CN109422850B - Self-crosslinking fluorine-containing macromolecular emulsifier, fluorine-containing emulsion containing emulsifier, and preparation and use methods thereof - Google Patents

Self-crosslinking fluorine-containing macromolecular emulsifier, fluorine-containing emulsion containing emulsifier, and preparation and use methods thereof Download PDF

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CN109422850B
CN109422850B CN201811005734.3A CN201811005734A CN109422850B CN 109422850 B CN109422850 B CN 109422850B CN 201811005734 A CN201811005734 A CN 201811005734A CN 109422850 B CN109422850 B CN 109422850B
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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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    • 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
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    • 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
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    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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    • 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
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Abstract

The invention discloses a self-crosslinking fluorine-containing macromolecular emulsifier, a fluorine-containing emulsion containing the emulsifier, and preparation and use methods thereof. The self-crosslinking fluorine-containing macromolecular emulsifier is obtained by solution copolymerization of a fluorine-containing vinyl monomer and a self-crosslinking hydrophilic monomer in an organic solvent, and then the obtained polymer solution is used as an emulsifier to emulsify the fluorine-containing monomer and the comonomer to obtain the fluorine-containing emulsion. The fluorine-containing macromolecular emulsifier prepared by adopting the method of connecting the hydrophobic fluorine-containing side chain with the hydrophilic group has excellent emulsifying effect on fluorine-containing monomers, and the prepared fluorine-containing emulsion is extremely stable. The fluorine-containing emulsion can be coated on the surface of an object to be treated by a treatment method of dipping, coating and high-temperature drying, hydrophilic groups in the emulsifier can be self-crosslinked at high temperature to eliminate hydrophilic influence, and the fluorine-containing emulsion has excellent waterproof performance and better application prospect.

Description

Self-crosslinking fluorine-containing macromolecular emulsifier, fluorine-containing emulsion containing emulsifier, and preparation and use methods thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a self-crosslinking fluorine-containing macromolecular emulsifier, a fluorine-containing emulsion containing the emulsifier, and preparation and use methods thereof.
Background
Fluorine atoms have the properties of strong electronegativity, low polarizability, weak van der waals force, high bond energy (485.3kJ/mol) of C-F bonds and the like, so that the fluorine-containing polymer has the advantages of outstanding heat resistance, solvent resistance, unique low surface energy and the like, and the fluorine-containing polymer is coated on the surface of a material to endow the material with excellent hydrophobic, oleophobic and self-cleaning properties. The effective component of most of the existing waterproof finishing agents is fluorine-containing copolymer.
Since the fluorine-containing polymer is extremely inert, and the organic solvent used for polymerization has safety problems and environmental problems, the conventional fluorine-containing polymer is usually in the form of a water-dispersed emulsion. However, the existing emulsion type fluorine-containing emulsion is mostly emulsified by using a common non-fluorine surfactant, the surfactant activity is low and the dosage is large, and a fluorine-containing monomer cannot be completely emulsified and participates in polymerization, so that the fluorine content in a polymer is low, a polymerization system is unstable, the waterproof effect is influenced, the water contact angle of the coated surface of the emulsion is below 120 degrees, the emulsion cannot show good hydrophobic performance, and the application range of the fluorine-containing emulsion is greatly limited.
Chinese patent (CN101481438A) discloses a random copolymerization fluorine-containing macromolecular emulsifier and a preparation method thereof, wherein the macromolecular emulsifier consisting of fluorine-containing chain links and hydrophilic quaternary ammonium salt is prepared by adopting free radical polymerization. However, the emulsifier adopts strongly hydrophilic quaternary ammonium salt groups, the hydrophilic quaternary ammonium salt groups gradually migrate to the surface of the coating due to molecular diffusion in the using process of the coating, the hydrophilic groups enriched on the surface of the coating seriously affect the hydrophobicity, the anti-adhesion property, the hydrophobic stability and the long-acting property of the coating, and even elute the fluoropolymer on the coating under long-term contact with water environment, so that the performance is further reduced, and the hydrophobic property of the coating is seriously damaged. According to experiments, after the hydrophobic material prepared by using the quaternary ammonium salt type surfactant is soaked in water at normal temperature for 9 days, the contact angle is reduced from 140 degrees to 72 degrees, and the hydrophobic material basically does not have obvious hydrophobic property (see comparative example 28).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to solve the technical problems of providing a self-crosslinking fluorine-containing macromolecular emulsifier, a fluorine-containing emulsion containing the emulsifier, and a preparation method and a use method thereof, wherein the crosslinking fluorine-containing macromolecular emulsifier has a good emulsifying effect, is stable in emulsion, can generate self-crosslinking reaction on hydrophilic groups, prevents the hydrophilic groups from migrating to an air interface, and eliminates hydrophilic influence, so that the fluorine-containing emulsion has good hydrophobic property, the contact angles are all over 120 degrees, the good hydrophobic property is kept, the hydrophilic groups cannot migrate to the surface under the water environment, and the contact angle cannot change greatly after long-term contact with water.
