CN106632924B - A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof - Google Patents
A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof Download PDFInfo
- Publication number
- CN106632924B CN106632924B CN201611129010.0A CN201611129010A CN106632924B CN 106632924 B CN106632924 B CN 106632924B CN 201611129010 A CN201611129010 A CN 201611129010A CN 106632924 B CN106632924 B CN 106632924B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- polystyrene
- dimethyl silicone
- silicone polymer
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- 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
-
- 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
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- 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 present invention relates to Material Field, four block polymer of fluorine-silicon polyurethane and polystyrene is dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester.The preparation method of four block polymer of fluorine-silicon polyurethane and polystyrene, including, step 1, prepare dimethyl silicone polymer-polyurethane, Step 2: preparing the PolydimethylsiloxaneChain Chain initiator of halogen atom sealing end, step 3 prepares dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer, step 4 prepares dimethyl silicone polymer-polyurethane-b-polystyrene-b-four block polymer of polymethylacrylic acid hexafluoro butyl ester.The polyurethane segment introduced in reaction has higher adhesive force, greatly improves the adhesion property with target basal plane so that it can realize the function of firm attachment on various basal planes.
Description
Technical field
The present invention relates to Material Fields, 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 especially has become irreplaceable raw material in space flight and aviation, defence and military and high-technology field.In national oil chemical industry
Be fluorinated in " 12th Five-Year Plan " development plan work be one it is special a piece is single-row is planned, and be included in and work as by State Economic and Trade Commission, the Department of Science and Technology
One of the high-technology field that preceding state key is encouraged, given priority to, work office of national defence section are also included in " 12th Five-Year Plan " emphasis hair
The high end materials of exhibition.Fluorocarbon resin coating material is concerned due to its excellent physical and chemical performance, and China is after the U.S., day
Third possesses fluorocarbon coating synthetic technology and realizes the country of industrialization after this.China has become the world's largest fluorine at present
Chemical industry primary producing country and exported country, however apply research and development are insufficient, technical merit falls behind domestic fluorine chemical industry is allowed to be difficult to
Break away from low-end product surplus, the insufficient passive situation of high-end product.High-technology field, such as photovoltaic industry, communication electronics production
Industry, the appearance and development of New Energy Industry, the coating material of 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
The coating used in industry is although numerous, but antifouling automatic cleaning coating type and few.Current nonpolluting coating is limited primarily to propylene
Acid esters coating, the third coating of silicon and Fluorocarbon resin coating three classes.Coating performance made of being compounded due to single base-material is difficult to adapt to multiple
Miscellaneous external environment also appears in the newspapers to above-mentioned three kinds of coating modified products repeatly.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
Fruit is 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, improve coating performance using organosilicon, make coating have preferably it is heat-resisting, antifouling,
Characteristics, thus opposite acrylate coatings, the Technological Economy good combination property of the type coating, the anti-fouling effect such as do not after-tack under high temperature
Also it has some improvement.Compared with improving coating above, not improved Fluorocarbon resin coating has longer durability, more preferable
Antifouling property, but production cost it is high, using being limited to.In addition, even if outstanding Fluorocarbon resin coating still cannot achieve
It is antifouling from source, also, there is still a need for improve to adapt to external working environment for the weatherability of these materials, drug-resistant aspect of performance
It is required that.In short, comprehensive various aspects of performance, especially at antifouling aspect, fluor resin coating show at present it is most with prospects, and
Since its low-surface-energy also has good potential in terms of anti-friction.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 have a single function, although temporarily
Certain aspect functional requirement can be met, but generally existing life of product is short, dosage is big, or even there are secondary pollution defects.
