CN109422850A - The fluorine-containing macromole emulsifying agent of self-crosslinking, the fluorine-containing latex containing the emulsifier, its method of preparation and use - Google Patents

The fluorine-containing macromole emulsifying agent of self-crosslinking, the fluorine-containing latex containing the emulsifier, its method of preparation and use Download PDF

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CN109422850A
CN109422850A CN201811005734.3A CN201811005734A CN109422850A CN 109422850 A CN109422850 A CN 109422850A CN 201811005734 A CN201811005734 A CN 201811005734A CN 109422850 A CN109422850 A CN 109422850A
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fluorine
perfluor
monomer
acid esters
ethylene
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CN109422850B (en
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朱宝库
银雪
梁治樱
张斌
王文彬
宋有志
袁佳佳
张音
王纳川
闫妍
朱利平
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Zhejiang University ZJU
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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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F214/00—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 a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • 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
    • C08F214/00—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 a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • 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
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals

Abstract

The invention discloses a kind of fluorine-containing macromole emulsifying agent of self-crosslinking, the fluorine-containing latex containing the emulsifier, its methods of preparation and use.The fluorine-containing macromole emulsifying agent of self-crosslinking is obtained by solution copolymerization in organic solvent by fluorine-containing vinyl monomer and self-crosslinkable hydrophilic monomer, and fluorine-containing latex then is made as emulsifier fluorochemical monomer and comonomer using obtained polymer solution.The present invention is connected fluorine-containing macromole emulsifying agent made from method using hydrophobic fluorine-containing side chain with hydrophilic radical, and to the monomer of fluorinated with excellent emulsifying effectiveness, fluorine-containing latex obtained is extremely stable.Fluorine-containing latex of the invention can be coated on treated object surface by impregnating, smearing again the processing method of high temperature drying, and the hydrophilic radical self-crosslinkable in emulsified dose of high temperature eliminates hydrophilic influence, and waterproof performance is excellent, with good application prospect.

Description

The fluorine-containing macromole emulsifying agent of self-crosslinking, the fluorine-containing latex containing the emulsifier, its preparation And application method
Technical field
The invention belongs to polymeric material field more particularly to a kind of fluorine-containing macromole emulsifying agent of self-crosslinking, contain the cream The fluorine-containing latex of agent, its method of preparation and use.
Background technique
Fluorine atom has the high bond energy (485.3kJ/mol) of strong electronegativity, hypopolarization rate, weak Van der Waals force and C~F key Etc. properties so that fluoropolymer has the advantages such as heat-resisting, solvent resistant outstanding and unique low-surface-energy, by fluoropolymer Object be coated on material surface, can assign material brilliance hydrophobic oleophobic and self-cleaning performance.Existing majority water-proof aagent Active principle be all fluorinated copolymer.
Because fluoropolymer inertia is extremely strong, polymerize used in organic solvent there is safety problem and environmental problem, So existing fluoropolymer is mostly water dispersion emulsion-type.But existing emulsion type fluorine-containing lotion uses common non-fluorine surface more Activating agent is emulsified, and surfactant activity is low and dosage is big, and fluorochemical monomer cannot be emulsified completely and participate in polymerizeing, and is caused Fluorine content is lower in polymer, and polymerization system is unstable, influences waterproof effect, causes the water contact angle of lotion applicator surface to be mostly 120 ° hereinafter, make lotion that can not show good hydrophobic performance, significantly limit the application range of fluorine-containing latex.
Chinese patent (CN101481438A) discloses a kind of random copolymerization fluorine-containing macromole emulsifying agent and preparation method thereof, The macromole emulsifying agent of fluorine-containing chain link and hydrophilic quaternary ammonium salt composition is prepared using free radical polymerization.But it is used in emulsifier Be strong hydrophilicity quaternary ammonium salt group, these hydrophilic quaternary ammonium salt groups can in the use process of coating due to molecule spread make With coating surface is gradually moved to, the hydrophilic radical for being enriched in coating surface can seriously affect the hydrophobicity of coating, Adhesion Resistance And hydrophobic stability and long-term effect, can even elute the fluoropolymer on coating under Long Term Contact water environment lead to performance Further decline, the serious hydrophobic performance for destroying coating.It can be obtained according to experiment, be dredged using prepared by quaternary ammonium salt cationic surfactant After impregnating 9 days in water under water material room temperature, contact angle is down to 72 ° by initial 140 °, does not have apparent hydrophobicity substantially It can be (referring to comparative example 28).