According to the invention, the ternary fluorine-containing amphiphilic polymer obtained by solution polymerization is innovatively used as the fluorine-containing macromolecular emulsifier, on one hand, the emulsifier can adsorb more fluorine-containing monomers due to the interaction of fluorine elements, and more fluorine-containing monomers can enter an emulsifier micelle for polymerization, so that emulsion with high fluorine content is obtained; on the other hand, the non-fluorine chain segment is introduced into the emulsifier, so that not only can the production cost be controlled, but also the reactivity ratio of hydrophilic and hydrophobic monomers can be adjusted, and thus the hydrophilic and hydrophobic component proportion of the emulsifier is adjusted; more importantly, different from the prior art, the hydroxyl at the tail end of the side chain in the fluorine-containing macromolecular emulsifier can form a strong hydrogen bond effect with an adjacent amide group, the nucleophilicity of the hydroxyl is enhanced, and the tail hydroxyl can generate dehydration self-crosslinking reaction at high temperature so as to passivate a hydrophilic group. The prepared fluorine-containing emulsion has stable component content, higher fluorine content and excellent hydrophobic property.
Therefore, the invention adopts the following technical scheme:
the first purpose of the invention is to provide a self-crosslinking fluorine-containing macromolecular emulsifier, wherein the self-crosslinking fluorine-containing macromolecular emulsifier is a polymer consisting of fluorine-containing chain links, non-fluorine chain links and hydrophilic chain links, and the emulsifier is one or more of compounds with the structural formula shown as the following formula
Figure BDA0001783950890000024
In the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is as follows;
Figure BDA0001783950890000022
the non-fluorine chain link is polymerized by a non-fluorine functional monomer B, and the structure of the functional chain link-B-is as follows:
Figure BDA0001783950890000023
the hydrophilic chain link is formed by polymerizing a hydrophilic functional monomer C, and the structure of a hydrophilic chain link unit-C-is as follows:
Figure BDA0001783950890000031
in the formula:
R1selected from H, CH3；
R2Is selected 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 (CH)2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
j is an integer from 0 to 17;
R4selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
a. b and c are integers more than 1; preferably, a/b is 1/50-4/1, and a/c is 1/1-1/20.
Further, the structural formula of the fluorine-containing monomer A is as follows:
Figure BDA0001783950890000032
in the formula:
R1selected from H, CH3；
R2Is selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF(CF2CF3)(CH(CF3)2)；
m is 3, 5, 7, 9, 11, 13, 15;
preferably, the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorononyl ethylene, perfluorododecyl ethylene, perfluorotetradecyl ethylene, perfluorohexadecyl ethylene, perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorododecyl ethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl methacrylate, perfluorononyl ethyl methacrylate, perfluorododecyl ethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorodecyl ethyl acrylate, perfluoro, Perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate.
Further, the structural formula of the non-fluorine functional monomer B is as follows:
Figure BDA0001783950890000041
in the formula:
R1selected from H, CH3；
R3Selected from COO (CH)2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
j is an integer from 0 to 17;
preferably, the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (meth) acrylate with a carbon chain number of 1-18.
Further, the structural formula of the hydrophilic functionalized monomer C is as follows:
Figure BDA0001783950890000042
in the formula:
R1selected from H, CH3；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
Preferably, the hydrophilic functionalized monomer C is selected from any one or more of hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
The second purpose of the invention is to provide a preparation method of the self-crosslinking fluorine-containing macromolecular emulsifier, which comprises the following steps: weighing 10-50 wt% of fluorine-containing monomer A, 20-80 wt% of hydrophilic functional monomer C, 10-70 wt% of non-fluorine functional monomer B and 0.1-5 wt% of initiator based on the total weight of the monomers, adding the monomers into 10-400 wt% of organic solvent based on the total weight of the monomers, uniformly mixing, and carrying out solution polymerization at the temperature of 40-120 ℃ to obtain the self-crosslinking fluorine-containing macromolecular emulsifier; the total weight of the monomers is the total weight of the fluorine-containing monomer A, the non-fluorine functional monomer B and the hydrophilic functional monomer C.
