CN1687150A - Method for preparing stable latex of copolymer containing fluorinated acrylic ester - Google Patents
Method for preparing stable latex of copolymer containing fluorinated acrylic ester Download PDFInfo
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Abstract
The present method of fluorine-contained acrylic ester copolymer stable emulsion includes the following steps: in the container equipped with stirrer, reflux condenser tube, N2 gas protection and charging device adding anionic/non-ionic composite emulsifier, then placing the water, polymerization monomer, acetone, chain transfer agent and initiator into said container, severaly stirring for 0.5-2 hr at normal temperature to obtain uniform pre-emulsion; dividing said pre-emulsion into two portions, heating one-third of the pre-emulsion to 55 deg.C-75 deg.C ioinitiate polymerization reaction, after the reaction liquor produces blue light, drop-adding residual pre-emulsion, drop-adding time is 1.5h-2.5h, after the drop additionis completed, adding residual initiator, heat-insulating reaction for 2-6 hr, stirring and cooling to room temperature so as to obtain the invented product.
Description
Technical field
The present invention relates to prepare the method for the stable fluoro-acrylate copolymer emulsion that is used to give the fabric waterproof oil preventing performance.
Background technology
Fluoro-acrylate copolymer emulsion surface tension can be low to moderate 10～15dyn/cm, can be used as the textile surface treatment agent, shows excellent waterproof and grease proofness.Fluorinated acrylate polymer contains the perfluoroalkyl of 3 or 3 above carbon atoms of side extension usually, these perfluoro alkyl groups generally are connected on the not fluorine-containing skeleton polymer chain by various linking groups, and these skeleton polymers can be (methyl) acrylate, vinyl, vinylidene or other group.Prepare simultaneously and adopted some non-fluorine monomers when the fluoro-acrylate copolymer emulsion is synthesized, the use of these non-fluorine monomers is mainly used to regulate the performance of fabric finishing agent, be used for the fabric face group crosslinked, to improve the connectivity of polymeric film and fiber, can also reduce production cost of products.Although the effect of disclosed fluoro-acrylate copolymer emulsion under some application conditions is gratifying in the prior art, emulsion is poor stability under some conditions.For example: in high temperature, low temperature, high potential of hydrogen environment, or placed for a long time, emulsion can produce flocculation or deposited phenomenon, has reduced the performance of emulsion, has influenced the application of emulsion.Therefore, preparation all can be given the method for the stable fluoro-acrylate copolymer emulsion of the excellent waterproof and oilproof performance of fabric under various special environment conditions, promotes for the quality product of textiles and Clothing industry to have crucial meaning.
Summary of the invention
Technical problem: the preparation method who the purpose of this invention is to provide a kind of fluoro-acrylate copolymer stable emulsion, the emulsion that obtains with this method has good storing stability, dilution stability, high-temperature stability, freeze-thaw stability and pH stability, can give the waterproof and oilproof performance of fabric excellence simultaneously.
Technical scheme:
The present invention includes the method for preparing the fluoro-acrylate copolymer stable emulsion:
Step 1), stirring, reflux condensing tube, N are being housed
2Add the moon/nonionic compound emulsifier in the four-hole boiling flask of gas shiled and feeding device, again water, polymerization single polymerization monomer, acetone, chain-transfer agent and initiator are placed the flask vigorous stirring to obtain uniform pre-emulsion in 0.5～2 hour;
Step 2), with the pre-emulsion separated into two parts, wherein 1/3rd be heated to 55 ℃～75 ℃ initiated polymerizations, after blue light appears in question response liquid, drip the residue pre-emulsion;
Step 3), dropwise after, will remain initiator again and add, insulation reaction 2～6 hours stirs and is cooled to room temperature.
Wherein, polymerization single polymerization monomer comprises:
Perfluor alkyl ethide acrylate (C
nF
2n+1CH
2CH
2OCOCH=CH
2); Alkyl acrylate; Hydroxy ethyl methacrylate; N hydroxymethyl acrylamide etc.
