~7.2, after reaction terminates, filtering is dissolved in dichloromethane after separation, molten with sodium acid carbonate saturation successively
Liquid and watery hydrochloric acid washing at least one times, are filtered again, and poly- the two of purified product chlorine atom end-blocking are obtained after filtrate decompression is distilled
Methylsiloxane-polyurethane copolymer；
Step 3, prepares dimethyl silicone polymer-epoxy-b-polymethyl methacrylate triblock copolymer：Protected in nitrogen
Under shield, the dimethyl silicone polymer-epoxy di-block copolymer using chlorine atom end-blocking as initiator, with stannous chloride to urge
Agent, with diethylenetriamine as part, according to mol ratio methyl methacrylate：Catalyst：Macromole evocating agent：Part=
10-5000:1:1:2 carry out ATRP in dimethylbenzene, and temperature heats polymerization 10-24 between 50-80 degree
Individual hour, dchloromethane is used after cooling, and precipitated, obtain after at least three times repeatedly dimethyl silicone polymer-epoxy-
B-polymethyl methacrylate triblock copolymer；
Step 4, prepares dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-polymethylacrylic acid hexafluoro fourth
The block polymer of ester four：Under nitrogen protection, the dimethyl silicone polymer-epoxy-b-polymethyl for being obtained with step 3
Sour methyl esters triblock copolymer as macromole evocating agent, with stannous chloride as catalyst, with diethylenetriamine as part, according to
Mol ratio polymethylacrylic acid hexafluoro butyl ester：Catalyst：Macromole evocating agent：Part=10-100:1:1:2 enter in dimethylbenzene
Row ATRP, temperature is heating 10-24 hour of polymerization, dilute with dichloromethane after cooling between 50-80 degree
Release, and precipitate, obtain dimethyl silicone polymer-epoxy-b-poly-methyl acrylate-b-poly- first after at least three times repeatedly
The block polymer of base hexafluorobutyl acrylate four.
3. the preparation method of fluorine silicon epoxy according to claim 2 and the block polymer of polyacrylate four, its feature exists
In in step one, both-end hydroxyl-dimethyl silicone polymer is substituted with containing two monomers of isocyanate groups.
4. the preparation method of a kind of fluorine silicon epoxy according to claim 3 and the block polymer of polyacrylate four, it is special
Levy and be, in step one, both-end hydroxyl-dimethyl silicone polymer '-diphenylmethane diisocyanate or the isocyanide of isophorone two
Acid esters replaces.
5. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polyacrylate four, it is special
Levy and be, 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 polyacrylate four, it is special
Levy and be, in step 2, add bromo-derivative, but the dimethyl silicone polymer-b-polyurethane for being bromine atoms end-blocking for obtaining
Copolymer, instead of dimethyl silicone polymer-polyurethane copolymer that chlorine atom is blocked.
7. the preparation method of a kind of fluorine silicon epoxy according to claim 6 and the block polymer of polyacrylate four, it is special
Levy and be, 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 polyacrylate four, it is special
Levy and be, in step 3 and/or step 4, catalyst replaces stannous chloride with cuprous bromide, or, part is with three (2- pyridines)
Methyl amine replaces diethylenetriamine.
9. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polyacrylate four, it is special
Levy and be, in step 3, methyl methacrylate EMA, butyl methacrylate replaces.
10. the preparation method of a kind of fluorine silicon epoxy according to claim 2 and the block polymer of polyacrylate four, it is special
Levy and be, in step 4, polymethylacrylic acid hexafluoro butyl ester the fluorine butyl ester of methacrylic acid seven or other wholes or portion
The alkyl chain of fluoro is divided to replace.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215363A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Method for synthesizing organic silicon di-block copolymers |
| CN101215364A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Fluorine silicon tri-block copolymers and preparation method thereof |
| CN101215362A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Silicon-acrylic tri-block copolymer with low surface energy and preparing method thereof |
| CN103408707A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Amphiphilic crosslinkable fluorosilicon resin, water-borne coating and super-amphiphobic coating prepared through water-borne coating |
| CN103483966A (en) * | 2013-09-17 | 2014-01-01 | 三棵树涂料股份有限公司 | Pollution-prevention self-cleaning building outer wall coating based on fluorine-silicon block polymer and preparing method thereof |
| CN103635764A (en) * | 2011-04-20 | 2014-03-12 | 阿塞里克股份有限公司 | Refrigerator with efficient cooling evaporator |
| CN104193923A (en) * | 2014-10-13 | 2014-12-10 | 陕西省石油化工研究设计院 | Hydrophobic/oleophobic fluorosilicone triblock polymer and preparation method thereof |
-
2016
- 2016-12-09 CN CN201611128550.7A patent/CN106699998A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215363A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Method for synthesizing organic silicon di-block copolymers |
| CN101215364A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Fluorine silicon tri-block copolymers and preparation method thereof |
| CN101215362A (en) * | 2008-01-08 | 2008-07-09 | 厦门大学 | Silicon-acrylic tri-block copolymer with low surface energy and preparing method thereof |
| CN103635764A (en) * | 2011-04-20 | 2014-03-12 | 阿塞里克股份有限公司 | Refrigerator with efficient cooling evaporator |
| CN103408707A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Amphiphilic crosslinkable fluorosilicon resin, water-borne coating and super-amphiphobic coating prepared through water-borne coating |
| CN103483966A (en) * | 2013-09-17 | 2014-01-01 | 三棵树涂料股份有限公司 | Pollution-prevention self-cleaning building outer wall coating based on fluorine-silicon block polymer and preparing method thereof |
| CN104193923A (en) * | 2014-10-13 | 2014-12-10 | 陕西省石油化工研究设计院 | Hydrophobic/oleophobic fluorosilicone triblock polymer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 宫大军 等: ""端羟基聚二甲基硅氧烷改性环氧树脂的研究"", 《化学与黏合》 * |
| 戴震: ""环氧、丙烯酸改性水性聚氨酯的合成及性能"", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
| 蔡元婧: ""环氧改性聚二甲基硅氧烷的合成及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 龚蔚: ""双酚A型聚羟基醚-聚二甲基硅氧烷交替嵌段共聚物的合成、表征及其用于热固性环氧树脂的改性研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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Application publication date: 20170524 |