Summary of the invention
For overcome the deficiencies in the prior art, it is fluorine-containing big that technical problem to be solved by the invention is to provide a kind of self-crosslinkings Molecule emulsifier, the fluorine-containing latex containing the emulsifier, its method of preparation and use, the fluorine-containing macromole emulsifying agent of crosslinking Emulsifying effectiveness is good, and emulsion-stabilizing and hydrophilic radical may occur from cross-linking reaction, and hydrophilic radical is prevented to migrate to Air Interface, eliminates Hydrophilic influence, so that the fluorine-containing latex has good hydrophobic performance, contact angle maintains very well all at 120 ° or more Hydrophobic performance, and under water environment hydrophilic radical will not to surface migration, for a long time with water contact contact angle there will not be it is larger Variation.
It is of the invention innovative to obtain the fluorine-containing amphipathic polymer of ternary as fluorine-containing macromole emulsifying agent using polymerisation in solution, The emulsifier on the one hand because fluorine element interaction can adsorb more fluorochemical monomers, more fluorochemical monomer be able into Enter into emulsifier micella and polymerize, to obtain the lotion of high fluorinated volume；On the other hand non-fluorine is introduced in emulsifier Segment not only can control production cost, but also the reactivity ratio of adjustable close and distant aqueous monomer, to adjust the close and distant of emulsifier Water component ratio；More importantly unlike the prior art, the hydroxyl of side chain terminal in the fluorine-containing macromole emulsifying agent of the present invention Stronger hydrogen bond action, the nucleophilicity enhancing of hydroxyl can be formed with the amide group closed on, terminal hydroxyl can occur at high temperature Dehydration self-crosslinking reaction is to be passivated hydrophilic radical.Fluorine-containing latex obtained not only stablize by constituent content, and fluorine content is higher, has Excellent hydrophobic performance.
For this purpose, the present invention adopts the following technical scheme that:
The first purpose of the invention is to provide a kind of fluorine-containing macromole emulsifying agent of self-crosslinking, the self-crosslinking is fluorine-containing big Molecule emulsifier is by the polymer of fluorine-containing chain link, non-fluorine chain link and hydrophilic chain link composition, and the emulsifier is with following institute One of compound of structural formula shown is a variety of
In formula:
The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
The non-fluorine chain link is polymerized by non-fluorine functional monomer B, the structure of the functionalization chain link-B- are as follows:
The hydrophilic chain link is polymerized by hydrophile function monomer C, the structure of the hydrophilic link units-C- Are as follows:
In formula:
R1Selected from H, CH3；
R2Selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
R3Selected from COO (CH2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
J is the integer of 0-17；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
A, b, c are the integer greater than 1；Preferably, a/b=1/50~4/1, a/c=1/1~1/20.
Further, the structural formula of the fluorochemical monomer A is as follows:
In formula:
R1Selected from H, CH3；
R2Selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid three Fluorine ethyl ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl second It is alkene, perfluorododecyl ethylene, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, complete Fluorine hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl Acrylate, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl third Olefin(e) acid ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl-methyl propylene Acid esters, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl second Methyl acrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of.
Further, the structural formula of the non-fluorine functional monomer B is as follows:
In formula:
R1Selected from H, CH3；
R3Selected from COO (CH2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
J is the integer of 0-17；
Preferably, the non-fluorine functional monomer B is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain Number be (methyl) alkyl acrylates of 1-18 any one or it is any a variety of.
Further, the structural formula of the hydrophile function monomer C is as follows:
In formula:
R1Selected from H, CH3；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
Preferably, the hydrophile function monomer C is selected from times of hydroxyethyl acrylamide, hydroxypropyhnethacrylamide It anticipates a kind of or any a variety of.
A second object of the present invention is to provide the preparation method of the fluorine-containing macromole emulsifying agent of the self-crosslinking, the system Preparation Method comprises the following steps: weighing the fluorochemical monomer A of 10~50wt% of total monomer weight, the hydrophile function of 20~80wt% Change the initiation that monomer C, the non-fluorine functional monomer B of 10~70wt% and weight are the 0.1%~5wt% of total monomer weight Agent, be added in the organic solvent of 10%~400wt% of total monomer weight be uniformly mixed, at 40 DEG C~120 DEG C of temperature in Polymerisation in solution is carried out, the fluorine-containing macromole emulsifying agent of self-crosslinking is obtained；The total monomer weight is fluorochemical monomer A, non- The total weight of fluorine functional monomer B and hydrophile function monomer C.
