CN106543374A - Fluoro-acrylate copolymer emulsion and preparation method thereof and prepare latex film method - Google Patents
Fluoro-acrylate copolymer emulsion and preparation method thereof and prepare latex film method Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F2/16—Aqueous medium
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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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
- C08F220/10—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
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08F220/10—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
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The present invention relates to a kind of copolymer emulsion, specially fluoro-acrylate copolymer emulsion and preparation method thereof and prepare latex film method.By reaction monomers, obtained using semi-continuous emulsion polymerizing method in compound emulsifying agent, initiator, crosslinking agent, the reaction system of deionized water composition；Reaction monomers are made up of with fluorinated acrylate monomer non-fluorine-containing carbon carbon double bond monomer, and the fluorinated acrylate monomer in reaction monomers accounts for the 0 20% of reaction monomers gross mass.Fluoro-acrylate copolymer emulsion breaking obtained in the method that the present invention is provided, fluorine-containing part is made to occur to be polymerized in shell, simultaneously in film forming procedure, fluorine-containing groupses are to film surface migration such that it is able to which reach makes latex film keep the excellent surface property of fluorinated acrylate in the case where fluorochemical monomer consumption is substantially reduced.
Description
Technical field
The present invention relates to a kind of copolymer emulsion, specially fluoro-acrylate copolymer emulsion and preparation method thereof and system
Standby latex film method.
Background technology
Fluorine is the maximum element of electronegativity in the periodic table of elements, and with rudimentary polarizability, atomic radius is only second to hydrogen.C-
F keys are extremely short, and bond energy is very big, up to 485KJ/mol.Fluorin radical in fluorinated acrylate polymer is located at the side chain of polymer
On, during film forming, in fluorinated acrylate polymer, fluorine-containing alkyl can be enriched to the interface of polymer and air, and to
Stretch in air, due to strand spirality, perfluorinated side chains are orientated outwardly, form " shielding guarantor to main chain and its interior molecules
Shield " effect.Secondly, fluorine atom radius ratio hydrogen atom radius is bigger, but less than the atomic radius of other elements, can be carbon carbon backbone chain
Tight encases so as to by the good protection of surrounding fluorine atom, even if the atom of minimum is also difficult to be inserted into carbochain so that fluorine-containing
Polymer physicochemical stability, good endurance.Fluorine atom polarizability is minimum in all elements, causes C-F bond polarities stronger, C-
The share electron pair of F keys is partial to fluorine atom significantly, forms one layer of negative electrical charge protection, makes electronegative nucleopilic reagent be close to carbon
Atom and there is chemical reaction.
The wider fluorocarbon polymer of application mainly has polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF) etc. at present.But
The main chain rigidity of PTFE is higher, and its processability, dissolubility, compatibility are poor；The coating film gloss degree of PVDF coating is low, it is impossible to room temperature
Solidification, also fails to meet the requirement of functional coating to a certain extent.On the one hand fluorinated acrylate polymer emulsion retains
The good film forming of polyacrylate dispersion, adhesive force and colour retention：On the other hand, due to having used fluorinated acrylate list
Body, introduces fluoro-containing group on polymer side chain, changes the structure of strand, significantly improves acrylate copolymer
Surface property, makes copolymer have low surface energy, low frictional properties, self-cleaning property and good weather-proof, corrosion-resistant, heat resistance,
For the exploitation of new material, theoretical research and practical application, there is very high application in fields such as high-performance coating, textile finishings
Prospect.
Fluorinated acrylate monomer has different solubility factors and relative density from general acrylate monomer, so general
The condition system used by logical monomer polymerization reactions can not make fluorinated acrylate monomer sufficiently be emulsified and be caused, and cause
Fluorochemical monomer can not effectively participate in copolyreaction, and the fluorochemical monomer market price is expensive, then maximize fluorochemical monomer
While performance, reducing its usage amount just becomes an important problem as far as possible.
With hud typed fluoro-acrylate copolymer prepared by trace inequality semi-continuous seed emulsion polymerization method, will be a small amount of fluorine-containing
Acrylate monomer introduces shell and participates in polymerisation, as the fluorine-containing groupses for being distributed in shell are intended to think in film forming procedure
Latex film outer surface is migrated, and forms C-F enriched layers on its top layer, so that the maximization of utility of its low-surface-energy, reaches " low fluorine
Result efficiently ".When latex film is exposed in polarizable medium for a long time, the fluorine-containing groupses on film top layer can occur induction restructuring, C-F
Enriched layer can be destroyed, and make the surface property of latex film be affected.And after adding crosslinking agent, you can opposing adhesion molecule
Infiltration, the fluorine-containing groupses for aligning can be secured firmly to latex film surface again, prevent fluorine migration after latex film table
Face molecular rearrangement so that the latex film in polarizable medium or wet environment remains to keep excellent surface property.
One of prior art, is first dissolved in benzoyl peroxide in a certain amount of dimethylbenzene and is configured to initiator solution,
Take which 2/3 to be placed in the 250mL four-hole boiling flasks equipped with electric blender, thermometer and condenser pipe.Separately by methacrylic acid perfluor
Alkyl ethyl ester FMA is dissolved in standby in a certain amount of fluorous solvent.Temperature is adjusted to into 95 DEG C, by reactant monomer (methacrylic acid
Methyl esters MMA+ butyl acrylate BA+ hydroxy-ethyl acrylate HEA) mix in proportion after with constant pressure funnel instill flask in, together
When fluorine-containing solution is added dropwise, the time is 4h.Remaining initiator solution is added after finishing by monomer dropping, is reacted 1.5h, is obtained fluorine-containing
Acrylate random copolymers resin.
Due to adopting solution polymerization process, during the course of the reaction using dimethylbenzene and containing fluorous solvent, environment may be caused not
Good impact
The two of prior art, sequentially add deionization in equipped with agitator, the 100mL four-hole boiling flasks of reflux condensing tube
Water, composite emulsifier and NaHCO3, stirring is warming up to 70-75 DEG C, while being slowly added dropwise about 5% mix monomer of mass fraction and drawing
The agent aqueous solution is sent out, 20-30min is incubated, residual monomer and initiator is then added dropwise, about 2h is dripped off, then insulation reaction 2h, is cooled to
Room temperature, adjusts pH=8-9 with ammoniacal liquor, obtains in blue-fluorescence emulsion.Wherein, emulsifying agent be 0.1g lauryl sodium sulfate SDS and
0.2g OP-10, initiator are 0.1g potassium peroxydisulfate KPS.Monomer be methyl methacrylate MMA and butyl acrylate BA, quality
Than for 1:4, monomer total amount 10g, fluorinated acrylate monomer are N- methyl-N-p- perfluorinated nonene epoxide benzene sulfonic acid ammoniums ethyl third
Olefin(e) acid ester, the percentage for accounting for monomer gross mass are respectively 0,10%, 15%, 20%, 25%.
The method, the fluorine-containing carbon number for reacting the fluorinated acrylate monomer for adopting are more than 8, and biological half-life is long, can
Energy meeting generation environment delay is difficult to degrade, and biological accumulation in the mankind and animal tissue etc. affects；
If not adding crosslinking agent, resulting latex film to be exposed in polar environment for a long time during the course of the reaction,
Strand can be caused to reset, the fluorine-containing part on film surface is internally migrated, decline water and oil repellant.
The content of the invention
For above-mentioned technical problem, it is an object of the present invention to provide a kind of fluoro-acrylate copolymer emulsion and its breast
The preparation method of glued membrane.During the course of the reaction, do not use dissolvent residual is likely to result in containing fluorous solvent etc. and has the fluorine-containing of environmental hazard
Solvent etc., gained emulsion require that dilution stability, the latex film by obtained in the emulsion have excellent with good bin stability
Good heat endurance, water and oil repellant, and long-term exposure can also keep these performances not receive considerable influence in the environment.
Concrete technical scheme is：
Fluoro-acrylate copolymer emulsion, by reaction monomers, in compound emulsifying agent, initiator, crosslinking agent, deionized water
Obtained using semi-continuous emulsion polymerizing method in the reaction system of composition；
Described reaction monomers are made up of with fluorinated acrylate monomer non-fluorine-containing carbon carbon double bond monomer, in reaction monomers
Fluorinated acrylate monomer accounts for the 0-20% of reaction monomers gross mass.
In whole reaction system, described reaction monomers account for the 20-40% of gross mass；
1-5% of the consumption of compound emulsifying agent for reaction monomers quality；
0.5-3% of the consumption of initiator for reaction monomers quality；
0.5-3% of the consumption of crosslinking agent for reaction monomers quality；
Compound emulsifying agent is 1 according to mass ratio by anion emulsifier and nonionic emulsifier:1-1:4 compositions.
Described non-fluorine-containing carbon carbon double bond monomer is methyl acrylate, methyl methacrylate, butyl acrylate, benzene second
One or more mixtures in alkene, ethyl acrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate.
Described fluorinated acrylate monomer is hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid
Ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, perluorooctyl acrylate, ten trifluoro monooctyl ester of methacrylic acid, acrylic acid 17
One of fluorine last of the ten Heavenly stems ester, 17 fluorine last of the ten Heavenly stems ester of methacrylic acid.
Described compound emulsifying agent is made up of anion emulsifier and nonionic emulsifier, and anion emulsifier is 12
One kind in sodium alkyl sulfate, neopelex；Nonionic emulsifier is APES class, isomery alcohol gathers
One or more mixtures in oxygen ethene ethers, nonionic fluorocarbon surfactant.
Described initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, azodiisobutyronitrile, ABVN, ring
One or more combination in azo amidine class initiator VA-044.
Described crosslinking agent is selected from acrylamide, N hydroxymethyl acrylamide, DAAM, hydroxyethyl methacrylate
Ethyl ester, hydroxy-ethyl acrylate, oxalyl dihydrazide, GDMA, trimethylol-propane trimethacrylate, first
One or more in base acryloxypropyl trimethoxy silane, vinyltriethylsilane, methacrylic acid, acrylic acid
Combination.
Crosslinking agent is added in core-shell emulsion polymerization reaction system so that in polymerization and film forming procedure in stratum nucleare, shell
One or both is crosslinked, and is generated interpenetrating polymer networks emulsion, is significantly improved water proofing property, heat resistance, optical property, machine
Tool performance and performance of technical process, and due to there occurs crosslinking, when material is exposed in polar environment, strand is not easy
Moving generation rearrangements causes water and oil repellant to decline.
The preparation method of fluoro-acrylate copolymer emulsion, comprises the following steps：
(1) pre-emulsification：
I phase of mixture constituted by non-fluorine-containing carbon carbon double bond monomer, emulsifying agent, initiator, crosslinking agent and deionized water
Stirring and ultrasonic emulsification 30-60min；Fluorinated acrylate monomer, emulsifying agent, initiator, crosslinking agent and deionized water composition
Mixture II mutually stirring and ultrasonic emulsification 30-60min at normal temperatures；
(2) nuclear phase polymerization：
The pre-emulsion that mixture I is mutually formed is placed in and is introduced equipped with reflux condensing tube, constant pressure funnel, thermometer, N2
In the corner flask of device, 60-75 DEG C is heated to, reacts 2-3h；
(3) shell phase polymerization is added dropwise：
The pre-emulsion and initiator solution that mixture II is mutually formed is added dropwise over described four by dropping funel
In the flask of angle, polymerisation is participated in, time for adding is 2-5h；
(4) obtain fluoro-acrylate copolymer emulsion
After completion of dropping, temperature is risen to into 80-95 DEG C of reaction 1-3h, emulsion is obtained after stopping reaction, is cooled to 35-
45 DEG C, it is 6-7 to add pH adjusting agent to adjust pH, you can obtain fluoro-acrylate copolymer emulsion.Described pH adjusting agent choosing
From ammoniacal liquor, bicarbonate, hydrophosphate.
Fluoro-acrylate copolymer emulsion is used to prepare fluorinated acrylate latex film.
The preparation method of fluorinated acrylate latex film, including procedure below：
Obtained fluoro-acrylate copolymer emulsion is directly coated on base material, drying and forming-film.Base material selected from glass,
Polytetrafluoroethylene (PTFE), aluminium flake.
Or, by fluoro-acrylate copolymer emulsion breaking, latex is formed, and deionized water is rinsed, drying；By drying
Good latex is dissolved in solvent, then deionized water is precipitated out, the latex for precipitating is dissolved in solvent be configured to it is molten
Liquid, film；Dry in 20-120 DEG C, fluorinated acrylate latex film is obtained.
During emulsion breaking, adoptable method is selected from centrifugation, low temperature, dropwise addition salting liquid.
Described dissolving latex solvent for use is selected from acetone, toluene, dimethylbenzene, methyl alcohol, carbon tetrachloride, tetrahydrofuran.
In film-forming process, the method that the high temperature anneal can be adopted, when vitrification point of the temperature higher than material, point
Subchain is easily moved, and the fluorine-containing groupses for making surface energy low more readily migrate into surface, and arrangement is more neat, increases water and oil repellant
Property.
Fluoro-acrylate copolymer emulsion breaking obtained in the method that the present invention is provided, makes fluorine-containing part occur in shell
Polymerization, while in film forming procedure, fluorine-containing groupses are to film surface migration such that it is able to reach and substantially reducing fluorochemical monomer consumption
In the case of make latex film keep the excellent surface property of fluorinated acrylate.
The specific beneficial effect of technical scheme that the present invention is provided has：
1. adopted raw material monomer of reaction etc. all commercially can be bought, and it is convenient to originate.
2. course of reaction will not generation environment harm problem.
3. products therefrom emulsion is deposited six months and is still stablized afterwards, is not layered demulsifying phenomenon.
4. gained latex film has preferable water and oil repellant.
5. there is polymerisation in shell in fluorochemical monomer, and low fluorine content can also obtain preferable water and oil repellant effect, effectively
Relatively low cost.
Specific embodiment
It is described in conjunction with the embodiments the specific embodiment of the present invention.
Embodiment 1
Reaction monomers are：Methyl methacrylate, butyl acrylate
Take lauryl sodium sulfate SDS 0.45g, emulsifier op-10 0.90g to be dissolved in deionized water, be configured to 5%
Compound emulsifying agent solution for standby.
By butyl acrylate 20g, methyl methacrylate 10g, potassium peroxydisulfate 0.12g, composite emulsifying agent solution 13.5g,
Mixture I and the butyl acrylate 5g of deionized water 22.26g composition, methyl methacrylate 10g, potassium peroxydisulfate 0.12g,
Composite emulsifying agent solution 13.5g, the II of deionized water 15.6g composition mutually stir 30min, ultrasonic 10min respectively, form mixing equal
Even pre-emulsion.
Under nitrogen protection, I phase pre-emulsion is caused into polymerization 2h at 70 DEG C.
The persulfate aqueous solution of 2.4g 5% and II phase pre-emulsion are separately added in reaction flask by dropping funel,
Time for adding is 3h.
After polymer is incubated 2h at 80 DEG C, stops reaction, be cooled to 35-45 DEG C, add ammoniacal liquor its pH to be adjusted for 6-
7.Acrylate copolymer emulsion is obtained.
By resulting emulsion, at -18 DEG C, breakdown of emulsion forms latex, and deionized water repeatedly rinses drying, by drying
Latex is dissolved in excessive acetone, then deionized water is precipitated out, and rinses drying.The latex for processing is dissolved in
20% acetone soln is formed in acetone, solvent evaporation method is adopted on clean sheet glass, (fluorine-containing) is obtained in 30 DEG C of constant temperature
Acrylic emulsion film.
Embodiment 2
Reaction monomers are：Dodecafluoroheptyl methacrylate (5g), methyl methacrylate, butyl acrylate
Take lauryl sodium sulfate SDS 0.5g, emulsifier op-10 1.0g to be dissolved in deionized water, be configured to 5% and answer
Co-emulsifier solution for standby.
By butyl acrylate 20g, methyl methacrylate 10g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, go
The mixture I and butyl acrylate 5g, methyl methacrylate 10g, ten difluoro of methacrylic acid of ionized water 24.73g compositions
Heptyl ester 5g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, the II of deionized water 17.33g composition mutually stir respectively
30min, ultrasonic 10min, form the pre-emulsion being well mixed.
Under nitrogen protection, I phase pre-emulsion is caused into polymerization 2h at 70 DEG C.
The persulfate aqueous solution of 2.66g 5% and II phase pre-emulsion are separately added into into reaction flask by dropping funel
In, time for adding is 3h.
Remaining step is with embodiment 1.Fluoro-acrylate copolymer latex film is obtained.
Embodiment 3
Reaction monomers are：Ten trifluoro monooctyl ester (5g) of methacrylic acid, methyl methacrylate, butyl acrylate
Take lauryl sodium sulfate SDS 0.5g, OP-10 1.0g to be dissolved in deionized water, be configured to 5% composite emulsifying
Agent solution is standby.
By butyl acrylate 20g, methyl methacrylate 10g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, go
The mixture I and butyl acrylate 5g, methyl methacrylate 10g, ten trifluoro of methacrylic acid of ionized water 24.73g compositions
Monooctyl ester 5g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, the II of deionized water 17.33g composition mutually stir respectively
30min, ultrasonic 10min, form the pre-emulsion being well mixed.
Remaining step is with embodiment 2.
Embodiment 4
Reaction monomers are：Hexafluorobutyl mathacrylate (5g), methyl methacrylate, butyl acrylate
Take lauryl sodium sulfate SDS 0.5g, emulsifier op-10 1.0g to be dissolved in deionized water, be configured to 5% and answer
Co-emulsifier solution for standby.
By butyl acrylate 20g, methyl methacrylate 10g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, go
The mixture I and butyl acrylate 5g, methyl methacrylate 10g, methacrylic acid hexafluoro fourth of ionized water 24.73g compositions
Ester 5g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, the II of deionized water 17.33g composition mutually stir 30min respectively,
Ultrasonic 10min, forms the pre-emulsion being well mixed.
Remaining step is with embodiment 2.
Embodiment 5
Reaction monomers are：Dodecafluoroheptyl methacrylate (5g), methyl methacrylate, butyl acrylate
Take lauryl sodium sulfate SDS 0.5g, emulsifier op-10 1.0g to be dissolved in deionized water, be configured to 5% and answer
Co-emulsifier solution for standby.
By butyl acrylate 20g, methyl methacrylate 10g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, N-
NMA 0.375g, acrylic acid 0.25g, mixture I and the butyl acrylate 5g of deionized water 23.98g composition,
Methyl methacrylate 10g, dodecafluoroheptyl methacrylate 5g, potassium peroxydisulfate 0.133g, composite emulsifying agent solution 15g, N-
NMA 0.25g, acrylic acid 0.25g, the II of deionized water 16.83g composition mutually stir 30min respectively, ultrasound
10min, forms the pre-emulsion being well mixed.
Under nitrogen protection, I phase pre-emulsion is caused into polymerization 2h at 70 DEG C.
The persulfate aqueous solution of 2.66g 5% and II phase pre-emulsion are separately added into into reaction flask by dropping funel
In, time for adding is 3h.
After polymer is incubated 2h at 80 DEG C, 35-45 DEG C is cooled to, add ammoniacal liquor its pH to be adjusted for 6-7.Third is obtained
Olefin(e) acid ester copolymer emulsion.
By the lotion applicator of gained on clean sheet glass, drying at room temperature film forming.Deionized water successively, ethanol punching
Wash.30 DEG C of drying are placed in, crosslinking fluorinated acrylate latex film is obtained.
Fluoro-acrylate copolymer latex film water and oil repellant performance obtained by above example is tested, test result
Such as table 1.
Table 1：Fluoro-acrylate copolymer latex film water and oil repellant performance in embodiment
Above example is intended to further illustrate and non-limiting technical scheme.
Claims (10)
1. fluoro-acrylate copolymer emulsion, it is characterised in that by reaction monomers, in compound emulsifying agent, initiator, crosslinking
Obtained using semi-continuous emulsion polymerizing method in agent, the reaction system of deionized water composition；
Described reaction monomers are made up of with fluorinated acrylate monomer non-fluorine-containing carbon carbon double bond monomer, fluorine-containing in reaction monomers
Acrylate monomer accounts for the 0-20% of reaction monomers gross mass.
2. fluoro-acrylate copolymer emulsion according to claim 1, it is characterised in that in whole reaction system,
Described reaction monomers account for the 20-40% of gross mass；
1-5% of the consumption of compound emulsifying agent for reaction monomers quality；
0.5-3% of the consumption of initiator for reaction monomers quality；
0.5-3% of the consumption of crosslinking agent for reaction monomers quality.
3. fluoro-acrylate copolymer emulsion according to claim 2, it is characterised in that described compound emulsifying agent by
Anion emulsifier and nonionic emulsifier are 1 according to mass ratio:1-1:4 compositions.
4. the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3, it is characterised in that described is non-
Fluorine-containing carbon carbon double bond monomer is methyl acrylate, methyl methacrylate, butyl acrylate, styrene, ethyl acrylate, propylene
One or more mixtures in sour hydroxyl ethyl ester, hydroxyethyl methacrylate.
5. the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3, it is characterised in that described contains
Fluoroacrylate monomers are hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, acrylic acid
Ten difluoro heptyl esters, perluorooctyl acrylate, ten trifluoro monooctyl ester of methacrylic acid, 17 fluorine last of the ten Heavenly stems ester of acrylic acid, methacrylic acid
One of 17 fluorine last of the ten Heavenly stems esters.
6. the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3, it is characterised in that described answers
Co-emulsifier is made up of anion emulsifier and nonionic emulsifier, anion emulsifier be lauryl sodium sulfate, 12
One kind in sodium alkyl benzene sulfonate；Nonionic emulsifier be APES class, isomeric alcohol polyethenoxy ether class, it is non-from
One or more mixtures in subtype fluorocarbon surfactant；
Described initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, azodiisobutyronitrile, ABVN, ring azo
One or more combination in amidine class initiator VA-044；
Described crosslinking agent is selected from acrylamide, N hydroxymethyl acrylamide, DAAM, hydroxyethyl methacrylate second
Ester, hydroxy-ethyl acrylate, oxalyl dihydrazide, GDMA, trimethylol-propane trimethacrylate, methyl
One or more groups in acryloxypropyl trimethoxy silane, vinyltriethylsilane, methacrylic acid, acrylic acid
Close.
7. the preparation method of the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3, its feature exist
In comprising the following steps：
(1) pre-emulsification：
The mixture I constituted by non-fluorine-containing carbon carbon double bond monomer, emulsifying agent, initiator, crosslinking agent and deionized water is mutually stirred
And ultrasonic emulsification 30-60min；It is mixed that fluorinated acrylate monomer, emulsifying agent, initiator, crosslinking agent and deionized water are constituted
Compound II is mutually stirred and ultrasonic emulsification 30-60min at normal temperatures；
(2) nuclear phase polymerization：
The pre-emulsion that mixture I is mutually formed is placed in equipped with reflux condensing tube, constant pressure funnel, thermometer, N2 introducing devices
Corner flask in, be heated to 60-75 DEG C, react 2-3h；
(3) shell phase polymerization is added dropwise：
The pre-emulsion and initiator solution that mixture II is mutually formed is added dropwise over described corner by dropping funel and burns
In bottle, polymerisation is participated in, time for adding is 2-5h；
(4) obtain fluoro-acrylate copolymer emulsion
After completion of dropping, temperature is risen to into 80-95 DEG C of reaction 1-3h, emulsion is obtained after stopping reaction, is cooled to 35-45
DEG C, it is 6-7 to add pH adjusting agent to adjust pH, you can obtain fluoro-acrylate copolymer emulsion.
8. the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3 is used for the method for preparing latex film,
Characterized in that, including procedure below：
Obtained fluoro-acrylate copolymer emulsion is directly coated on base material, drying and forming-film.
9. the fluoro-acrylate copolymer emulsion according to any one of Claim 1-3 is used for the method for preparing latex film,
Characterized in that, by fluoro-acrylate copolymer emulsion breaking, latex is formed, and deionized water is rinsed, drying；By drying
Good latex is dissolved in solvent, then deionized water is precipitated out, the latex for precipitating is dissolved in solvent be configured to it is molten
Liquid, film；Dry in 20-120 DEG C, fluorinated acrylate latex film is obtained.
10. fluoro-acrylate copolymer emulsion according to claim 9 is used for the method for preparing latex film, and its feature exists
In described dissolving latex solvent for use is selected from acetone, toluene, dimethylbenzene, methyl alcohol, carbon tetrachloride, tetrahydrofuran.
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| CN109294139A (en) * | 2018-10-08 | 2019-02-01 | 长春理工大学 | A method of self-supporting film is prepared using salting liquid |
| TWI819152B (en) * | 2018-12-03 | 2023-10-21 | 日商Ｄｉｃ股份有限公司 | Adhesive composition and laminated film using the same |
| CN111087523A (en) * | 2019-12-31 | 2020-05-01 | 山东华夏神舟新材料有限公司 | Normal-temperature curing fluorocarbon resin emulsion for back plate film and preparation method and application thereof |
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Application publication date: 20170329 |