The current research for having had some in fluorosilicic block copolymer forward position, for example positive letter of sieve etc. is adopted in CN101215364A
It is prepared for the poly- seven fluorine butyl methyls of dimethyl silicone polymer-b-polymethyl methacrylate-b-third with 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 base's stress variation, is easy to cause cracking phenomena；In CN103435764A big vast outstanding person et al. sieve just
The concentration of catalyst is improved on the basis of letter, but target product is almost the same；Cheng Xitao et al. is used in CN104193923A
The method of micro- heating equally uses 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
Object；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 copolymers of organic fluorinated silicone-polyurethane blocks and are produced in field of textiles in CN105646828A
Effect.
These researchs focus mostly on using silicone backbone, and fluorine-containing functional group pendant has reached the fundamental characteristics of fluorine silicon,
Some researchs consider cost, some researchs consider flexibility.But it there is no research for building and marine anti-pollution two
Targetedly product is developed in market.
Invention content
The present invention for the problem in research at present, it is innovative propose it is a kind of can be with the target of industrialization production
Polymer, i.e. dimethyl silicone polymer-polyurethane-b-polystyrene-b-four block of polymethylacrylic acid hexafluoro butyl ester are poly-
Close object, four block polymer of abbreviation fluorine-silicon polyurethane and polystyrene.
The present invention also aims to provide a kind of preparation method of fluorine-silicon polyurethane and four block polymer of polystyrene.
Following technical scheme may be used to realize in technical problem solved by the invention：
Four block polymer of fluorine-silicon polyurethane and polystyrene, which is characterized in that be the poly- ammonia of dimethyl silicone polymer-
Ester-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester, structural formula are
Wherein m, n, x, y are each segment degree of polymerization.
This polymer is due to introducing polystyrene chain segment inexpensively, can be with by controlling the molecular weight of the segment
The cost of control targe product reaches the surface characteristic for both having F-Si hydrophobic oleophobic, is provided simultaneously with higher adhesive force and strong
Degree, also can cost it is cheap, achieve the purpose that industrial volume production.
The preparation method of four block polymer of fluorine-silicon polyurethane and polystyrene, which is characterized in that
Step 1 prepares dimethyl silicone polymer-polyurethane：Under nitrogen protection, by 1, hexamethylene-diisocyanate and double
Terminal hydroxy group-dimethyl silicone polymer is according to molar ratio 1：1.1 ratio is added in reaction bulb, reacts 2-6 hour at room temperature, obtains
To dimethyl silicone polymer-polyurethane；
Step 2 prepares dimethyl silicone polymer-polyurethane：Under nitrogen protection, by poly dimethyl made from step 1
Siloxanes-polyurethane is sufficiently stirred 10-15 hour at room temperature with 2- chlorine isobutyryl chloride and triethylamine, wherein reaction rubs
You are than being dimethyl silicone polymer-polyurethane：2- chlorine isobutyryl chlorides：Triethylamine=1:1.4~3.8:3.8~7.2, reaction
After, filtering dissolves in methylene chloride after separation, washs at least one with saturated solution of sodium bicarbonate and dilute hydrochloric acid successively
It is secondary, it filters again, dimethyl silicone polymer-polyurethane of purified product chlorine atom sealing end is obtained after filtrate decompression is distilled；
Step 3 prepares dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer：In nitrogen protection
Under, the dimethyl silicone polymer-polyurethane blocked using chlorine atom is as initiator, using stannous chloride as catalyst, with divinyl
Triamine is ligand, according to molar ratio styrene：Catalyst：Macromole evocating agent：Ligand=10-5000:1:1:2 in dimethylbenzene
Atom transfer radical polymerization is carried out, temperature heating 10-24 hour of polymerization, dichloromethane is used after cooling between 50-80 degree
Dilution, and precipitate, at least obtain dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer afterwards three times repeatedly
Object；
Step 4 prepares dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethylacrylic acid hexafluoro fourth
Four block polymer of ester：Under nitrogen protection, the dimethyl silicone polymer-polyurethane-b-polystyrene obtained with step 3
Triblock copolymer is as macromole evocating agent, using stannous chloride as catalyst, using diethylenetriamine as ligand, according to molar ratio
Polymethylacrylic acid hexafluoro butyl ester：Catalyst：Macromole evocating agent：Ligand=10-100:1:1:2 carry out atom in dimethylbenzene
Transferring free-radical polymerization, temperature heating 10-24 hour of polymerization, are diluted after cooling with dichloromethane between 50-80 degree, and
Precipitation, at least obtains dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethylacrylic acid six afterwards three times repeatedly
Four block polymer of fluorine butyl ester.