Wherein: perfluor alkyl ethide acrylate (C
nF
2n+1CH
2CH
2OCOC=CH
2), can be changed to
Methyl perfluor alkyl ethide acrylate [C
nF
2n+1CH
2CH
2OCOCH (CH
3)=CH
2];
Alkyl acrylate also can be changed to alkyl methacrylate,
Consisting of of polymerization single polymerization monomer:
(a) based on the mixture of the perfluor alkyl ethide acrylate monomer of total monomer weight 50wt%～75wt% with following formula:
CF
3CF
2(CF
2)
kCH
2CH
2OC(O)C(R)＝CH
2
Wherein R is H or CH
3
K is an even number, wherein k=4,6,8,10 monomeric being distributed as:
The monomer of 25wt%-70wt%k=4,
The monomer of 20wt%-40wt%k=6,
The monomer of 5wt%-25wt%k=8,
The monomer of 0wt%-15wt%k=10.
(b) based on alkyl methacrylate or the alkyl acrylate of total monomer weight 10wt%～30wt% from alkyl chain length with 2～18 carbon atoms;
(c) 0.1wt%～5wt% (based on total monomer weight) N hydroxymethyl acrylamide;
(d) 0.1wt%～10wt% (based on total monomer weight) hydroxyethyl (methyl) acrylate;
In step 1), the moon/nonionic compound emulsifier comprises:
(e) nonionic surface active agent of 1wt%～10wt% (by total monomer weight) can be the condensation product of ethylene oxide and fatty alcohol or the condensation product of ethylene oxide and alkylphenol.As ethylene oxide copolymer, epoxy propane copolymer, oxyethane has hexylphenol, C12～C16 chain alkyl thioalcohol, the anhydro sorbitol list (condensation product of the fatty acid ester of C7～C10) or C7～C10 alkylamine with it.
(f) by the anion surfactant of total monomer weight 1wt%～5wt%, can be an alkali metal salt of alkylsulphonic acid of long-chain and an alkali metal salt of sweet-smelling alkyl sulfonic acid, as: sodium laurylsulfonate, Sodium dodecylbenzene sulfonate etc.
In the step 1), chain-transfer agent is adjusted the polymkeric substance chain length, and as using alkyl sulfhydryl, tetracol phenixin or triphenyl methane etc., consumption is counted 0.03wt%～0.1wt% by total monomer weight;
In step 1), initiator can be used persulphate, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc., or azo-compound, as: hydrochloric acid azo two NSC 18620, Diisopropyl azodicarboxylate etc., the usage quantity of initiator is counted 0.1wt%～1.5wt% by total monomer weight.
Of the present invention being described in detail:
The invention provides a kind of method for preparing the fluoro-acrylate copolymer stable emulsion, this emulsion has advantages of higher stability under conditions such as high temperature, low temperature or high potential of hydrogen (hot environment is meant at 60 ℃ and placed five days continuously down, low temperature environment is meant-20 ℃ environment, typical high potential of hydrogen condition refers to that pH is between 2～12), the textiles of wherethrough reason has excellent waterproof and oil preventing performance.
Characteristics of the present invention are:
(1) adopts the semicontinuous dripping method of monomer.Promptly drip the polymerization process of remaining comonomer in emulsion prepolymerization system continuously, the quantity of monomer droplet can reduce relatively in the system like this, can reduce the generation of condensation product.The emulsion that the semicontinuous dripping method of monomer makes with respect to feeding method, its latex particle size is of moderate size, even size distribution, stability of emulsion obviously improves.
(2) adopted the moon/nonionic compound emulsifier.Emulsifier type and consumption are very big to the stability of emulsion influence, and the size of stability of emulsion can be weighed with its characteristic parameter ζDian Shi, and the absolute value of ζDian Shi is big more, and its emulsion is stable more.Adopt the emulsion ζDian Shi value of sun/nonionic compound emulsifier preparation generally less, stability of emulsion is relatively poor.Under same reaction conditions, the present invention adopts the moon/nonionic compound emulsifier to prepare fluorine-containing copolymer emulsion, and the absolute value of its ζDian Shi obviously increases, and the stability of its emulsion improves greatly.The ratio of finding the moon/nonionic emulsifying agent simultaneously also has remarkable influence to ζDian Shi, and when ratio increased, ζDian Shi increased thereupon, and the stability of emulsion increases.Emulsion prepared by this method all can keep the stable dispersion state in high temperature, low temperature, high potential of hydrogen environment.