Preferably, the organic solvent is selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N, N dimethyl first Amide, N, N dimethyl acetamide, ethyl acetate, butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether and N- alkylated pyrazole Any one or more in pyrrolidone；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid three Fluorine ethyl ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl second It is alkene, perfluorododecyl ethylene, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, complete Fluorine hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl Acrylate, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl third Olefin(e) acid ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl-methyl propylene Acid esters, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl second Methyl acrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；
Preferably, the non-fluorine functional monomer B is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain Number be (methyl) alkyl acrylates of 1-18 any one or it is any a variety of；
Preferably, the hydrophile function monomer C is selected from times of hydroxyethyl acrylamide, hydroxypropyhnethacrylamide It anticipates a kind of or any a variety of.
Preferably, the initiator is azodiisobutyronitrile, any one in benzoyl peroxide.
Preferably, the organic solvent is selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N, N dimethyl first Amide, N, N dimethyl acetamide, ethyl acetate, butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether and N- alkylated pyrazole One of pyrrolidone is a variety of.
Preferably, the macromole emulsifying agent is made of the organic solvent of 10~50wt% of monomer and surplus.
Preferably, the monomer configuration quality ratio are as follows: fluorochemical monomer 10~50%, hydrophile function monomer 20~ 90% and non-fluorine functional monomer 0~70%.More there is a choosing, 20~30wt% of fluorochemical monomer, hydrophile function monomer 20~ 50wt%, 20~60wt% of non-fluorine monomer.
Preferably, closing the time is 1~20 hour.
Third object of the present invention is to provide a kind of fluorine-containing latex, the fluorine-containing latex includes foregoing fluorine-containing Macromole emulsifying agent.
Further, the fluorine-containing latex by 2~50wt% of monomer, 0~5wt% of fluorine-containing macromole emulsifying agent solution, 0~15wt% of organic solvent and surplus are water composition, and on the basis of the total weight of the monomer, the monomer is by fluorochemical monomer 10~70wt% of A and 30~90wt% of non-fluorine functional monomer B is constituted；
Further, the organic solvent is selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N, N dimethyl Formamide, N, N dimethyl acetamide, ethyl acetate, butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether and N- alkyl One of pyrrolidones is a variety of.
Further, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid Trifluoro ethyl ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl second It is alkene, perfluorododecyl ethylene, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, complete Fluorine hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl Acrylate, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl third Olefin(e) acid ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl-methyl propylene Acid esters, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl second Methyl acrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；It is described Non- fluorine functional monomer B be selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, (methyl) third that carbochain number is 1-18 Olefin(e) acid Arrcostab any one or it is any a variety of.
Fourth object of the present invention is to provide a kind of preparation method and application of fluorine-containing latex, comprises the following steps:
1) emulsion synthesizes: by fluorochemical monomer A and non-fluorine functional monomer B, fluorine-containing macromole emulsifying agent solution, You Jirong Disperse after agent, water mixing, obtains emulsion；
2) fluorine-containing latex synthesizes: be added that weight is the total monomer weight into emulsion obtained by step 1) 0.1%~ The initiator of 5wt% carries out polymerization reaction 1~24 hour at 40 DEG C~120 DEG C of temperature, and reaction terminates to get described fluorine-containing Lotion；
3) fluorine-containing latex dilutes: fluorine-containing latex obtained by step (3) is diluted with the mixed solvent of water or water and ethyl alcohol, Then processing material surface is impregnated or is applied to, high temperature drying 1~10 minute at 100~220 DEG C.
Preferably, fluorochemical monomer A described in step (1) be selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, Acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor Nonyl ethylene, perfluorododecyl ethylene, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene Acid esters, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluor 12 Alkyl ethyl propylene acid esters, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl second Methyl acrylate, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl Methacrylate, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor ten Six alkyl ethylmethyl acrylates, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any It is a variety of.
Preferably, non-fluorine functional monomer B described in step (1) is selected from selected from vinyl acetate, vinyl butyrate, pungent Vinyl acetate, (methyl) alkyl acrylate that carbochain number is 1-18 any one or it is any a variety of；
Preferably, emulsion described in step (1) by 2~50wt% of monomer, 0.2~5wt% of macromole emulsifying agent, have 0~15wt% of solvent and surplus are water composition.
Preferably, mix monomer configuration quality ratio described in step (1) are as follows: 10~70wt% of fluorochemical monomer and non-fluorine 30~90wt% of functionalization monomer.More there are choosing, 20~50wt% of fluorochemical monomer, 50~80wt% of non-fluorine functional monomer.