In step 1, both-end hydroxyl-dimethyl silicone polymer can use '-diphenylmethane diisocyanate or different fluorine that
Ketone diisocyanate etc. is containing there are two the monomers of isocyanate groups to substitute.
In step 2,2- chlorine isobutyryl chlorides can be replaced with bromo-derivative, but what is obtained is poly- the two of bromine atom sealing end
Methylsiloxane-b-polyurethane copolymer is used for replacing dimethyl silicone polymer-polyurethane of chlorine atom sealing end.
In step 3, catalyst can replace stannous chloride, ligand that can use three (2- pyridines) methyl amines with cuprous bromide
Instead of diethylenetriamine.The styrene of selection is a kind of monomer inexpensively, while the step can also be used other cheap
Styrene or benzyl ethylene monomer such as p-methylstyrene, 2,5- dimethyl styrenes etc.；If wanted to end of the chain flexibility
It asks higher, the third vinyl monomer of substituted ethylene or substitution can be selected.
In step 4, catalyst can replace stannous chloride, ligand that can use three (2- pyridines) methyl amines with cuprous bromide
Instead of diethylenetriamine.Fluorochemical monomer can equally select other kinds, for example, seven fluorine butyl ester of methacrylic acid or other
The alkyl chain of all or part of fluoro.
Advantageous effect：Compared with the silicon-fluorine polymer object in existing literature patent, the present invention has the effect of special be：
1. using atom transfer radical polymerization, reaction is mild, product yield high, narrow molecular weight distribution；
2. in reaction 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 polyurethane segment introduced in reaction has higher adhesive force, greatly improve attached with target basal plane
Performance so that it can realize the function of realizing firm attachment on various basal planes.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, below into
One step illustrates the present invention.
Subject polymer dimethyl silicone polymer-polyurethane-b-poly- methyl of polystyrene-b-of the present invention
Hexafluorobutyl acrylate, structural formula are as follows：
Wherein m, n, x, y are each segment degree of polymerization
The preparation method of four above-mentioned block polymers is：
Step 1 prepares dimethyl silicone polymer-polyurethane di-block copolymer macromolecular chain initiator
Under nitrogen protection, by 1, hexamethylene-diisocyanate and both-end hydroxyl-dimethyl silicone polymer are according to molar ratio 1：
1.1 ratio is added in reaction bulb, reacts 2-6 hour at room temperature, and it is total to obtain two block of dimethyl silicone polymer-polyurethane
Polymers.Wherein isocyanates can also select other types, such as '-diphenylmethane diisocyanate, paraphenylene diisocyanate or
Isoflurane chalcone diisocyanate etc. contains the monomer there are two isocyanate groups.
Step 2 prepares the PolydimethylsiloxaneChain Chain initiator of halogen atom sealing end
Under nitrogen protection, di-block copolymer macromolecular obtained above is existed with 2- chlorine isobutyryl chloride and triethylamine
It is sufficiently stirred 10-15 hour at room temperature, after reaction, filtering dissolves in methylene chloride after separation, uses bicarbonate successively
Sodium saturated solution and dilute hydrochloric acid washing are at least once.It filters again, purified product chlorine atom envelope is obtained after filtrate decompression is distilled
The dimethyl silicone polymer at end-polyurethane copolymer macromole evocating agent.It can also be used bromo-derivative such as 2- bromines different in this reaction
Butyl acylbromide, but dimethyl silicone polymer-b-polyurethane macromolecular initiator of obtained as bromine atom sealing end.