(3) polymerization technique is optimized.Temperature of reaction, monomer dropping time, chain transfer agent concentration, aqueous solvent can influence latex particle size size and distribution of sizes with monomer mass than all, thereby influence stability of emulsion, and the present invention carries out global optimization to these influence factors.
Beneficial effect:
Temperature of reaction is controlled between 55 ℃～75 ℃ in embodiments of the invention, the pre-emulsified monomer dropping time is 1.5h～2.5h, chain transfer agent concentration is 0.03wt%～0.1wt% (by a total monomer weight), solvent is 3: 1～10: 1 with the monomer mass ratio, the moon/nonionic emulsifying agent mass ratio is 2: 5～2: 7, and the consumption of compound emulsifying agent is 2wt%～15wt% (by a total monomer weight).The median size that makes the emulsion emulsion particle is 70nm～100nm, and average poly value is 0.1～0.4, and size distribution is even, and the absolute value of average ζDian Shi is 35mv～50mv, the good stability of emulsion.
The non-fluorine monomer that is used to prepare emulsion of the present invention comprises the alkyl acrylate or the alkyl methacrylate of the alkyl chain length that contains 2～18 carbon atoms, in order to have optimum performance, the usage quantity of this alkyl acrylate is 10wt%～30wt% (by a total monomer weight), further preferred, best alkyl acrylate should be butyl acrylate or Isooctyl acrylate monomer.The non-fluorine monomer that is used to prepare emulsion of the present invention comprises that also consumption is N hydroxymethyl acrylamide and 0.1wt%～10wt% (based on total monomer weight) hydroxyethyl (methyl) acrylate of 0.1wt%～5wt% (based on total monomer weight), further preferred, the consumption of N hydroxymethyl acrylamide is 1wt%～2wt% (based on a total monomer weight), and the consumption of hydroxyethyl (methyl) acrylate is 3wt%～5wt% (based on a total monomer weight).
Nonionic surface active agent is used in combination with anion surfactant.The add-on of nonionic surface active agent is 1wt%～10wt% (by a total monomer weight), and further preferred, its add-on is 3wt%～6wt% (by a total monomer weight).The add-on of anion surfactant is 1wt%～5wt% (by a total monomer weight), and further preferred, its add-on is 2wt%～3wt% (by a total monomer weight).
The sample median size and the size distribution poly value of PCS subparticle analysis-e/or determining emulsion, the poly value is the characteristic constant that this instrument is used for representing size distribution, the big more expression size distribution of its value is wide more, on the contrary the expression size distribution is even more.
ζDian Shi is that emulsification is pulled on measuring of electric charge, measures with Delsa 440 SX Zita Potential Analyzer.
In the method for the invention, use the emulsion copolymerization method to prepare multipolymer of the present invention.This method is that stirring, reflux condensing tube, N are being housed
2Add compound emulsifying agent in the four-hole boiling flask of gas shiled and feeding device; to treat that again those monomers of polymeric, water, chain-transfer agent and a part of initiator place the flask vigorous stirring to obtain uniform pre-emulsion; be divided into two portions; wherein 1/3rd be heated to 55 ℃～75 ℃; initiated polymerization, question response liquid occur dripping remaining pre-emulsion again behind the blue light.
The water miscible liquid of the present invention's preparation can be diluted to 0.5wt%～1wt%, directly is applied on the textiles that need give waterproof and oil preventing performance.Emulsion of the present invention is coated on the textiles by methods such as spraying, dipping or letter dye usually.After removing unnecessary treatment solution, the fabric of handling is carried out preliminarily dried, textiles after will handling at last is cured processing at a certain temperature, as: 110 ℃～190 ℃ following solidification treatment 60～180 seconds, this solidification process was mainly used in water-repellancy, grease proofness and the washing fastness on reinforced fabric surface.Emulsion of the present invention can be used to give the waterproof and oilproof performance of substrate surfaces such as textiles, fiber with excellence.Stable emulsion of the present invention can be used under various special environment conditions.
Embodiment
The preparation method of fluoro-acrylate copolymer stable emulsion of the present invention is:
Step 1) is being equipped with stirring, reflux condensing tube, N
2Add the moon/nonionic compound emulsifier in the container of gas shiled and feeding device, again water, polymerization single polymerization monomer, acetone, chain-transfer agent and initiator are placed the container vigorous stirring to obtain uniform pre-emulsion in 0.5～2 hour;
Step 2) with the pre-emulsion separated into two parts, wherein 1/3rd be heated to 55 ℃～75 ℃ initiated polymerizations, after blue light appears in question response liquid, drip the residue pre-emulsion, the pre-emulsified monomer dropping time is 1.5h～2.5h;
After step 3) dropwises, will remain initiator again and add, insulation reaction 2～6 hours stirs and is cooled to room temperature, obtains the fluoro-acrylate copolymer stable emulsion.
Polymerization single polymerization monomer comprises:
A) based on the mixture of the perfluor alkyl ethide acrylate monomer of total monomer weight 50wt%～75wt% with following formula:
CF
3CF
2(CF
2)
kCH
2CH
2OC(O)C(R)＝CH
2
Wherein R=H or CH
3
K is an even number, wherein k=4,6,8,10 monomeric being distributed as:
The monomer of 25wt%-70wt%k=4,
The monomer of 20wt%-40wt%k=6,
The monomer of 5wt%-25wt%k=8,
The monomer of 0wt%-15wt%k=10;
B) based on the alkyl methacrylate or the alkyl acrylate of the alkyl chain length of total monomer weight 10wt%～30wt% with 2～18 carbon atoms;
C) based on the N hydroxymethyl acrylamide of total monomer weight 0.1～5wt%;
D) based on the hydroxyethyl meth acrylate of total monomer weight 0.1～10wt%.
The moon/nonionic compound emulsifier comprises:
E) by the nonionic surface active agent of total monomer weight 1wt%～10wt%; Can be the condensation product of ethylene oxide and fatty alcohol or the condensation product of ethylene oxide and alkylphenol.As ethylene oxide copolymer, epoxy propane copolymer, oxyethane has hexylphenol, C12～C16 chain alkyl thioalcohol, the anhydro sorbitol list (condensation product of the fatty acid ester of C7～C10) or C7～C10 alkylamine with it.
(f) anion surfactant of 1wt%～5wt% (by total monomer weight) can be an alkali metal salt of alkylsulphonic acid of long-chain and an alkali metal salt of sweet-smelling alkyl sulfonic acid, as: sodium laurylsulfonate, Sodium dodecylbenzene sulfonate etc.
The chain-transfer agent that is used for adjusting the polymkeric substance chain length is alkyl sulfhydryl, tetracol phenixin or triphenyl methane etc., and consumption is by total monomer weight 0.03wt%～0.1wt%.
The following persulphate of initiator, that is: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, or azo-compound: hydrochloric acid azo two NSC 18620, Diisopropyl azodicarboxylate etc., the usage quantity of initiator accounts for the 0.1wt%～1.5wt% of total monomer weight.
Embodiment 1
Present embodiment has illustrated with method of the present invention and has prepared sample.Stirring, reflux condensing tube, N are being housed
2Add the moon/nonionic compound emulsifier in the four-hole boiling flask of gas shiled and feeding device; again 4 kinds of acrylic ester polymerization monomers, acetone, Dodecyl Mercaptan and a part of initiator are placed flask; vigorous stirring 1h obtains uniform pre-emulsion under the normal temperature; be divided into two portions, wherein 1/3rd be heated to 70 ℃ of initiated polymerizations, question response liquid occurs dripping the residue pre-emulsion behind the blue light; after dropwising; to remain initiator again and add, insulation reaction 4h stirs and is cooled to discharging after the room temperature.
Wherein polymerization single polymerization monomer comprises:
A) 60wt% or 65wt% or 70wt% (by total monomer weight) have the mixture of the perfluor alkyl ethide acrylate monomer of following formula:
CF
3CF
2(CF
2)
kCH
2CH
2OC(O)C(R)＝CH
2
Wherein R=H or CH
3
K is an even number, wherein k=4,6,8,10 monomeric being distributed as:
The monomer of 25wt%-70wt%k=4,
The monomer of 20wt%-40wt%k=6,
The monomer of 5wt%-25wt%k=8,
The monomer of 0wt%-15wt%k=10;
B) by the alkyl acrylate of the alkyl chain length of total monomer weight 28wt% or 24wt% or 20wt% with 2-18 carbon atom;
C) 2wt% (by total monomer weight) N hydroxymethyl acrylamide;
D) 5wt% (by total monomer weight) hydroxyethyl (methyl) acrylate.
Comparative Examples A
This embodiment has illustrated with the embodiment of the invention 1 and has prepared sample similarly, just changed anion surfactant into cats product.
Comparative example B
This embodiment has illustrated with the embodiment of the invention 1 and has prepared sample similarly, just changes the continuous dripping method of monomer into monomer feeding method.Stirring, reflux condensing tube, N are being housed
2Add a certain proportion of the moon/nonionic compound emulsifier in the four-hole boiling flask of gas shiled and feeding device; again perfluor alkyl ethide acrylate, Isooctyl acrylate monomer, hydroxy ethyl methacrylate and 4 kinds of acrylate monomers of N hydroxymethyl acrylamide, water, acetone and Dodecyl Mercaptan are added wherein; vigorous stirring 1h under the normal temperature gets pre-emulsion.Drip initiator again,, continue to stir, be cooled to room temperature in 70 ℃ of reaction 6h.
Following sequence-checking routine is used for embodiment.
The stability test program:
(1) freeze-thaw stability: emulsion was frozen 18 hours in refrigerator and cooled, at room temperature melted then 6 hours, repeatable operation is six times like this, observes emulsion and whether produces gel and demulsifying phenomenon.
(2) high-temperature stability: emulsion is put into baking oven, be incubated 6 days down, observe emulsion and whether produce gel and demulsifying phenomenon at 60 ℃.
(3) pH value stabilization: get two test tubes and add emulsion sample respectively, in two test tubes, add certain density hydrochloric acid or sodium hydroxide solution respectively, and commove, the pH value is progressively reduced or raise, observe the pH value stabilization of emulsion under the acid-basicity condition.
(4) dilution stability: it is 0.5%～3% that emulsion is diluted with water to solid content, and the emulsion after the dilution is poured in the test tube, places a week, and whether observe emulsion has the breakdown of emulsion layering.
Stable fine from the emulsion of embodiment 1.Emulsion was frozen 18 hours in refrigerator and cooled, at room temperature melted then 6 hours, after the repeatable operation six times, emulsion still keeps the stable dispersion state like this.Emulsion is put into baking oven, be incubated 6 days down at 60 ℃, emulsion does not produce gel and demulsifying phenomenon.Add acid or alkali respectively to emulsion sample, when the pH value changed in 2～12 scopes, it is stable that emulsion keeps.It is 0.5wt～3wt% that emulsion is diluted to solid content, does not have the breakdown of emulsion layering after placing for two weeks.
Fabric treating:
Earlier copolymer emulsion is diluted with water to 0.5wt%～1wt%, more pending cloth was dipped in wherein 15～20 minutes, make the finishing composition particle that is scattered in the water be adsorbed in fabric face.Take out the back and dries at normal temperatures earlier, through 150 ℃ of preliminary dryings 3 minutes, 160 ℃ baked 3 minutes again, made treatment agent in the fabric face film forming then.
Water-repellancy
Carry out waterproofing tests by the 3M-II-1988 method, a series of Virahols of joining with table 1 and the mixture of water drop in solvent on the textile sample as test solvent.From minimum number test soln, drip a drop of liquid (the about 5mm of diameter) respectively in three places at a distance of at least 5 centimetres.Drop observed for 10 seconds, when if two drops still are circular or oval after ten seconds, getting three higher leveled test liquids drips in position adjacent, observed for 10 seconds, so carry out, in three, there are two drops all can not keep circular or oval, the grade of classification of waterproof drop correspondence just at the highest level.Water-repellancy is divided 12 grades, is the superlative degree with 12 grades.
Table 1 waterproofing tests reference liquid
| Classification of waterproof 123456 | Standardized solution is formed | Classification of waterproof 789 10 11 12 | Standardized solution is formed | ||
| Virahol (%) 25 10 20 30 40 | Water (%) 98 95 90 80 70 60 | Virahol (%) 50 60 70 80 90 100 | Water (%) 50 40 30 20 10 0 | ||
Grease proofness
Carry out the grease proofness test with FZ/T 01067-1999 method.Respectively various standard test solutions (seeing Table 2) are dropped on the fabric face with dropper, observe its wetting situation and decide.The progression of at last not wetting alkane correspondence is the grease proofing progression of test fabric.Eight grades of grease proofing fractions are the superlative degree with the 8th grade.
Table 2 grease proofness testing standard liquid
| Grease proofing test progression | Component | Surface tension (mN/m, 25 ℃) |
| ????1 ????2 | Nujol oil (whiteruss) Nujol oil/n-hexadecane (65/35,21 ℃) | ????31.2 ????28.7 |
| ????3 ????4 ????5 ????6 ????7 ????8 | Tetradecane n-dodecane n-decane octane normal heptane | ????27.1 ????26.1 ????25.1 ????23.5 ????21.3 ????19.8 |
The emulsion emulsion particle median size that embodiment 1 makes is 75nm, and even size distribution, and the poly value is about 0.22, and zeta-potential is-45mv.Adopt stability test routine check product stability, prepared emulsion has been passed through check.Handle fabric by method noted earlier, and testing water-proof and oil preventing performance, the water-repellancy of fabric face reaches 12 grades, and grease proofness reaches 7 grades, demonstrates excellent water and oil-resistant.
The copolymer emulsion emulsion zeta-potential that Comparative Examples A makes is 16.3mv, adopts the moon/nonionic compound emulsifier to prepare the zeta-potential absolute value 46.5mv of emulsion much smaller than embodiment 1.Adopting the Detection of Stability program to detect shows: the copolymer emulsion instability that embodiment A makes.This has illustrated and has adopted cloudy tensio-active agent to have important effect for the stability of copolymer emulsion in copolyreaction.
The emulsion particle median size of the prepared copolymer emulsion of Embodiment B is 319.1nm, and average poly value is 0.825, and emulsion can not be by the stability test routine check.This embodiment has illustrated that the emulsion latex particle size that feeding method makes is big, and distribution of sizes is inhomogeneous, poor stability.
Claims (5)
1, a kind of preparation method of fluoro-acrylate copolymer stable emulsion is characterized in that the step for preparing is:
Step 1) is being equipped with stirring, reflux condensing tube, N
2Add the moon/nonionic compound emulsifier in the container of gas shiled and feeding device, again water, polymerization single polymerization monomer, acetone, chain-transfer agent and initiator are placed container, vigorous stirring obtained uniform pre-emulsion in 0.5～2 hour under the normal temperature;
Step 2) with the pre-emulsion separated into two parts, wherein 1/3rd be heated to 55 ℃～75 ℃ initiated polymerizations, after blue light appears in question response liquid, drip the residue pre-emulsion, the dropping time is 1.5h～2.5h;
After step 3) dropwises, will remain initiator again and add, insulation reaction 2～6 hours stirs and is cooled to room temperature, obtains the fluoro-acrylate copolymer stable emulsion.
2, the preparation method of fluoro-acrylate copolymer stable emulsion according to claim 1 is characterized in that described polymerization single polymerization monomer comprises:
A) based on the mixture of the perfluor alkyl ethide acrylate monomer of total monomer weight 50wt%～75wt% with following formula:
CF
3CF
2(CF
2)
kCH
2CH
2OC(O)C(R)＝CH
2
Wherein R=H or CH
3
K is an even number, wherein k=4,6,8,10 monomeric being distributed as:
The monomer of 25wt%-70wt%k=4,
The monomer of 20wt%-40wt%k=6,
The monomer of 5wt%-25wt%k=8,
The monomer of 0wt%-15wt%k=10;
B) based on the alkyl methacrylate or the alkyl acrylate of the alkyl chain length of total monomer weight 10wt%～30wt% with 2-18 carbon atom;
C) based on the N hydroxymethyl acrylamide of total monomer weight 0.1～2wt%;
D) based on the hydroxyethyl meth acrylate of total monomer weight 0.1～5wt%.