Preferably, the organic solvent is any one or more selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and N-alkyl pyrrolidone;
preferably, the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorononyl ethylene, perfluorododecyl ethylene, perfluorotetradecyl ethylene, perfluorohexadecyl ethylene, perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorododecyl ethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl methacrylate, perfluorononyl ethyl methacrylate, perfluorododecyl ethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorodecyl ethyl acrylate, perfluoro, One or more of perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate;
preferably, the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (meth) acrylate with a carbon chain number of 1-18;
preferably, the hydrophilic functionalized monomer C is selected from any one or more of hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
Preferably, the initiator is any one of azobisisobutyronitrile and benzoyl peroxide.
Preferably, the organic solvent is one or more selected from the group consisting of acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and N-alkyl pyrrolidone.
Preferably, the macromolecular emulsifier consists of 10-50 wt% of monomers and the balance of organic solvent.
Preferably, the monomer configuration mass ratio is as follows: 10-50% of fluorine-containing monomer, 20-90% of hydrophilic functional monomer and 0-70% of non-fluorine functional monomer. More preferably, 20 to 30 wt% of fluorine-containing monomer, 20 to 50wt% of hydrophilic functionalized monomer and 20 to 60 wt% of non-fluorine monomer.
Preferably, the total time is 1 to 20 hours.
The third purpose of the invention is to provide a fluorine-containing emulsion, which contains the fluorine-containing macromolecular emulsifier.
Further, the fluorine-containing emulsion comprises 2-50 wt% of a monomer, 0-5 wt% of a fluorine-containing macromolecular emulsifier solution, 0-15 wt% of an organic solvent and the balance of water, wherein the monomer comprises 10-70 wt% of a fluorine-containing monomer A and 30-90 wt% of a non-fluorine functional monomer B based on the total weight of the monomer;
further, the organic solvent is one or more selected from acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and N-alkyl pyrrolidone.
Further, the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorononyl ethylene, perfluorododecyl ethylene, perfluorotetradecyl ethylene, perfluorohexadecyl ethylene, perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorododecyl ethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl methacrylate, perfluorononyl ethyl methacrylate, perfluorododecyl ethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorododecyl ethyl methacrylate, perfluorodecyl ethyl acrylate, perfluorodecyl ethyl, One or more of perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate; the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (methyl) acrylate with carbon chain number of 1-18.
The fourth purpose of the invention is to provide a preparation method and application of fluorine-containing emulsion, comprising the following steps:
1) emulsion synthesis: mixing and dispersing a fluorine-containing monomer A and a non-fluorine functional monomer B, a fluorine-containing macromolecular emulsifier solution, an organic solvent and water to obtain an emulsion;
2) synthesizing fluorine-containing emulsion: adding an initiator with the weight of 0.1-5 wt% of the total weight of the monomers into the emulsion obtained in the step 1), and carrying out polymerization reaction for 1-24 hours at the temperature of 40-120 ℃ to obtain the fluorine-containing emulsion after the reaction is finished;
3) diluting the fluorine-containing emulsion: diluting the fluorine-containing emulsion obtained in the step (3) by using water or a mixed solvent of water and ethanol, then dipping or coating the diluted fluorine-containing emulsion on the surface of a treatment material, and drying the treated material at a high temperature of 100-220 ℃ for 1-10 minutes.
Preferably, the fluorine-containing monomer A in the step (1) is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorononyl ethylene, perfluorododecyl ethylene, perfluorotetradecyl ethylene, perfluorohexadecyl ethylene, perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorododecyl ethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl methacrylate, perfluorononyl ethyl methacrylate, perfluorododecyl ethyl methacrylate, perfluorodecyl ethyl methacrylate, perfluorotetradecylethyl methacrylate, perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate, and dodecafluoroheptyl methacrylate.