Wherein reaction molar ratio is dimethyl silicone polymer-polyurethane：2- chlorine isobutyryl chlorides：Triethylamine=1:1.4~
3.8:3.8~7.2, further preferred 1:1.7:3.8~7.2, still further preferably 1:1.7:3.9.
Step 3 prepares dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer macromolecular chain and draws
Send out agent
The atom transfer radical polymerization carries out under nitrogen protection, poly- with the dimethyl silicone polymer-of chlorine atom sealing end
Urethane macromolecular is as initiator, using stannous chloride as catalyst, using diethylenetriamine as ligand, according to molar ratio styrene：
Catalyst：Macromole evocating agent：Ligand=10-5000:1:1:2, further preferred 4000-5000:1:1:2, then preferably into one
5000:1:1:2.Atom transfer radical polymerization is carried out in dimethylbenzene, temperature is between 50-80 degree, heating polymerization 10-24
Hour, it is diluted with dichloromethane after cooling, and precipitate.At least obtain dimethyl silicone polymer-polyurethane-afterwards three times repeatedly
B-polystyrene triblock copolymer macromolecular chain initiator.Wherein catalyst is alternatively cuprous bromide, and ligand also may be selected three
(2- pyridines) methyl amine.
Step 4 prepares target product dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethyl
Sour hexafluoro butyl ester
It prepares target product equally to carry out under nitrogen protection, be drawn using the target product in above-mentioned step 3 as macromolecular
Agent is sent out, using stannous chloride as catalyst, using diethylenetriamine as ligand, according to molar ratio polymethylacrylic acid hexafluoro butyl ester：It urges
Agent：Macromole evocating agent：Ligand=10-100:1:1:2, further preferred 20-40:1:1:2, still further preferably, 40:1:
1:2.Atom transfer radical polymerization is carried out in dimethylbenzene, temperature is heating 10-24 hour of polymerization, cold between 50-80 degree
But it is diluted, and precipitated with dichloromethane afterwards.At least obtain dimethyl silicone polymer-polyurethane-b-polyphenyl second afterwards three times repeatedly
Alkene-b-polymethylacrylic acid hexafluoro butyl ester Tetrablock copolymer macromolecular chain initiator.Wherein catalyst is alternatively protobromide
Three (2- pyridines) methyl amines also may be selected in copper, ligand.
Dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer macromolecular chain described in step 3
The preparation method of initiator, the styrene that it is selected is a kind of monomer inexpensively, while other benzene can also be used in the step
Ethylene or benzyl ethylene monomer such as p-methylstyrene, 2,5- dimethyl styrenes etc.；If to end of the chain flexibility requirements
It is higher, the third vinyl monomer of substituted ethylene or substitution can be selected.
Fluorochemical monomer can equally select other kinds, such as methacrylic acid seven in 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 object in existing literature patent, the present invention has the effect of special be：Turned using atom
Free radical polymerization is moved, reaction is mild, product yield high, narrow molecular weight distribution；It 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 is introduced in reaction
Polyurethane segment have certain flexibility, greatly improve the bullet extensional energy of target product so that its can stress compared with
Big basal plane realizes the function of cracking resistance.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
1. the preparation method of four block polymer of fluorine-silicon polyurethane and polystyrene, which is characterized in that
Step 1 prepares dimethyl silicone polymer-polyurethane：Under nitrogen protection, by 1, hexamethylene-diisocyanate and both-end hydroxyl