Preferably, the pre-emulsification time described in step (1) is 5~120min,
Preferably, initiator described in step (2) is azodiisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, mistake Potassium sulfate, hydrogen peroxide, azo diisobutyl amidine hydrochloride, in dicetyl peroxydicarbonate two (2- ethyl hexyl) ester any one or appoint It anticipates a variety of.
Preferably, churned mechanically revolving speed described in step (2) is 200~800r/min.
Preferably, the reaction time is 1~24 hour in step (2).
Preferably, the mixed proportion of water and ethyl alcohol is 50/1~1/5 in step (3), it is furthermore preferred that water and ethyl alcohol mixing ratio Example is 10/1~1/1.
Preferably, extension rate is 1~100 times in step (3).
Preferably, drying temperature is 160~200 DEG C in step (3).
Preferably, drying time is 3~6 minutes in step (3).
In step of the present invention, non-fluorine functional monomer is copolymerized at step (2) with fluorochemical monomer, adjustable fluorine component Content, improve the filming performance and waterproof performance of lotion, optimize preparation cost, so that fluorine-containing latex prepared by step (2) Best performance.Fluorine-containing latex obtained by step (2) is diluted by production requirement in step (3), further optimization is produced into This, and ethyl alcohol, which is added, can improve the wetting property of lotion, increase the application range of fluorine-containing latex.Fluorine-containing latex obtained by step (3) In fluorine-containing side chain can increase the hydrophobic effect on surface at high temperature from being sent to surface enrichment.And unique existing parent in lotion Self-crosslinking can occur at high temperature and form hydrophobic cross-linker network for water base group --- hydroxyl, hydrophilic influence further be eliminated, to mention The hydrophobic effect of high lotion.
Compared with the prior art, the invention has the advantages that:
1) a kind of fluorine-containing latex containing the fluorine-containing macromole emulsifying agent of self-crosslinking provided by the invention is using homemade fluorine-containing Macromole emulsifying agent has preferable emulsifying effectiveness to fluorochemical monomer, in resulting fluorine-containing latex fluorine content may be up to 70wt% and The interference emulsified is not easy by fluorine monomer inertia；And the non-fluorine functional monomer component ratio can 30~90wt% it Between arbitrarily adjust so that fluorine-containing latex provided by the invention have biggish application range.What is contained in resulting lotion is hydrophilic Group high-temperature self-crosslinking can be all passivated in post-processing, to obtain the higher processing surface of hydrophobicity.
2) present invention synthesizes fluorine-containing macromole emulsifying agent using polymerisation in solution, and polymerization process is simple to operation, and molecular weight is easy In regulation, the non-fluorine functional monomer regulates and controls the reactivity ratio of hydrophobic fluorochemical monomer and hydrophile function monomer, and increase contains The adjustable extent of fluorine macromole emulsifying agent HLB value, make fluorine-containing macromole emulsifying agent has very flexible applicability；And it closes At solution may be directly applied to after emulsion polymerization among, do not generate any industrial wastewater exhaust gas.
3) the emulsion polymerization polymerization speed that the present invention uses is fast, and reaction process is short, and molecular weight is high, and gained lotion can be direct Reach waterproof effect by the method for impregnating, smearing to material, operation equipment is simple, is suitble to large-scale production.
Detailed description of the invention
E27 applies contact angle comparison diagram before and after coated with PET film in Fig. 1 embodiment 27.
Specific embodiment
Below with the specific embodiment technical solution that the present invention will be described in detail.The implementation steps of all embodiments with invention Implementation steps described in content are identical, and parameter is every implementation condition and obtains the structure of copolymer in table.Emulsion synthesis The fluorochemical monomer A and non-fluorine comonomer B of use can be with the fluorochemical monomer A and non-fluorine comonomer in fluorine-containing macromole emulsifying agent B is identical, can also be different.It should be noted that the embodiment is not construed as limiting the invention, the ordinary skill of this field All deformations that personnel directly can export or associate from present disclosure, are considered as protection model of the invention It encloses.
