CN100999563A - Preparation process of containing emulsion with surfactant low transportting performance - Google Patents
Preparation process of containing emulsion with surfactant low transportting performance Download PDFInfo
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- CN100999563A CN100999563A CN 200610105350 CN200610105350A CN100999563A CN 100999563 A CN100999563 A CN 100999563A CN 200610105350 CN200610105350 CN 200610105350 CN 200610105350 A CN200610105350 A CN 200610105350A CN 100999563 A CN100999563 A CN 100999563A
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Abstract
The present invention discloses preparation process of fluoric emulsion with low mobility surfactant. The preparation process of the fluoric emulsion includes the following steps: mixing (methyl) acrylic acid, vinyl monomer, fluoric (methyl) acrylate and liposoluble initiator, polymerizing of the mixture in organic solvent and alkali neutralizing to obtain water soluble fluoric copolymer; mixing the water soluble fluoric copolymer and cationic surfactant to obtain surfactant complex; mixing vinyl monomer, the surfactant complex and deionized water to pre-emulsify; and initiating with initiator to polymerize to obtain the fluoric emulsion with low mobility surfactant. The present invention can reduce the mobility of small molecular weight emulsifier in the coating, raise the stability of the emulsion polymerizing process, raise the application performance and production performance of fluoric emulsion product and eliminate organic volatile in product.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of preparation method of fluorine-containing latex of tensio-active agent low migration energy.
Background technology
Fluoropolymer is owing to " the three Senior Two are hated " performance with high surface, high heat-resistant stability, high unreactiveness, hydrophobic nature and oil repellency is used widely, and emulsion is its main application form.At present, the preparation method of fluorine-containing latex mainly contains following several: (1) homopolymerization or copolymerization of fluorochemical monomer under conventional emulsifier/fluorine-containing emulsifier acting in conjunction; (2) homopolymerization or the copolymerization of fluorochemical monomer under conventional emulsifier/organic solvent effect; (3) simple blend of ptfe emulsion and conventional emulsions.But no matter adopt which kind of preparation method, all contain in the finished product great amount of conventional emulsifying agent or (with) organic solvent.Wherein, the emulsifying agent molecule is that the mode with physical adsorption is present in the latex particle surface, this suction type make the emulsifying agent molecule very easily from the fluorine-containing coat internal migration to coatingsurface and with the interface of base material on, reduce the surface property and the interface performance of coating; Simultaneously, the existence of organic solvent has increased the organic volatile content of product, is unfavorable for environment protection.So in common fluorine-containing latex, a large amount of emulsifying agent and organic solvents that exist with physical adsorption way are all unfavorable to fluorine-containing latex product application performance and environment protection, especially the surface property of fluorine-containing coat and with the interface performance of base material.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of can improve the fluorine-containing coat surface property and with the interface performance of base material, do not contain the preparation method of organic solvent, fluorine-containing latex that the emulsifying agent molecular migration is extremely low.
For achieving the above object, the technical solution used in the present invention is: with acrylic or methacrylic acid and vinyl monomer, fluorine-containing methacrylate or fluorinated acrylate by 1: the mass ratio of 0.1-2: 0.01-1 mixes and makes solution A; With solution A and oil-soluble initiator by 100: the mass ratio of 0.05-5 mixes and obtains solution B, under 60 ℃-90 ℃, solution B is added drop-wise in the organic solvent then, wherein the mass ratio of solution B and organic solvent is 100: 10-2000, the dropping time is 0.5-3 hour, continues to obtain after polymerase 10 .5-3 hour the organic solvent solution C of fluorinated copolymer then; Interpolation water and alkali stir in solution C, wherein the mass ratio of solution C, water and alkali is 100: 80-5000: 0.3-80, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and alkali in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and alkali is 100: 80-5000: 5-80; Dephlegmate obtains water-soluble fluorinated copolymer then; Water-soluble fluorinated copolymer, cats product and water are pressed 1: the quality of 0.0001-1: 0.5-5000 makes tensio-active agent complex solution D than mixing and stirring; With vinyl monomer, solution D and water soluble starter by 1: the mass ratio of 0.5-100: 0.002-0.02 joins in the water soluble starter after with vinyl monomer, solution D mixing and stirring, can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 30-90 ℃ of following polymerization 2-6 hour.
Vinyl monomer of the present invention is methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate, vinylbenzene, vinyl toluene, Hydroxyethyl acrylate or hydroxyethyl methylacrylate; Fluorinated acrylate is vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, vinylformic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-ethyl propenoate base) sulphonamide or perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide; Said fluorine-containing methacrylate is trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters, methacrylic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide; Oil-soluble initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Organic solvent is acetone, methylethylketone, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, isopropyl acetate, N, dinethylformamide, N,N-dimethylacetamide, normal hexane, hexanaphthene, octane-iso, acetonitrile, sherwood oil or N-Methyl pyrrolidone; Alkali is ammonia, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, Trimethylamine 99, triethylamine or trolamine; Cats product is dodecylbenzyl alkyl dimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl benzyl dimethyl ammonium chloride or octadecyl benzyl dimethyl brometo de amonio; Water soluble starter is ammonium persulphate, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine.
Adopt the present invention can reduce the migration performance of small-molecular emulsifier in coating significantly, thereby help improving the application performance of fluorine-containing latex product, can eliminate the harm of organic solvent fully simultaneously physical environment.
Embodiment
Embodiment 1, vinylformic acid and methyl acrylate, vinylformic acid trifluoro ethyl ester mixed by 1: 0.1: 0.001 mass ratio make solution A; Solution A and Diisopropyl azodicarboxylate mixed by 100: 0.05 mass ratio obtain solution B, under 60 ℃, solution B is added drop-wise in the machine solvent methylethylketone then, wherein the mass ratio of solution B and organic solvent is 100: 10, the dropping time is 0.5 hour, continues to obtain behind the polyase 13 hour the organic solvent solution C of fluorinated copolymer then; Interpolation water and ammonia stir in solution C, wherein the mass ratio of solution C, water and ammonia is 100: 80: 80, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and sodium hydroxide in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and sodium hydroxide is 100: 80: 80; Dephlegmate obtains water-soluble fluorinated copolymer then; With water-soluble fluorinated copolymer, dodecylbenzyl alkyl dimethyl ammonium chloride and water by 1: 1: 0.5 quality than mixing and stirring, make tensio-active agent complex solution D; Methyl acrylate, solution D and water soluble starter ammonium persulphate are joined in the water soluble starter after with methyl acrylate, solution D mixing and stirring by 1: 100: 0.002 mass ratio, can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 2 hours in 90 ℃ of following polymerizations.
Embodiment 2, methacrylic acid and ethyl propenoate, trifluoroethyl methacrylate are mixed by 1: 0.5: 0.1 mass ratio make solution A; Solution A and benzoyl peroxide mixed by 100: 0.1 mass ratio obtain solution B, under 70 ℃, solution B is added drop-wise in the machine solvents tetrahydrofurane then, wherein the mass ratio of solution B and organic solvent is 100: 100, the dropping time is 1 hour, continues polymerization obtains fluorinated copolymer after 2.5 hours organic solvent solution C then; Interpolation water and potassium hydroxide stir in solution C, wherein the mass ratio of solution C, water and potassium hydroxide is 100: 200: 40, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and yellow soda ash in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and yellow soda ash is 100: 200: 40; Dephlegmate obtains water-soluble fluorinated copolymer then; With water-soluble fluorinated copolymer, Trimethyllaurylammonium bromide and water by 1: 0.1: 100 quality than mixing and stirring, make tensio-active agent complex solution D; Ethyl propenoate, solution D and water soluble starter Potassium Persulphate are joined in the water soluble starter after with ethyl propenoate, solution D mixing and stirring by 1: 60: 0.008 mass ratio, hour can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 85 ℃ of following polyase 13s.