Base-dimethyl silicone polymer is according to molar ratio 1：1.1 ratio is added in reaction bulb, reacts 2-6 hour at room temperature, is gathered
Dimethyl siloxane-polyurethane；
Step 2 prepares dimethyl silicone polymer-polyurethane of chlorine atom sealing end：It under nitrogen protection, will be made from step 1
Dimethyl silicone polymer-polyurethane is sufficiently stirred 10-15 hour at room temperature with 2- chlorine isobutyryl chloride and triethylamine,
Middle reaction molar ratio is dimethyl silicone polymer-polyurethane：2- chlorine isobutyryl chlorides：Triethylamine=1:1.4~3.8:3.8~
7.2, after reaction, filtering is dissolved in methylene chloride after separation, is washed successively with saturated solution of sodium bicarbonate and dilute hydrochloric acid
At least once, it filters again, the dimethyl silicone polymer-that purified product chlorine atom sealing end is obtained after filtrate decompression is distilled is poly-
Urethane；
Step 3 prepares dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer：Under nitrogen protection,
Dimethyl silicone polymer-the polyurethane blocked using chlorine atom is as initiator, using stannous chloride as catalyst, with divinyl three
Amine is ligand, according to molar ratio styrene：Catalyst：Initiator：Ligand=10-5000:1:1:2 carry out atom in dimethylbenzene
Transferring free-radical polymerization, temperature heating 10-24 hour of polymerization, are diluted after cooling with dichloromethane between 50-80 degree, and
Precipitation, at least obtains dimethyl silicone polymer-polyurethane-b-polystyrene triblock copolymer afterwards three times repeatedly；
Step 4 prepares dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester four
Block polymer：Under nitrogen protection, the dimethyl silicone polymer-polyurethane-b-polystyrene three obtained with step 3 is embedding
Section copolymer is as macromole evocating agent, using stannous chloride as catalyst, using diethylenetriamine as ligand, according to molar ratio methyl
Hexafluorobutyl acrylate：Catalyst：Macromole evocating agent：Ligand=10-100:1:1:2 carry out atom transfer certainly in dimethylbenzene
It is polymerize by base, temperature heating 10-24 hour of polymerization, is diluted after cooling with dichloromethane, and precipitate, instead between 50-80 degree
It is multiple at least to obtain dimethyl silicone polymer-polyurethane-b-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester afterwards three times
Four block polymers.
2. the preparation method of four block polymer of a kind of fluorine-silicon polyurethane according to claim 1 and polystyrene, special
Sign is, in step 2,2- chlorine isobutyryl chlorides are replaced with bromo-derivative, but the poly dimethyl silicon of obtained as bromine atom sealing end
Oxygen alkane-polyurethane copolymer, it is 2- to be used for replacing dimethyl silicone polymer-polyurethane of chlorine atom sealing end, the bromo-derivative
Bromine isobutyl group acylbromide.
3. the preparation method of four block polymer of a kind of fluorine-silicon polyurethane according to claim 1 and polystyrene, special
Sign is that in step 3 and/or step 4, catalyst replaces stannous chloride with cuprous bromide, alternatively, three (2- pyridines) of ligand
Methyl amine replaces diethylenetriamine.
4. the preparation method of four block polymer of a kind of fluorine-silicon polyurethane according to claim 1 and polystyrene, special
Sign is, in step 3, any one replacement in styrene methyl styrene, 2,5- dimethyl styrenes.
5. the preparation method of four block polymer of a kind of fluorine-silicon polyurethane according to claim 1 and polystyrene, special
Sign is, in step 4, Hexafluorobutyl mathacrylate is replaced with seven fluorine butyl ester of methacrylic acid.