Preferably, the non-fluorine functionalized monomer B in the step (1) is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl octanoate and alkyl (meth) acrylate with carbon chain number of 1-18;
preferably, the emulsion in the step (1) consists of 2-50 wt% of monomers, 0.2-5 wt% of macromolecular emulsifier, 0-15 wt% of organic solvent and the balance of water.
Preferably, the mixed monomers in the step (1) are prepared in the following mass ratio: 10-70 wt% of fluorine-containing monomer and 30-90 wt% of non-fluorine functional monomer. More preferably, the fluorine-containing monomer accounts for 20-50 wt%, and the non-fluorine functional monomer accounts for 50-80 wt%.
Preferably, the pre-emulsification time in the step (1) is 5-120 min,
preferably, the initiator in the step (2) is any one or more of azobisisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutylamidine hydrochloride and bis (2-ethylhexyl) peroxydicarbonate.
Preferably, the rotation speed of the mechanical stirring in the step (2) is 200-800 r/min.
Preferably, the reaction time in the step (2) is 1-24 hours.
Preferably, the mixing ratio of the water and the ethanol in the step (3) is 50/1-1/5, and more preferably, the mixing ratio of the water and the ethanol is 10/1-1/1.
Preferably, the dilution factor in the step (3) is 1-100 times.
Preferably, the drying temperature in the step (3) is 160-200 ℃.
Preferably, the drying time in the step (3) is 3 to 6 minutes.
In the steps of the invention, the non-fluorine functional monomer is copolymerized with the fluorine-containing monomer in the step (2), so that the content of the fluorine-containing component can be adjusted, the film-forming property and the waterproof property of the emulsion are improved, the preparation cost is optimized, and the performance of the fluorine-containing emulsion prepared in the step (2) is optimal. And (3) diluting the fluorine-containing emulsion obtained in the step (2) according to the production requirement, further optimizing the production cost, and adding ethanol can improve the infiltration performance of the emulsion and enlarge the application range of the fluorine-containing emulsion. And (4) the fluorine-containing side chain in the fluorine-containing emulsion obtained in the step (3) can be spontaneously enriched to the surface at high temperature, so that the hydrophobic effect of the surface is increased. And the only hydrophilic group-hydroxyl group in the emulsion can generate self-crosslinking at high temperature to form a hydrophobic crosslinking network, so that the hydrophilic influence is further eliminated, and the hydrophobic effect of the emulsion is improved.
Compared with the prior art, the invention has the beneficial effects that:
1) the fluorine-containing emulsion containing the self-crosslinking fluorine-containing macromolecular emulsifier provided by the invention adopts the self-made fluorine-containing macromolecular emulsifier, has a good emulsifying effect on the fluorine-containing monomer, and the fluorine content in the obtained fluorine-containing emulsion can reach 70 wt% without being interfered by the inertia of the fluorine monomer and difficult to emulsify; and the proportion of the non-fluorine functional monomer component can be adjusted at will between 30 and 90 weight percent, so that the fluorine-containing emulsion provided by the invention has a wider application range. The hydrophilic groups contained in the obtained emulsion can be passivated by high-temperature self-crosslinking during post-treatment, so that a treated surface with higher hydrophobicity is obtained.
2) The fluorine-containing macromolecular emulsifier is synthesized by solution polymerization, the polymerization process is simple and easy to operate, the molecular weight is easy to regulate, the reactivity ratio of the hydrophobic fluorine-containing monomer and the hydrophilic functional monomer is regulated and controlled by the non-fluorine functional monomer, the adjustable range of the HLB value of the fluorine-containing macromolecular emulsifier is enlarged, and the fluorine-containing macromolecular emulsifier has very flexible applicability; and the synthesized solution can be directly applied to the subsequent emulsion polymerization without generating any industrial waste water and waste gas.
3) The emulsion polymerization method adopted by the invention has the advantages of high polymerization speed, short reaction flow and high molecular weight, the obtained emulsion can directly achieve the waterproof effect by the method of dipping and smearing the material, the operation equipment is simple, and the method is suitable for large-scale production.
Drawings
FIG. 1 comparison of contact angles before and after E27 coating of PET film in example 27.
Detailed Description
The technical solution of the present invention will be described in detail with reference to specific examples. The procedure was the same as described in the summary of the invention for all examples, and the parameters in the table are the respective conditions of execution and the structure of the copolymer obtained. The fluorine-containing monomer A and the non-fluorine comonomer B used for emulsion synthesis can be the same as or different from the fluorine-containing monomer A and the non-fluorine comonomer B in the fluorine-containing macromolecular emulsifier. It should be noted that the embodiments described are not intended to limit the invention, and all modifications that can be derived or suggested by those skilled in the art from the disclosure of the present invention should be considered within the scope of the present invention.
Example 1
Synthesis of fluorine-containing emulsion E1 containing self-crosslinking fluorine-containing macromolecular emulsifier:
100ml of N, N-Dimethylacetamide (DMAC), 6g of perfluorooctylethylacrylate, 6g of methyl methacrylate, 8g of hydroxyethylacrylamide and 0.2g of Benzoyl Peroxide (BPO) as an initiator were charged into a reactor, and dissolved and stirred at room temperature for 30 minutes under nitrogen atmosphere to remove oxygen in the system. The temperature was raised to 60 ℃ in the presence of reflux to carry out the polymerization. And stopping heating after 6 hours of reaction, and introducing air to stop the reaction to prepare the fluorine-containing macromolecular emulsifier. After discharging, 300g of perfluorooctyl ethyl acrylate, 300g of methyl methacrylate, 50g of the prepared fluorine-containing macromolecular emulsifier solution and 2000ml of deionized water are pre-emulsified for 30 minutes at room temperature by an ultrasonic emulsifying machine to obtain an emulsion, the emulsion is placed into a four-neck flask with a stirring paddle, a thermometer and a reflux pipe nitrogen-introducing device, 6g of ammonium persulfate is added, and the temperature is increased to 80 ℃ to start polymerization, so that blue-emitting white emulsion E1 is obtained.
The structure and performance of the obtained fluorine-containing emulsion E1 are characterized by comprising the following steps:
1. structural characterization: demulsifying the fluorine-containing emulsion with alcohol, precipitating, washing off emulsifier, oven drying at 60 deg.C to constant weight, dissolving the obtained polymer in Tetrahydrofuran (THF), analyzing molecular weight by Gel Permeation Chromatography (GPC), and dissolving the polymer in deuterated chloroform1H-NMR nuclear magnetic resonance spectrum analysis of the structure.
2. And (3) performance characterization: diluting E1 by 10 times in 15wt% alcohol water solution, immersing a piece of glass fiber non-woven fabric membrane in the emulsion, taking out after one minute, vacuum-rolling out the redundant emulsion, drying at 170 ℃ for 5 minutes, and measuring the contact angle of the glass fiber non-woven fabric membrane before and after treatment by using a contact angle meter.
Example 2
Synthesis of fluorine-containing emulsion E2 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E2 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E2 is the same as that of example 1. E2 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E2 coating film treatment is shown in Table 4.
Example 3:
synthesis of fluorine-containing emulsion E3 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E3 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E3 is the same as that of example 1. E3 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E3 coating film treatment is shown in Table 4.
Example 4:
synthesis of fluorine-containing emulsion E4 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E4 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E4 is the same as that of example 1. E4 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E4 coating film treatment is shown in Table 4.
Example 5:
synthesis of fluorine-containing emulsion E5 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E5 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E5 is the same as that of example 1. E5 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E5 coating film treatment is shown in Table 4.
Example 6:
synthesis of fluorine-containing emulsion E6 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E6 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E6 is the same as that of example 1. E6 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E6 coating film treatment is shown in Table 4.
Example 7:
synthesis of fluorine-containing emulsion E7 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E7 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E7 is the same as that of example 1. E7 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E7 coating film treatment is shown in Table 4.
Example 8:
synthesis of fluorine-containing emulsion E8 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E8 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E8 is the same as that of example 1. E8 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E8 coating film treatment is shown in Table 4.
Example 9:
synthesis of fluorine-containing emulsion E9 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E9 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E9 is the same as that of example 1. E2 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E2 coating film treatment is shown in Table 4.
Example 10:
synthesis of fluorine-containing emulsion E10 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E10 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E10 is the same as that of example 1. E10 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E10 coating film treatment is shown in Table 4.
Example 11:
synthesis of fluorine-containing emulsion E11 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E11 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E11 is the same as that of example 1. E11 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E11 coating film treatment is shown in Table 4.