Embodiment 1
The synthesis of fluorine-containing latex E1 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
100mlN, N dimethyl acetamide (DMAC), perfluorooctylethyl group acrylate 6g, methyl are added in the reactor Methyl acrylate 6g, hydroxyethyl acrylamide 8g, initiator benzoyl peroxide (BPO) 0.2g, room temperature is molten in the case of leading to nitrogen Oxygen in solution 30 minutes exclusion systems of stirring.It is warming up to 60 DEG C of polymerization temperatures in the case where there is reflux, carries out polymerization reaction.Instead It answers stopping in 6 hours to heat, is passed through air and terminates reaction, fluorine-containing macromole emulsifying agent is made.After discharging, by perfluorooctylethyl group Acrylate 300g, methyl methacrylate 300g, fluorine-containing macromole emulsifying agent solution 50g obtained above, deionized water 2000ml obtained emulsion with ultrasonic emulsifier pre-emulsification 30 minutes at room temperature, emulsion is placed in agitating paddle, temperature Meter, return pipe lead in the four-hole boiling flask of nitrogen device, and ammonium persulfate 6g is added, is warming up to 80 DEG C and starts to polymerize, obtain the white of blueing light Color lotion E1.
The structure of gained fluorine-containing latex E1 and the characterizing method of performance:
1, fluorine-containing latex: being demulsified by structural characterization with alcohol, and precipitating washes away emulsifier, drying to constant weight at 60 DEG C, obtains To polymer be dissolved in tetrahydrofuran (THF), using gel permeation chromatography (GPC) test analysis molecular weight, and will polymerization Object is dissolved in deuterated chloroform and carries out1Its structure of H~nuclear magnetic resonance spectrum analysis.
2, performance characterization: E1 is diluted 10 times in the aqueous solution of 15wt% alcohol, takes a piece of glass fibre non-woven film It is immersed in lotion, is taken out after one minute, vacuum shuts out extra lotion, is dried 5 minutes at 170 DEG C, utilizes contact angle Instrument measure glass fibre non-woven film before treatment after contact angle.
Embodiment 2
The synthesis of fluorine-containing latex E2 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E2 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E2 structure and performance characterization method are identical as the method for embodiment 1.E2 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E2 coating problems of glass fibre non-woven film.
Embodiment 3:
The synthesis of fluorine-containing latex E3 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E3 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E3 structure and performance characterization method are identical as the method for embodiment 1.E3 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E3 coating problems of glass fibre non-woven film.
Embodiment 4:
The synthesis of fluorine-containing latex E4 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E4 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E4 structure and performance characterization method are identical as the method for embodiment 1.E4 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E4 coating problems of glass fibre non-woven film.
Embodiment 5:
The synthesis of fluorine-containing latex E5 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E5 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E5 structure and performance characterization method are identical as the method for embodiment 1.E5 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E5 coating problems of glass fibre non-woven film.
Embodiment 6:
The synthesis of fluorine-containing latex E6 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E6 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E6 structure and performance characterization method are identical as the method for embodiment 1.E6 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E6 coating problems of glass fibre non-woven film.
Embodiment 7:
The synthesis of fluorine-containing latex E7 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E7 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E7 structure and performance characterization method are identical as the method for embodiment 1.E7 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E7 coating problems of glass fibre non-woven film.
Embodiment 8:
The synthesis of fluorine-containing latex E8 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E8 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E8 structure and performance characterization method are identical as the method for embodiment 1.E8 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E8 coating problems of glass fibre non-woven film.
Embodiment 9:
The synthesis of fluorine-containing latex E9 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E9 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E9 structure and performance characterization method are identical as the method for embodiment 1.E2 molecular weight and molecular weight distribution and fluorine content Such as table 3；The contact angle variation such as table 4 before and after through E2 coating problems of glass fibre non-woven film.
Embodiment 10:
The synthesis of fluorine-containing latex E10 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E10 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E10 structure and performance characterization method are identical as the method for embodiment 1.E10 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E10 coating problems of glass fibre non-woven film.
Embodiment 11:
The synthesis of fluorine-containing latex E11 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E11 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E11 structure and performance characterization method are identical as the method for embodiment 1.E11 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E11 coating problems of glass fibre non-woven film.
Embodiment 12:
The synthesis of fluorine-containing latex E12 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E12 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E12 structure and performance characterization method are identical as the method for embodiment 1.E12 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E12 coating problems of glass fibre non-woven film.
Embodiment 13:
The synthesis of fluorine-containing latex E13 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E13 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E13 structure and performance characterization method are identical as the method for embodiment 1.E13 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E13 coating problems of glass fibre non-woven film.
Embodiment 14:
The synthesis of fluorine-containing latex E14 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E14 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E14 structure and performance characterization method are identical as the method for embodiment 1.E14 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E14 coating problems of glass fibre non-woven film.
Embodiment 15:
The synthesis of fluorine-containing latex E15 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E15 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E15 structure and performance characterization method are identical as the method for embodiment 1.E15 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E15 coating problems of glass fibre non-woven film.
Embodiment 16:
The synthesis of fluorine-containing latex E16 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E16 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E16 structure and performance characterization method are identical as the method for embodiment 1.E16 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E16 coating problems of glass fibre non-woven film.
Embodiment 17:
The synthesis of fluorine-containing latex E17 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E17 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E17 structure and performance characterization method are identical as the method for embodiment 1.E17 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E17 coating problems of glass fibre non-woven film.
Embodiment 18:
The synthesis of fluorine-containing latex E18 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E18 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E18 structure and performance characterization method are identical as the method for embodiment 1.E18 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E18 coating problems of glass fibre non-woven film.
Embodiment 19:
The synthesis of fluorine-containing latex E19 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E19 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E19 structure and performance characterization method are identical as the method for embodiment 1.E19 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E19 coating problems of glass fibre non-woven film.
Embodiment 20:
The synthesis of fluorine-containing latex E20 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E20 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E20 structure and performance characterization method are identical as the method for embodiment 1.E20 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E20 coating problems of glass fibre non-woven film.
Embodiment 21:
The synthesis of fluorine-containing latex E21 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E21 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E21 structure and performance characterization method are identical as the method for embodiment 1.E21 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E21 coating problems of glass fibre non-woven film.
Embodiment 22:
The synthesis of fluorine-containing latex E22 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E22 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E22 structure and performance characterization method are identical as the method for embodiment 1.E22 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E22 coating problems of glass fibre non-woven film.
Embodiment 23:
The synthesis of fluorine-containing latex E23 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E23 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E23 structure and performance characterization method are identical as the method for embodiment 1.E23 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E23 coating problems of glass fibre non-woven film.
Embodiment 24:
The synthesis of fluorine-containing latex E24 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E24 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E24 structure and performance characterization method are identical as the method for embodiment 1.E24 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E24 coating problems of glass fibre non-woven film.
Embodiment 25:
The synthesis of fluorine-containing latex E25 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E25 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E25 structure and performance characterization method are identical as the method for embodiment 1.E25 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E25 coating problems of glass fibre non-woven film.
Embodiment 26:
The synthesis of fluorine-containing latex E26 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E26 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E26 structure and performance characterization method are identical as the method for embodiment 1.E26 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E26 coating problems of glass fibre non-woven film.
Embodiment 27:
The synthesis of fluorine-containing latex E27 containing the fluorine-containing macromole emulsifying agent of self-crosslinking:
E27 synthesis process reference embodiment 1, formula and technological parameter are respectively as shown in table 1, table 2.
E27 structure and performance characterization method are identical as the method for embodiment 1.E27 molecular weight and molecular weight distribution and fluorine contain Amount such as table 3；The contact angle variation such as table 4 before and after through E27 coating problems of glass fibre non-woven film.
Comparative example 28:
It is prepared for referring to Chinese patent (CN101481438A) containing strong hydrophilicity group (such as quaternary) emulsifier The synthesis of fluorine-containing latex E28:
E28 uses trimethylallylammonium chloride as hydrophilic monomer, and synthesis process, formula and technological parameter are referring to implementation Example 1, as shown in table 1, table 2.
Comparative example 29:
The synthesis of fluorine-containing latex E29 containing hydroxymethyl acrylate emulsifier:
E29 uses hydroxymethyl acrylate as hydrophilic monomer, synthesis process, formula and technological parameter referring to embodiment 1, As shown in table 1, table 2.
Comparative example 30:
The synthesis of fluorine-containing latex E30 containing hydroxy ethyl methacrylate emulsifier:
E30 uses hydroxy ethyl methacrylate as hydrophilic monomer, synthesis process, formula and technological parameter referring to embodiment 1, As shown in table 1, table 2.
E1, E28, E29 and E30 are diluted to identical multiple respectively and are coated on glass fibre non-woven film, and is existed simultaneously It is 5 minutes dry at 180 DEG C.Test initial contact angle, will treated glass fibre non-woven film soak at room temperature 10 days in water. Contact angle is tested after drying again, the results are shown in Table 5.
Table 5 illustrates using the fluorine-containing latex E1 of self-crosslinking macromolecular fluorine-containing emulsifier of the present invention to glass fibre non-woven film It is coated, impregnates 10 days contact angles in water and be also reduced only by 2 °, within the error range, illustrate fluorine-containing cream of the invention Liquid maintains good hydrophobic performance, illustrates that the hydrophilic radical of the fluorine-containing latex under water environment will not be to surface migration；But it adopts After the E28 of the quaternary emulsifier of strong hydrophilicity and coating, contact angle just drops to 72 ° from 140 ° after impregnating 10 days, dredges It is aqueous to decline 50%.And use other oh types macromole emulsifying agent E29 and E30 coating after, contact angle also from 140 ° or so drop near 80 °, illustrate that the hydroxyl not being connected with amide group can not carry out self-crosslinking, and then can not prevent Hydrophilic radical is to surface migration, so hydrophobic performance decline still has dropped 45%.
Table 1
Table 2
Table 3
Table 4
Table 5
Film number Starting film contact angle/° Soaked rear contact angle/°
E1 150 148
E28 140 72
E29 141 78
E30 139 79

Claims (10)

1. a kind of fluorine-containing macromole emulsifying agent of self-crosslinking, it is characterised in that: the fluorine-containing macromole emulsifying agent of the self-crosslinking is served as reasons Fluorine-containing chain link, the polymer of non-fluorine chain link and hydrophilic chain link composition, the fluorine-containing macromole emulsifying agent structural formula are as follows:
In formula:
The fluorine-containing chain link is polymerized by fluorochemical monomer A, the structure of the fluorine-containing link units-A- are as follows:
The non-fluorine chain link is polymerized by non-fluorine functional monomer B, the structure of the functionalization chain link-B- are as follows:
The hydrophilic chain link is polymerized by hydrophile function monomer C, the structure of the hydrophilic link units-C- are as follows:
In formula:
R1Selected from H, CH3；
R2Selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
R3Selected from COO (CH2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
J is the integer of 0-17；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
A, b, c are the integer more than or equal to 1；Preferably, a/b=1/50~4/1, a/c=1/1~1/20.
2. fluorine-containing macromole emulsifying agent according to claim 1, it is characterised in that: the structural formula of the fluorochemical monomer A It is as follows:
In formula:
R1Selected from H, CH3；
R2Selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro second It is ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethylene, complete Fluorine dodecyl vinyl, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluor oneself Base ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene Acid esters, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl methacrylate Ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl methacrylate Ester, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethyl Methacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of.
3. fluorine-containing macromole emulsifying agent according to claim 1, it is characterised in that: the non-fluorine functional monomer B's Structural formula is as follows:
In formula:
R1Selected from H, CH3；
R3Selected from COO (CH2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
J is the integer of 0-17；
Preferably, the non-fluorine functional monomer B is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain number (methyl) alkyl acrylate of 1-18 any one or it is any a variety of.
4. fluorine-containing macromole emulsifying agent according to claim 1, it is characterised in that: the hydrophile function monomer C's Structural formula is as follows:
In formula:
R1Selected from H, CH3；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
Preferably, the hydrophile function monomer C be selected from hydroxyethyl acrylamide, hydroxypropyhnethacrylamide it is any one Kind is any a variety of.
5. a kind of preparation method of the fluorine-containing macromole emulsifying agent of self-crosslinking described in claim 1, which is characterized in that the system Preparation Method comprises the following steps: weighing the fluorochemical monomer A of 10~50wt% of total monomer weight, the hydrophile function of 20~80wt% Change the initiation that monomer C, the non-fluorine functional monomer B of 10~70wt% and weight are the 0.1%~5wt% of total monomer weight Agent, be added in the organic solvent of 10%~400wt% of total monomer weight be uniformly mixed, at 40 DEG C~120 DEG C of temperature in Polymerisation in solution is carried out, the fluorine-containing macromole emulsifying agent of self-crosslinking is obtained；Preferably, the organic solvent is selected from third Ketone, methyl ethyl ketone, ethylene glycol, propylene glycol, n,N dimethylformamide, N, N dimethyl acetamide, ethyl acetate, acetic acid fourth Any one or more in ester, glycol monoethyl ether, ethylene glycol monoethyl ether and N- alkyl pyrrolidone；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro second It is ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethylene, complete Fluorine dodecyl vinyl, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluor oneself Base ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene Acid esters, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl methacrylate Ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl methacrylate Ester, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethyl Methacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；It is preferred that , it is 1-18's that the non-fluorine functional monomer B, which is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain number, (methyl) alkyl acrylate any one or it is any a variety of；
Preferably, the hydrophile function monomer C be selected from hydroxyethyl acrylamide, hydroxypropyhnethacrylamide it is any one Kind is any a variety of.
6. a kind of fluorine-containing latex, it is characterised in that: the fluorine-containing latex includes claim 1-5 described in any item fluorine-containing big Molecule emulsifier；Preferably, the fluorine-containing latex by 2~50wt% of monomer, 0~5wt% of fluorine-containing macromole emulsifying agent solution, 0~15wt% of organic solvent and surplus are water composition, and on the basis of the total weight of the monomer, the monomer is by fluorochemical monomer 10~70wt% of A and 30~90wt% of non-fluorine functional monomer B is constituted；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro second It is ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethylene, complete Fluorine dodecyl vinyl, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluor oneself Base ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene Acid esters, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl methacrylate Ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl methacrylate Ester, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethyl Methacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；It is preferred that , it is 1-18's that the non-fluorine functional monomer B, which is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain number, (methyl) alkyl acrylate any one or it is any a variety of.
7. a kind of preparation method of fluorine-containing latex, which is characterized in that the preparation method comprises the following steps:
1) emulsion synthesizes: by fluorochemical monomer A and non-fluorine functional monomer B, fluorine-containing macromole emulsifying agent solution, organic solvent, Disperse after water mixing, obtains emulsion；
2) fluorine-containing latex synthesizes: 0.1%~5wt% that weight is the total monomer weight being added into emulsion obtained by step 1) Initiator, carried out polymerization reaction 1~24 hour at 40 DEG C~120 DEG C of temperature, reaction terminate to get the fluorine-containing latex；
Preferably, the fluorochemical monomer A is selected from hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro second It is ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethylene, complete Fluorine dodecyl vinyl, perfluor myristyl ethylene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluor oneself Base ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene Acid esters, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl methacrylate Ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethyl methacrylate Ester, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethyl Methacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；It is preferred that , it is 1-18's that the non-fluorine functional monomer B, which is selected from vinyl acetate, vinyl butyrate, sad vinyl acetate, carbochain number, (methyl) alkyl acrylate any one or it is any a variety of.
8. a kind of hydrophobic material, which is characterized in that the hydrophobic material includes fluorine-containing latex as claimed in claim 6.
9. hydrophobic material according to claim 8, which is characterized in that the hydrophobic material is coating or water and oil repellant Agent.
10. the application method of the hydrophobic material of claim 8 or 9, which is characterized in that by hydrophobic material according to any one of claims 8 Material by dipping, smear again high temperature drying processing method be coated on treated object surface, obtain 120 ° of contact angle or more dredge Water surface；Preferably, the temperature of the high temperature drying is selected from 100~220 DEG C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160486A (en) * 2022-07-29 2022-10-11 同济大学 Antibacterial fluorine-containing emulsifier and preparation method thereof
CN115197362A (en) * 2022-07-29 2022-10-18 同济大学 Super-hydrophobic antibacterial emulsion and preparation and application thereof
CN115260384A (en) * 2022-07-29 2022-11-01 同济大学 Fluorine-containing copolymer emulsion for cement base, super-hydrophobic concrete based on emulsion and preparation method thereof

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CN1120847A (en) * 1993-04-14 1996-04-17 纳幕尔杜邦公司 Water- and oil-repellent fluoro(meth)acrylate copolymers

Patent Citations (1)

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CN1120847A (en) * 1993-04-14 1996-04-17 纳幕尔杜邦公司 Water- and oil-repellent fluoro(meth)acrylate copolymers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160486A (en) * 2022-07-29 2022-10-11 同济大学 Antibacterial fluorine-containing emulsifier and preparation method thereof
CN115197362A (en) * 2022-07-29 2022-10-18 同济大学 Super-hydrophobic antibacterial emulsion and preparation and application thereof
CN115260384A (en) * 2022-07-29 2022-11-01 同济大学 Fluorine-containing copolymer emulsion for cement base, super-hydrophobic concrete based on emulsion and preparation method thereof
CN115260384B (en) * 2022-07-29 2023-11-03 同济大学 Fluorine-containing copolymer emulsion for cement base, super-hydrophobic concrete based on emulsion and preparation method of super-hydrophobic concrete
CN115160486B (en) * 2022-07-29 2023-11-03 同济大学 Antibacterial fluorine-containing emulsifier and preparation method thereof
CN115197362B (en) * 2022-07-29 2023-11-03 同济大学 Super-hydrophobic antibacterial emulsion and preparation and application thereof

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