6. four block polymer of fluorine-silicon polyurethane and polystyrene, which is characterized in that be dimethyl silicone polymer-polyurethane-
B-polystyrene-b-polymethylacrylic acid hexafluoro butyl ester, structural formula are
Wherein m, n, x, y are each segment degree of polymerization, and wherein R isFour block of the fluorine-silicon polyurethane and polystyrene
Polymer is prepared by method described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611129010.0A CN106632924B (en) | 2016-12-09 | 2016-12-09 | A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611129010.0A CN106632924B (en) | 2016-12-09 | 2016-12-09 | A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632924A CN106632924A (en) | 2017-05-10 |
| CN106632924B true CN106632924B (en) | 2018-10-30 |
Family
ID=58824069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611129010.0A Active CN106632924B (en) | 2016-12-09 | 2016-12-09 | A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632924B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041651A (en) * | 2022-12-15 | 2023-05-02 | 中国石油大学(北京) | Organosilicon polymer for thickening carbon dioxide, preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215364B (en) * | 2008-01-08 | 2010-06-30 | 厦门大学 | Fluorine silicon tri-block copolymers and preparation method thereof |
| US8283390B2 (en) * | 2009-09-10 | 2012-10-09 | Sabic Innovative Plastics Ip B.V. | Siloxane block copolymer nanoporous foams, methods of manufacture thereof and articles comprising the same |
| CN102993404B (en) * | 2012-10-19 | 2014-10-08 | 北京化工大学 | Photosensitive fluorosilicone segmented urethane acrylate oligomer and preparation method thereof |
| CN105646828A (en) * | 2016-03-31 | 2016-06-08 | 青岛科技大学 | Organic fluorine-silicone-polyurethane block copolymer synthesizing method |
-
2016
- 2016-12-09 CN CN201611129010.0A patent/CN106632924B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632924A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104403301B (en) | Self-cleaning material for signal lines and preparation method thereof | |
| CN109082202B (en) | Environment-friendly high-strength polyaniline composite coating and preparation method thereof | |
| CN102977291A (en) | Cross-linkable fluorine-containing polymer, and its application in preparation of super-amphiphobic surfaces | |
| CN105778693A (en) | Self-cleaning coating material polymer and preparation method and application thereof | |
| CN102964544B (en) | Water-dispersible crosslinking type fluoropolymer and application of fluoropolymer in preparation of super-amphiphobic surfaces | |
| CN102977292B (en) | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface | |
| CN103408692A (en) | Aqueous dispersion crosslinkable random fluoropolymer and constructed super-amphiphobic coat through aqueous dispersion crosslinkable random fluoropolymer | |
| CN104039909A (en) | Adhesive tape for preventing aquatic biofouling | |
| CN102964546A (en) | Water-dispersible ultraviolet crosslinking fluorine-containing polymer and application thereof | |
| CN106632924B (en) | A kind of fluorine-silicon polyurethane and four block polymer of polystyrene and preparation method thereof | |
| CN102964545B (en) | Ultraviolet-crosslinking fluorine-containing polymer and application thereof in preparing super-amphiphobic surface | |
| CN105431490B (en) | Include constituent and coated article containing the fluoropolymer selected from least one of the group being made up of polymerizable functional group and cross-linking functional group group | |
| CN113773436B (en) | Amphiphilic organic silicon coating and preparation method and application thereof | |
| CN106674451B (en) | A kind of fluorine silicon epoxy and four block polymer of polystyrene and preparation method thereof | |
| CN106632923B (en) | A kind of fluorine-silicon polyurethane and four block polymer of polyacrylate and preparation method thereof | |
| CN103756464A (en) | Waterproof paint, and preparation method thereof | |
| CN103601891A (en) | Cross-linkable fluorosilicon resin as well as preparation method and application thereof in super-amphiphobic material | |
| Li et al. | Novel coating system on poly (ethylene terephthalate) fabrics with mechanically durable liquid-repellence: Application as flexible materials with striking loading capacity | |
| CN104788608B (en) | Fluorine-containing polymer for low-energy surface coating and preparation method of fluorine-containing polymer | |
| CN106189391A (en) | High antifouling inorganic silicate coating of a kind of fluorochemical oligomer and its preparation method and application | |
| CN113527977A (en) | Silicone-acrylic resin coating and preparation method and application thereof | |
| CN106699998A (en) | Fluorine-silicon epoxy and polyacrylate tetra-block polymer and preparation method for same | |
| CN109295733B (en) | Preparation method of water-based fluorine-free super-hydrophobic fabric | |
| CN110655840A (en) | Viaduct fluorocarbon primer and preparation method thereof | |
| CN105401441A (en) | Coating agent for down jackets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |