CN103864982A - Preparation method of fluorinated acrylate emulsion - Google Patents

Preparation method of fluorinated acrylate emulsion Download PDF

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Publication number
CN103864982A
CN103864982A CN201310695104.4A CN201310695104A CN103864982A CN 103864982 A CN103864982 A CN 103864982A CN 201310695104 A CN201310695104 A CN 201310695104A CN 103864982 A CN103864982 A CN 103864982A
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emulsion
acrylate
monomer
sodium
methyl
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CN201310695104.4A
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CN103864982B (en
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李义涛
郑炳发
汤诚
杨策宇
王寅飞
邹智杰
游孟梦
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东莞市长安东阳光铝业研发有限公司
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Abstract

The invention relates to a preparation method of a fluorinated acrylate emulsion. A method of semi-continuous seed emulsion polymerization is used, so that a fluorine monomer is concentrated in a copolymer shell; meanwhile, a reactive emulsifier is used, so that emulsifier molecules are combined on the surface of emulsion particles via stable covalent bonds. Specific method comprises the following steps: firstly, preparing a nuclear emulsion, dropping a shell preemulsion on the basis of the shell preemulsion, and polymerizing through a semi-continuous seed method to obtain an aqueous fluorinated acrylate shell emulsion. Due to the preparation technique, a fluorine-containing monomer is placed in the shell, so that the efficiency is maximized, advantages of a fluorine-containing polymer is shown as much as possible; the emulsion obtained through the method has excellent storage stability, calcium ion stability, freeze-thaw stability and mechanical stability.

Description

A kind of preparation method of fluorinated acrylate emulsion
Technical field
The present invention relates to coating emulsion and production technical field, be specifically related to a kind of preparation method of fluorinated acrylate emulsion.
Background technology
Water-based (methyl) series of acrylate coating has that good film-forming property, application property are good, the alkali resistance of film and the advantage such as tint retention is good, pollution-free, has obtained application widely.But (methyl) Emulsion acrylic resin high thermal resistance is poor, in building coating application, the most obvious shortcoming is that high temperature after-tacks, and causes contamination resistance to decline, and water tolerance and weather resisteant are poor, so its use range is restricted.In order to obtain the coating of excellent performance, the fluorochemical monomer of people's grafting some amount in acrylic resin carries out modification, can keep the original advantage of acrylate copolymer, give again the features such as its excellent weathering resistance, water tolerance, oil-proofness, thermotolerance and contamination resistance, thereby be with a wide range of applications, but the price of fluorinated acrylate monomer is very high, such monomer of excessive use, will certainly improve the price of the acrylic ester polymer after modification.
Therefore, maximizing under the prerequisite of fluoropolymer plurality of advantages, how to reduce fluorinated acrylate emulsion cost and become the focus that people pay close attention to.Because being easily subject to the impact of external environment, the conventional emulsifier molecule using in letex polymerization resolves simultaneously, make emulsion particle collision cohesion, and after emulsion film forming, remain in the emulsifying agent molecule in polymkeric substance, easily in polymkeric substance, generation is moved and is caused the water tolerance of polymeric film to decline.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the fluorinated acrylate emulsion with nucleocapsid structure, in the time reducing the consumption of fluorine monomer, make emulsion still there is excellent weathering resistance, resistance to soiling, water tolerance and resistance to acids and bases.Adopt reactive emulsifier simultaneously, make emulsifying agent molecule be combined in emulsion particle surface with more stable covalent, so that the emulsion obtaining has good package stability, Calcium ion stability, freeze-thaw stability and mechanical stability.
Hud typed fluorine-containing (methyl) of the present invention acrylic ester emulsion, by monomer, the moon/non-emulsifiers, reactive emulsifier, water, initiator and pH adjusting agent, adopts the polymerization of semi-continuous seed method to obtain after pre-emulsification.First prepare seed emulsion, then, by being rich in after the shell monomer mixture pre-emulsification of fluorine monomer to obtain shell pre-emulsion, adopt the method dripping that shell pre-emulsion is added drop-wise in seed emulsion and obtains target product after reaction.
Object of the present invention is achieved through the following technical solutions:
A technical scheme of the present invention provides a kind of preparation method of fluorinated acrylate emulsion, comprises following steps:
1) prepare pre-emulsion
I) preparation of core pre-emulsion
After anionic emulsifier, nonionic emulsifying agent, reactive emulsifier, initiator and deionized water and stirring are dissolved, add containing or methyl acrylic ester monomer and the acrylic ester monomer mixed solution of not fluorine-containing alkylacrylate monomer, stir pre-emulsification and prepare core pre-emulsion, wherein each constituent mass part is:
II) preparation of shell pre-emulsion
After anionic emulsifier, nonionic emulsifying agent, initiator and deionized water and stirring are dissolved, add the mixing solutions of fluorine-containing alkylacrylate monomer and functional monomer, stir pre-emulsification and prepare shell pre-emulsion, wherein each constituent mass part is:
2) preparation of seed emulsion
Get the 20-50% of the obtained core pre-emulsion of step 1), under protection of inert gas, stir, be warming up to 70-90 ℃, after temperature-stable, drip residual nucleus emulsion, insulation reaction afterwards, makes seed emulsion;
3) prepare fluorinated acrylate emulsion
Keep stirring; protection of inert gas; temperature maintains under 70-90 ℃ of condition; to step 2) gained seed emulsion drips the obtained shell pre-emulsion of step 1); drip complete insulation reaction, after reacting completely, be down to 10-30 ℃; dripping pH adjusting agent to pH value is 7.0-8.5, and mixed solution filters to obtain fluorinated acrylate emulsion.
The preparation method who provides according to technique scheme, in some embodiments, described acrylic ester monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, vinylformic acid laurate, Process Conditions of Cetane Acrylate or octadecyl acrylate.
The preparation method who provides according to technique scheme, in some embodiments, described methyl acrylic ester monomer is selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methacrylic acid cyclohexanol, lauryl methacrylate(LMA) or stearyl methacrylate.
The preparation method who provides according to technique scheme, in some embodiments, described fluorine-containing alkylacrylate monomer is compound shown in formula I
Wherein R 1be selected from H or methyl, R 2be selected from C 2-C 20containing fluoroalkyl.
In some embodiments, described fluorine-containing alkylacrylate monomer is selected from trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate, perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate, perfluoro capryl ethyl propylene acid esters or perfluoro capryl ethyl-methyl acrylate.
The preparation method who provides according to technique scheme, in some embodiments, described functional monomer is selected from methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, methacrylonitrile, vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinyl cyanide, acrylamide, N hydroxymethyl acrylamide, Ethylene glycol dimethacrylate, diacetone-acryloamide(DAA) or adipic acid dihydrazide.
The preparation method who provides according to technique scheme, in some embodiments, described reactive emulsifier is selected from 2-propenyl ether-3-hydroxy propane-1-sodium sulfonate, alkylphenol allyl polyether vitriol, 2-acrylamide-2-methyl propane sulfonic acid sodium salt, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, sodium vinyl sulfonate, allyl polyether vitriol or allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate.
The preparation method who provides according to technique scheme, in some embodiments, described anionic emulsifier is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, 1,2-dodecyl diether disulfonic acid disodium, decyl Soxylat A 25-7 monomester succinate disodium sulfonate salt, polyoxyethylene nonylphenol ether ammonium sulfate, polyoxyethylene nonylphenol ether monomester succinate disodium sulfonate salt or polyoxyethylenated alcohol sodium sulfate.
The preparation method that this provides according to technique scheme, in some embodiments, described nonionic emulsifying agent is fatty alcohol-polyoxyethylene ether, polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether.
The preparation method who provides according to technique scheme, in some embodiments, described initiator is persulphate.
In some embodiments, persulphate is selected from Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
The preparation method who provides according to technique scheme, in some embodiments, described pH adjusting agent is selected from ammoniacal liquor, alkali-metal carbonate, supercarbonate, phosphoric acid salt or hydrophosphate.
In other embodiments, pH adjusting agent of the present invention is selected from ammoniacal liquor, sodium carbonate, sodium bicarbonate, Sodium phosphate dibasic, salt of wormwood, potassium hydrogen phosphate or dipotassium hydrogen phosphate or its combination.
Fluorinated acrylate emulsion prepared by the method that another technical scheme of the present invention provides employing technique scheme to provide is for preparing the application of building coating.
Unless clearly state in contrast, otherwise all scopes that the present invention quotes comprised end value.For example, after being coated on base material, " being warming up to 70-90 ℃ " represents that the temperature range T heating up is 70 ℃≤T≤90 ℃.
The end value that the present invention quotes may comprise 0, and in the time that a certain end value is 0, the content that represents its representative is optional, for example, in composition list, " fluorine-containing alkylacrylate monomer 0-6.0 part " represents in certain embodiments, can not add fluorine-containing alkylacrylate monomer.
The term "or" that the present invention uses represents alternatives, if suitable, they can be combined, and that is to say, term "or" comprises each listed independent alternatives and their combination.For example, " pH adjusting agent is selected from ammoniacal liquor, alkali-metal carbonate, supercarbonate, phosphoric acid salt or hydrophosphate " represents that pH adjusting agent can be the one of ammoniacal liquor, alkali-metal carbonate, supercarbonate, phosphoric acid salt, hydrophosphate, can be also its more than one combination.
Beneficial effect of the present invention is: the present invention adopts (methyl) acrylic ester monomer and fluorine-containing alkylacrylate monomer by the method for semi-continuous seed emulsion polymerization, preparation has the fluorinated acrylate emulsion of nucleocapsid structure, the emulsion obtaining is keeping on the basis of (methyl) acrylic ester emulsion excellent properties, there is again the characteristic of fluorine, and because fluorochemical monomer is enriched on the surface of multipolymer, in the time having reduced the consumption of fluorine monomer, still fully demonstrate chemical resistant properties, uvioresistant and the antioxidant property of C-F excellence.Whole reaction process adopts dropping mode, the fluorinated acrylate emulsion solid content obtaining is greater than 40%, in emulsion, latex particle size is less simultaneously, size distribution is narrower, there is good package stability, dilution stability, freeze-thaw stability and mechanical stability, and preparation technology is simple, easy control of reaction conditions, can be widely used in the fields such as building, industrial coating, textile finishing and leather finish.
Embodiment
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, some distortion and the improvement made, all belong to protection scope of the present invention.
Embodiment 1
By after deionized water 125.0g, sodium lauryl sulphate 1.0g, polyoxyethylene octylphenol ether 2.0g, 2-propenyl ether-3-hydroxy propane-1-sodium sulfonate 1.5g, Potassium Persulphate 0.5g stirring and dissolving, slowly add the mixed solution of methyl methacrylate 58.0g and butyl acrylate 58.0g, high speed machine stirs pre-emulsification 45 minutes, obtains 246.0g pre-emulsion I;
By after deionized water 53.0g, sodium lauryl sulphate 0.4g, polyoxyethylene octylphenol ether 0.8g, Potassium Persulphate 0.25g stirring and dissolving, slowly add the mixed solution of trifluoroethyl methacrylate 40.0g and hydroxyethyl methylacrylate 7.5g, high speed machine stirs pre-emulsification 30 minutes, obtains 93.7g pre-emulsion II.
Keeping, in reaction unit nitrogen atmosphere, getting 80.0g pre-emulsion I, under 200 revs/min, stir, open water of condensation, be heated to 80 ℃.After temperature-stable, slowly drip residue pre-emulsion I, drip rear insulation reaction 1.5 hours, obtain seed emulsion.
On the seed emulsion basis of above-mentioned acquisition, drip pre-emulsion II, reaction stirring velocity is 175 revs/min, and temperature is controlled at 80 ℃, drips rear insulation 2.0 hours, stopped reaction.Emulsion is cooled to 35 ℃, and dripping 2.0g ammoniacal liquor adjust pH is 7.8, closes nitrogen, water of condensation, filters to obtain 335.85g emulsion.
Embodiment 2
By after deionized water 340.0g, Sodium dodecylbenzene sulfonate 4.8g, fatty alcohol-polyoxyethylene ether 4.8g, 2-acrylamide-2-methyl propane sulfonic acid sodium salt 6.4g, Potassium Persulphate 2.25g stirring and dissolving, slowly add the mixed solution of β-dimethyl-aminoethylmethacrylate 170.0g, ethyl propenoate 138.0g and vinylformic acid hexafluoro butyl ester 22.0g, high speed machine stirs pre-emulsification 1 hour, obtains 666.25g pre-emulsion I.
By after deionized water 70g, Sodium dodecylbenzene sulfonate 0.68g, fatty alcohol-polyoxyethylene ether 1.36g, 1.0g Potassium Persulphate stirring and dissolving, slowly add the mixed solution of vinylformic acid hexafluoro butyl ester 58.0g and methacrylonitrile 19.2g, high speed machine stirs pre-emulsification 45 minutes, obtains 149.24g pre-emulsion II.
Keeping, in reaction unit nitrogen atmosphere, getting 225.0g pre-emulsion I, under 250 revs/min, stir, open water of condensation, be heated to 75 ℃.After temperature-stable, slowly drip residue pre-emulsion I, drip insulation reaction 2.0 hours, obtain seed emulsion.
On the seed emulsion basis of above-mentioned acquisition, drip pre-emulsion II, reaction stirring velocity is 225 revs/min, and temperature is controlled at 75 ℃, drips rear insulation 3.0 hours, stopped reaction.Emulsion is cooled to 40 ℃, drips 5% sodium hydrogen carbonate solution 10.0g, adjust pH is 8.2, closes nitrogen, water of condensation, filters to obtain 818.64g emulsion.
Embodiment 3
By deionized water 165.0g, 1, after 2-dodecyl diether disulfonic acid disodium 1.6g, polyoxyethylene nonylphenol ether 2.0g, alkylphenol allyl polyether vitriol 2.2g, Sodium Persulfate 1.35g stirring and dissolving, slowly add the mixed solution of butyl methacrylate 70.0g, Process Conditions of Cetane Acrylate 90.0g and vinylformic acid ten trifluoro monooctyl ester 10.0g, high speed machine stirs pre-emulsification 30 minutes, obtains 332.15g pre-emulsion I.
By deionized water 40.0g, 1, after 2-dodecyl diether disulfonic acid disodium 0.7g, polyoxyethylene nonylphenol ether 0.7g, 0.40g Sodium Persulfate stirring and dissolving, slowly add the mixed solution of vinylformic acid ten trifluoro monooctyl ester 28.0g, N hydroxymethyl acrylamide 8.5g and methacrylic acid 3.0g, high speed machine stirs pre-emulsification 45 minutes, obtains 80.9g pre-emulsion II.
Keeping, in reaction unit nitrogen atmosphere, getting 100.0g pre-emulsion I, under 225 revs/min, stir, open water of condensation, be heated to 78 ℃.After temperature-stable, slowly drip residue pre-emulsion I, drip insulation reaction 1.0 hours, obtain seed emulsion.
On the seed emulsion basis of above-mentioned acquisition, drip pre-emulsion II, reaction stirring velocity is 200 revs/min, and temperature is controlled at 78 ℃, drips rear insulation 2.0 hours, stopped reaction.Emulsion is cooled to 20 ℃, drips 5% potassium hydrogen phosphate 8.5g, adjust pH is 8.5, closes nitrogen, water of condensation, filters to obtain 415.50g emulsion.
Embodiment 4
By after deionized water 460.0g, decyl Soxylat A 25-7 monomester succinate disodium sulfonate salt 3.75g, fatty alcohol-polyoxyethylene ether 3.50g, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate 6.25g, ammonium persulphate 3.75g stirring and dissolving, slowly add the mixed solution of lauryl methacrylate(LMA) 220.0g and vinylformic acid laurate 200.0g, high speed machine stirs pre-emulsification 1 hour, obtains 897.25g pre-emulsion I.
By after deionized water 110g, decyl Soxylat A 25-7 monomester succinate disodium sulfonate salt 1.15g, fatty alcohol-polyoxyethylene ether 1.05g, ammonium persulphate 1.5g stirring and dissolving, slowly add the mixed solution of perfluoro butyl ethyl propylene acid esters 96.0g, N hydroxymethyl acrylamide 9.5g and hydroxyethyl methylacrylate 18.5g, high speed machine stirs pre-emulsification 1 hour, obtains 236.2g pre-emulsion II.
Keeping, in reaction unit nitrogen atmosphere, getting 300.0g pre-emulsion I, under 300 revs/min, stir, open water of condensation, be heated to 82 ℃.After temperature-stable, slowly drip residue pre-emulsion I, drip insulation reaction 2.5 hours, obtain seed emulsion.
On the seed emulsion basis of above-mentioned acquisition, drip pre-emulsion II, reaction stirring velocity is 250 revs/min, and temperature is controlled at 82 ℃, drips rear insulation 3.0 hours, stopped reaction.Emulsion is cooled to 25 ℃, drips 5% salt of wormwood 12.5g, adjust pH is 8.0, closes nitrogen, water of condensation, filters to obtain 1138.84g emulsion.
Embodiment 5
By after deionized water 600.0g, polyoxyethylene nonylphenol ether ammonium sulfate 5.0g, polyoxyethylene octylphenol ether 8.0g, allyl polyether vitriol 8.0g, ammonium persulphate 1.8g stirring and dissolving, slowly add the mixed solution of stearyl methacrylate 225.0g and Isooctyl acrylate monomer 275.0g, high speed machine stirs pre-emulsification 30 minutes, obtains 1122.8g pre-emulsion I;
By after deionized water 175.0g, polyoxyethylene nonylphenol ether ammonium sulfate 2.6g, polyoxyethylene octylphenol ether 4.2g, ammonium persulphate 0.9g stirring and dissolving, slowly add the mixed solution of perfluoro hexyl ethyl-methyl acrylate 185.0g and Rocryl 410 40.5g, high speed machine stirs pre-emulsification 30 minutes, obtains 408.2g pre-emulsion II.
Keeping, in reaction unit nitrogen atmosphere, getting 380.0g pre-emulsion I, under 300 revs/min, stir, open water of condensation, be heated to 80 ℃.After temperature-stable, slowly drip residue pre-emulsion I, drip rear insulation reaction 2.0 hours, obtain seed emulsion.
On the seed emulsion basis of above-mentioned acquisition, drip pre-emulsion II, reaction stirring velocity is 250 revs/min, and temperature is controlled at 80 ℃, drips rear insulation 5.0 hours, stopped reaction.Emulsion is cooled to 30 ℃, drips 5% dipotassium hydrogen phosphate 18.5g, adjust pH is 8.4, closes nitrogen, water of condensation, filters to obtain 1518.7g emulsion.
Embodiment 6
To be mixed with emulsion paint by embodiment of the present invention 1-5 emulsion and detect, detection is seen for oneself table 1, and testing standard is HG/T4104-2009.
Table 1 is prepared the specific performance of emulsion

Claims (13)

1. a preparation method for fluorinated acrylate emulsion, is characterized in that comprising following steps:
1) prepare pre-emulsion
I) preparation of core pre-emulsion
After anionic emulsifier, nonionic emulsifying agent, reactive emulsifier, initiator and deionized water and stirring are dissolved, add containing or methyl acrylic ester monomer and the acrylic ester monomer mixed solution of not fluorine-containing alkylacrylate monomer, stir pre-emulsification and prepare core pre-emulsion, wherein each constituent mass part is:
II) preparation of shell pre-emulsion
After anionic emulsifier, nonionic emulsifying agent, initiator and deionized water and stirring are dissolved, add the mixing solutions of fluorine-containing alkylacrylate monomer and functional monomer, stir pre-emulsification and prepare shell pre-emulsion, wherein each constituent mass part is:
2) preparation of seed emulsion
The 20-50% that gets the obtained core pre-emulsion of step 1) stirs under protection of inert gas, is warming up to 70-90 ℃, after temperature-stable, drips residual nucleus emulsion, and insulation reaction afterwards, makes seed emulsion;
3) prepare fluorinated acrylate emulsion
Keep stirring; protection of inert gas; temperature maintains under 70-90 ℃ of condition; to step 2) gained seed emulsion drips the obtained shell pre-emulsion of step 1); drip complete insulation reaction, after reacting completely, be down to 10-30 ℃; dripping pH adjusting agent to pH value is 7.0-8.5, and mixed solution filters to obtain fluorinated acrylate emulsion.
2. preparation method according to claim 1, is characterized in that, described acrylic ester monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, vinylformic acid laurate, Process Conditions of Cetane Acrylate or octadecyl acrylate.
3. preparation method according to claim 1, it is characterized in that, described methyl acrylic ester monomer is selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methacrylic acid cyclohexanol, lauryl methacrylate(LMA) or stearyl methacrylate.
4. preparation method according to claim 1, is characterized in that, described fluorine-containing alkylacrylate monomer is formula I compound
Wherein R 1be selected from H or methyl, R 2be selected from C 2-C 20containing fluoroalkyl.
5. preparation method according to claim 4, it is characterized in that, described fluorine-containing alkylacrylate monomer is selected from trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate, perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate, perfluoro capryl ethyl propylene acid esters or perfluoro capryl ethyl-methyl acrylate.
6. preparation method according to claim 1, it is characterized in that, described functional monomer is selected from methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, methacrylonitrile, vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinyl cyanide, acrylamide, N hydroxymethyl acrylamide, Ethylene glycol dimethacrylate or diacetone-acryloamide(DAA) or its combination.
7. preparation method according to claim 1, it is characterized in that, described reactive emulsifier is selected from 2-propenyl ether-3-hydroxy propane-1-sodium sulfonate, alkylphenol allyl polyether vitriol, 2-acrylamide-2-methyl propane sulfonic acid sodium salt, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, sodium vinyl sulfonate, allyl polyether vitriol or allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate.
8. preparation method according to claim 1, it is characterized in that, described anionic emulsifier is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, 1,2-dodecyl diether disulfonic acid disodium, decyl Soxylat A 25-7 monomester succinate disodium sulfonate salt, polyoxyethylene nonylphenol ether ammonium sulfate, polyoxyethylene nonylphenol ether monomester succinate disodium sulfonate salt or polyoxyethylenated alcohol sodium sulfate.
9. preparation method according to claim 1, is characterized in that, described nonionic emulsifying agent is selected from fatty alcohol-polyoxyethylene ether, polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether.
10. preparation method according to claim 1, is characterized in that, described initiator is persulphate.
11. preparation methods according to claim 10, is characterized in that, described persulphate is selected from Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
12. preparation methods according to claim 1, is characterized in that, described pH adjusting agent is selected from ammoniacal liquor, alkali-metal carbonate, supercarbonate, phosphoric acid salt or hydrophosphate.
13. preparation methods according to claim 1, is characterized in that, described pH adjusting agent is selected from ammoniacal liquor, sodium carbonate, sodium bicarbonate, Sodium phosphate dibasic, salt of wormwood, potassium hydrogen phosphate or dipotassium hydrogen phosphate.
CN201310695104.4A 2012-12-15 2013-12-14 Preparation method of fluorinated acrylate emulsion CN103864982B (en)

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CN104403471A (en) * 2014-03-04 2015-03-11 上海大学 Polyacrylic acid emulsion hydrophobic coating material with low fluorine content and preparation method thereof
CN105440201A (en) * 2014-08-13 2016-03-30 南京理工大学 Core-shell type short-chain fluorine-containing acrylate emulsion and preparation method thereof
CN104387516A (en) * 2014-10-22 2015-03-04 陕西延长石油(集团)有限责任公司 Preparation method of fluoro-acrylate polymer nucleus/casing emulsion with graded distribution fluorine content
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CN106674416B (en) * 2015-11-05 2019-08-06 中昊晨光化工研究院有限公司 A kind of Fluorine-Containing Copolymer Emulsion and its synthetic method, application
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CN105801746A (en) * 2016-03-28 2016-07-27 齐齐哈尔大学 Organic fluorine-modified acrylate flax finishing agent and preparation method and application thereof
CN105837739A (en) * 2016-05-05 2016-08-10 常熟林润氟硅材料有限公司 Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion
CN105859949A (en) * 2016-06-27 2016-08-17 南京信息工程大学 Soap-free fluorocarbon emulsion prepared from perfluoroalkyl ethylenes through copolymerization and preparation method of soap-free fluorocarbon emulsion
CN105859949B (en) * 2016-06-27 2018-03-06 南京信息工程大学 A kind of copolymerization of perfluoro alkyl ethylene prepare without soap fluorine carbon emulsion and preparation method thereof
CN106189632A (en) * 2016-08-05 2016-12-07 宁波江东仑斯福环保科技有限公司 A kind of preparation method of fire-retardant water-retaining type thermal insulation coatings
CN106589216A (en) * 2016-12-03 2017-04-26 范进 Fluorine-containing polyacrylic acid latex and preparation method thereof
CN110540614A (en) * 2018-05-28 2019-12-06 中国科学院上海有机化学研究所 Water-based fluorine-containing acrylate copolymer, hybrid membrane, preparation method and application thereof
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