3, the preparation method of fluoro-acrylate copolymer stable emulsion according to claim 1 is characterized in that described the moon/nonionic compound emulsifier comprises:
E) by the nonionic surface active agent of total monomer weight 1wt%～10wt%; Can be the condensation product of ethylene oxide and fatty alcohol or the condensation product of ethylene oxide and alkylphenol; As ethylene oxide copolymer, epoxy propane copolymer, oxyethane have with it hexylphenol, C12～C16 chain alkyl thioalcohol, anhydro sorbitol list (condensation product of the fatty acid ester of C7～C10) or C7～C10 alkylamine,
(f), be an alkali metal salt of alkylsulphonic acid of long-chain and an alkali metal salt of sweet-smelling alkyl sulfonic acid by the anion surfactant of total monomer weight 1wt%～5wt%.
4, the preparation method of fluoro-acrylate copolymer stable emulsion according to claim 1, it is characterized in that the described chain-transfer agent that is used for adjusting the polymkeric substance chain length is alkyl sulfhydryl, tetracol phenixin or triphenyl methane etc., consumption is by total monomer weight 0.03wt%～0.1wt%.
5, the preparation method of fluoro-acrylate copolymer stable emulsion according to claim 1, it is characterized in that the following persulphate of described initiator, that is: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, or azo-compound: hydrochloric acid azo two NSC 18620, Diisopropyl azodicarboxylate, the usage quantity of initiator accounts for the 0.1wt%～1.5wt% of total monomer weight.
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| CNB2005100386506A CN1304437C (en) | 2005-04-01 | 2005-04-01 | Method for preparing stable latex of copolymer containing fluorinated acrylic ester |
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| DE4201604A1 (en) * | 1992-01-22 | 1993-07-29 | Bayer Ag | FLUORINE COPOLYMERISATE AND AQUEOUS DISPERSIONS MADE THEREOF |
| US5344903A (en) * | 1993-04-14 | 1994-09-06 | E. I. Du Pont De Nemours And Company | Water- and oil-repellent fluoro(meth)acrylate copolymers |
| CN1166709C (en) * | 2001-07-10 | 2004-09-15 | 华东理工大学 | Fluoroacrylic ester block polymer and its prpen. |
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|---|---|---|---|---|
| CN100436497C (en) * | 2005-11-04 | 2008-11-26 | 王志军 | Method for preparing polyacrylate, and fluorin modified polyacrylate obtained from the method |
| CN101225262B (en) * | 2008-01-30 | 2011-05-25 | 陈永康 | Fluorocarbon compound modified polyacrylate flow agent for coating ink and production method thereof |
| CN102174143A (en) * | 2011-01-29 | 2011-09-07 | 锦州惠发天合化学有限公司 | Method for preparing fluorine-containing acrylate emulsion |
| CN102174143B (en) * | 2011-01-29 | 2013-01-09 | 锦州惠发天合化学有限公司 | Method for preparing fluorine-containing acrylate emulsion |
| CN102493193A (en) * | 2011-12-14 | 2012-06-13 | 太仓中化环保化工有限公司 | Fluorine-containing water and oil repellant agent and preparing method thereof |
| CN102493193B (en) * | 2011-12-14 | 2014-01-29 | 太仓中化环保化工有限公司 | Fluorine-containing water and oil repellant agent and preparing method thereof |
| CN112574354A (en) * | 2020-12-10 | 2021-03-30 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
| CN114908579A (en) * | 2022-05-30 | 2022-08-16 | 南京中敖日化科技有限公司 | Water-proof and oil-resistant aerosol for surface and vamp of clothes and preparation method thereof |
| CN117050601A (en) * | 2023-08-21 | 2023-11-14 | 广东聚微新材料科技有限公司 | Fluorine electronic protective coating and preparation method thereof |
| CN117050601B (en) * | 2023-08-21 | 2024-04-16 | 广东聚微新材料科技有限公司 | Fluorine electronic protective coating and preparation method thereof |
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