Example 12:
synthesis of fluorine-containing emulsion E12 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E12 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E12 is the same as that of example 1. E12 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E12 coating film treatment is shown in Table 4.
Example 13:
synthesis of fluorine-containing emulsion E13 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E13 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E13 is the same as that of example 1. E13 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E13 coating film treatment is shown in Table 4.
Example 14:
synthesis of fluorine-containing emulsion E14 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E14 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E14 is the same as that of example 1. E14 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E14 coating film treatment is shown in Table 4.
Example 15:
synthesis of fluorine-containing emulsion E15 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E15 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E15 is the same as that of example 1. E15 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E15 coating film treatment is shown in Table 4.
Example 16:
synthesis of fluorine-containing emulsion E16 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E16 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E16 is the same as that of example 1. E16 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E16 coating film treatment is shown in Table 4.
Example 17:
synthesis of fluorine-containing emulsion E17 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E17 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E17 is the same as that of example 1. E17 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E17 coating film treatment is shown in Table 4.
Example 18:
synthesis of fluorine-containing emulsion E18 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E18 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E18 is the same as that of example 1. E18 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E18 coating film treatment is shown in Table 4.
Example 19:
synthesis of fluorine-containing emulsion E19 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E19 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E19 is the same as that of example 1. E19 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E19 coating film treatment is shown in Table 4.
Example 20:
synthesis of fluorine-containing emulsion E20 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E20 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E20 is the same as that of example 1. E20 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E20 coating film treatment is shown in Table 4.
Example 21:
synthesis of fluorine-containing emulsion E21 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E21 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E21 is the same as that of example 1. E21 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E21 coating film treatment is shown in Table 4.
Example 22:
synthesis of fluorine-containing emulsion E22 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E22 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E22 is the same as that of example 1. E22 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E22 coating film treatment is shown in Table 4.
Example 23:
synthesis of fluorine-containing emulsion E23 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E23 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E23 is the same as that of example 1. E23 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E23 coating film treatment is shown in Table 4.
Example 24:
synthesis of fluorine-containing emulsion E24 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E24 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E24 is the same as that of example 1. E24 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E24 coating film treatment is shown in Table 4.
Example 25:
synthesis of fluorine-containing emulsion E25 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E25 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E25 is the same as that of example 1. E25 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E25 coating film treatment is shown in Table 4.
Example 26:
synthesis of fluorine-containing emulsion E26 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E26 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E26 is the same as that of example 1. E26 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E26 coating film treatment is shown in Table 4.
Example 27:
synthesis of fluorine-containing emulsion E27 containing self-crosslinking fluorine-containing macromolecular emulsifier:
the synthesis of E27 is described in example 1, and the formula and process parameters are shown in tables 1 and 2, respectively.
The method for characterizing the structure and the performance of E27 is the same as that of example 1. E27 molecular weight and molecular weight distribution and fluorine content are shown in Table 3; the change in contact angle of the glass fiber nonwoven film before and after the E27 coating film treatment is shown in Table 4.
Comparative example 28:
the synthesis of a fluorine-containing emulsion E28 containing a strongly hydrophilic group (for example of the quaternary ammonium type) emulsifier was prepared with reference to chinese patent (CN 101481438A):
e28 synthesis, formulation and process parameters were referenced to example 1 using trimethyl allyl ammonium chloride as hydrophilic monomer as shown in tables 1 and 2.
Comparative example 29:
synthesis of a fluorinated emulsion E29 containing a hydroxymethyl acrylate emulsifier:
e29 reference is made to example 1 for the synthesis, formulation and process parameters using hydroxymethyl acrylate as hydrophilic monomer, as shown in tables 1 and 2.
Comparative example 30:
synthesis of fluorinated emulsion E30 containing hydroxyethyl acrylate emulsifier:
e30 reference is made to example 1 for the synthesis, formulation and process parameters using hydroxyethyl acrylate as hydrophilic monomer, as shown in tables 1 and 2.
E1, E28, E29 and E30 were each diluted in the same number and coated on a glass fiber nonwoven film and simultaneously dried at 180 ℃ for 5 minutes. And testing the initial contact angle, and soaking the treated glass fiber non-woven fabric film in water at normal temperature for 10 days. After drying the contact angle was again tested and the results are shown in table 5.
Table 5 shows that when the fluorine-containing emulsion E1 of the self-crosslinking macromolecular fluorine-containing emulsifier is used for coating a glass fiber non-woven fabric membrane, the contact angle is reduced by only 2 degrees after the non-woven fabric membrane is soaked in water for 10 days, and within an error range, the fluorine-containing emulsion of the invention keeps good hydrophobic property, and the hydrophilic group of the fluorine-containing emulsion can not migrate to the surface under the water environment; however, after E28 using a strongly hydrophilic quaternary ammonium emulsifier and coating, the contact angle dropped from 140 to 72 after 10 days of immersion, and the hydrophobic properties dropped by 50%. After the coating of E29 and E30 by using other hydroxyl macromolecular emulsifiers, the contact angle is also reduced from about 140 degrees to about 80 degrees, which indicates that the hydroxyl groups which are not connected with the amide groups can not carry out self-crosslinking and can not prevent the hydrophilic groups from migrating to the surface, so that the reduction of the hydrophobic property is still reduced by 45 percent.
TABLE 1
Figure BDA0001783950890000151
Figure BDA0001783950890000161
Figure BDA0001783950890000171
Figure BDA0001783950890000181
Figure BDA0001783950890000191
Figure BDA0001783950890000201
Figure BDA0001783950890000211
TABLE 2
Figure BDA0001783950890000221
Figure BDA0001783950890000231
TABLE 3
Figure BDA0001783950890000241
TABLE 4
Figure BDA0001783950890000251
TABLE 5
Film numbering Initial coating film contact Angle/° Contact angle/° after soaking in water
E1 150 148
E28 140 72
E29 141 78
E30 139 79

Claims (12)

1. A self-crosslinking fluorine-containing macromolecular emulsifier is characterized in that: the self-crosslinking fluorine-containing macromolecular emulsifier is a polymer consisting of fluorine-containing chain links, non-fluorine chain links and hydrophilic chain links, and the structural formula of the fluorine-containing macromolecular emulsifier is as follows:
Figure DEST_PATH_IMAGE001
in the formula:
the fluorine-containing chain link is formed by polymerizing a fluorine-containing monomer A, and the structure of the fluorine-containing chain link unit-A-is as follows:
Figure 760189DEST_PATH_IMAGE002
；
the non-fluorine chain link is polymerized by a non-fluorine functional monomer B, and the structure of the functional chain link-B-is as follows:
Figure DEST_PATH_IMAGE003
；
the hydrophilic chain link is formed by polymerizing a hydrophilic functional monomer C, and the structure of a hydrophilic chain link unit-C-is as follows:
Figure DEST_PATH_IMAGE005
；
in the formula:
R1selected from H, CH3；
R2Is selected 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 (CH)2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
j is an integer from 0 to 17;
R4selected from CONHCH2CH2OH、CONHCH2CHOHCH3;
a. b and c are integers greater than or equal to 1, a/b = 1/50-4/1, and a/c = 1/1-1/20.
2. The fluorine-containing macromolecular emulsifier according to claim 1, characterized in that: the structural formula of the fluorine-containing monomer A is as follows:
Figure 753029DEST_PATH_IMAGE006
；
in the formula:
R1selected from H, CH3；
R2Is selected from COOCH2CH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF(CF2CF3)(CH(CF3)2)；
m is 3, 5, 7, 9, 11, 13, 15;
the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorononylethylene, perfluorododecylethylene, perfluorotetradecylethylene, perfluorohexadecylethylene, perfluorobutylethyl acrylate, perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorononylethyl acrylate, perfluorododecylethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorononylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorooctylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorododecyl methyl, Perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate.
3. The fluorine-containing macromolecular emulsifier according to claim 1, characterized in that: the structural formula of the non-fluorine functional monomer B is as follows:
Figure DEST_PATH_IMAGE007
；
in the formula:
R1selected from H, CH3；
R3Selected from COO (CH)2)jCH3、OOCCH3、OOC(CH2)2CH3、OOC(CH2)6CH3；
j is an integer from 0 to 17;
the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (methyl) acrylate with carbon chain number of 1-18.
4. The fluorine-containing macromolecular emulsifier according to claim 1, characterized in that: the structural formula of the hydrophilic functionalized monomer C is as follows:
Figure 939290DEST_PATH_IMAGE008
in the formula:
R1selected from H, CH3；
R4Selected from CONHCH2CH2OH、CONHCH2CHOHCH3；
The hydrophilic functionalized monomer C is selected from any one or more of hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
5. The preparation method of the self-crosslinking fluorine-containing macromolecular emulsifier according to claim 1, characterized in that the preparation method comprises the following steps: weighing 10-50 wt% of fluorine-containing monomer A, 20-80 wt% of hydrophilic functional monomer C, 10-70 wt% of non-fluorine functional monomer B and 0.1-5 wt% of initiator based on the total weight of the monomers, adding the monomers into 10-400 wt% of organic solvent based on the total weight of the monomers, uniformly mixing, and carrying out solution polymerization at the temperature of 40-120 ℃ to obtain the self-crosslinking fluorine-containing macromolecular emulsifier;
the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorononylethylene, perfluorododecylethylene, perfluorotetradecylethylene, perfluorohexadecylethylene, perfluorobutylethyl acrylate, perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorononylethyl acrylate, perfluorododecylethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorononylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorooctylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorododecyl methyl, One or more of perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate;
the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (meth) acrylate with carbon chain number of 1-18;
the hydrophilic functionalized monomer C is selected from any one or more of hydroxyethyl acrylamide and hydroxypropyl methacrylamide.
6. The method according to claim 5, wherein the organic solvent is any one or more selected from the group consisting of acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, N dimethylformamide, N dimethylacetamide, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and N-alkylpyrrolidone.
7. A fluorine-containing emulsion is characterized in that: the fluorine-containing emulsion comprises the fluorine-containing macromolecular emulsifier according to any one of claims 1 to 5; the fluorine-containing emulsion comprises 2-50 wt% of a monomer, 0.2-5 wt% of a fluorine-containing macromolecular emulsifier, 0-15 wt% of an organic solvent and the balance of water, wherein the monomer comprises 10-70 wt% of a fluorine-containing monomer A and 30-90 wt% of a non-fluorine functional monomer B based on the total weight of the monomer;
the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorononylethylene, perfluorododecylethylene, perfluorotetradecylethylene, perfluorohexadecylethylene, perfluorobutylethyl acrylate, perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorononylethyl acrylate, perfluorododecylethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorononylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorooctylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorododecyl methyl, One or more of perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate;
the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (methyl) acrylate with carbon chain number of 1-18.
8. The preparation method of the fluorine-containing emulsion is characterized by comprising the following steps:
1) emulsion synthesis: mixing a fluorine-containing monomer A with a non-fluorine functional monomer B, the fluorine-containing macromolecular emulsifier of any one of claims 1 to 5, an organic solvent and water, and then dispersing to obtain an emulsion;
2) synthesizing fluorine-containing emulsion: adding an initiator with the weight of 0.1-5 wt% of the total weight of the monomers into the emulsion obtained in the step 1), and carrying out polymerization reaction for 1-24 hours at the temperature of 40-120 ℃ to obtain the fluorine-containing emulsion after the reaction is finished;
the fluorine-containing monomer A is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorononylethylene, perfluorododecylethylene, perfluorotetradecylethylene, perfluorohexadecylethylene, perfluorobutylethyl acrylate, perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorononylethyl acrylate, perfluorododecylethyl acrylate, perfluorotetradecyl ethyl acrylate, perfluorohexadecyl ethyl acrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl methacrylate, perfluorooctylethyl methacrylate, perfluorononylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorooctylethyl methacrylate, perfluorododecylethyl methacrylate, perfluorotetradecyl ethyl methacrylate, perfluorododecyl methyl, One or more of perfluorohexadecylethyl methacrylate, dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate;
the non-fluorine functional monomer B is selected from any one or more of vinyl acetate, vinyl butyrate, vinyl caprylate and alkyl (methyl) acrylate with carbon chain number of 1-18.
9. A hydrophobic material, wherein said hydrophobic material comprises the fluorine-containing emulsion of claim 7.
10. The hydrophobic material of claim 9, wherein the hydrophobic material is a paint or a water and oil repellent agent.
11. The method of using the hydrophobic material according to claim 9 or 10, wherein the hydrophobic material according to claim 9 is applied to the surface of an object to be treated by a method of dipping, painting and drying at high temperature to obtain a hydrophobic surface having a contact angle of 120 ° or more.
12. The use method according to claim 11, wherein the high-temperature drying temperature is selected from 100-220 ℃.
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