Embodiment 3, methacrylic acid and stearyl methacrylate, methacrylic acid hexafluoro butyl ester are mixed by 1: 1: 0.3 mass ratio make solution A; Solution A and Diisopropyl azodicarboxylate mixed by 100: 1 mass ratio obtain solution B, under 80 ℃, solution B is added drop-wise to machine solvent N then, in the dinethylformamide, wherein solution B is 100: 500 with the mass ratio that has, the dropping time is 1.5 hours, continues polymerization obtains fluorinated copolymer after 2 hours organic solvent solution C then; Interpolation water and sodium bicarbonate stir in solution C, wherein the mass ratio of solution C, water and sodium bicarbonate is 100: 500: 10, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and Trimethylamine 99 in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and Trimethylamine 99 is 100: 500: 30; Dephlegmate obtains water-soluble fluorinated copolymer then; With water-soluble fluorinated copolymer, palmityl trimethyl ammonium chloride and water by 1: 0.01: 500 quality than mixing and stirring, make tensio-active agent complex solution D; Stearyl methacrylate, solution D and water soluble starter ammonium persulphate are joined in the water soluble starter after with stearyl methacrylate, solution D mixing and stirring by 1: 20: 0.01 mass ratio, can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 4 hours in 80 ℃ of following polymerizations.
Embodiment 4, vinylformic acid and vinylbenzene, methacrylic acid 19 fluorine esters are mixed by 1: 1.5: 0.6 mass ratio make solution A; Solution A and benzoyl peroxide mixed by 100: 3 mass ratio obtain solution B, under 85 ℃, solution B is added drop-wise in the machine solvent acetic acid butyl ester then, wherein solution B is 100: 1000 with the mass ratio that has, the dropping time is 2 hours, continues polymerization obtains fluorinated copolymer after 1 hour organic solvent solution C then; Interpolation water and triethylamine stir in solution C, wherein the mass ratio of solution C, water and triethylamine is 100: 2000: 1, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and trolamine in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and trolamine is 100: 2000: 15; Dephlegmate obtains water-soluble fluorinated copolymer then; With water-soluble fluorinated copolymer, octadecyl trimethylammonium bromide and water by 1: 0.001: 2000 quality than mixing and stirring, make tensio-active agent complex solution D; With vinylbenzene, solution D and water soluble starter ammonium persulphate and sodium bisulfite by 1: 5: the mass ratio of (0.01: 0.005) joins in the water soluble starter after with vinylbenzene, solution D mixing and stirring, can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 5 hours in 40 ℃ of following polymerizations.
Embodiment 5, vinylformic acid and hydroxyethyl methylacrylate, dodecafluorhe-ptylacrylate are mixed by 1: 2: 1 mass ratio make solution A; Solution A and benzoyl peroxide mixed by 100: 5 mass ratio obtain solution B, under 90 ℃, solution B is added drop-wise in the machine solvent normal hexane then, wherein solution B is 100: 2000 with the mass ratio that has, the dropping time is 3 hours, continues to obtain after polymerase 10 .5 hour the organic solvent solution C of fluorinated copolymer then; Interpolation water and potassium hydroxide stir in solution C, wherein the mass ratio of solution C, water and potassium hydroxide is 100: 5000: 0.3, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and sodium hydroxide in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and sodium hydroxide is 100: 5000: 5; Dephlegmate obtains water-soluble fluorinated copolymer then; With water-soluble fluorinated copolymer, octadecyl benzyl dimethyl ammonium chloride and water by 1: 0.0001: 5000 quality than mixing and stirring, make tensio-active agent complex solution D; With hydroxyethyl methylacrylate, solution D and water soluble starter Potassium Persulphate and Sulfothiorine by 1: 0.5: the mass ratio of (0.012: 0.008) joins in the water soluble starter after with hydroxyethyl methylacrylate, solution D mixing and stirring, can obtain the extremely low fluorine-containing latex of emulsifying agent molecular migration in 6 hours in 30 ℃ of following polymerizations.
Claims (8)
1, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy is characterized in that:
1) with acrylic or methacrylic acid and vinyl monomer, fluorine-containing methacrylate or fluorinated acrylate by 1: the mass ratio of 0.1-2: 0.01-1 mixes and makes solution A;
2) with solution A and oil-soluble initiator by 100: the mass ratio of 0.05-5 mixes and obtains solution B, under 60 ℃-90 ℃, solution B is added drop-wise in the organic solvent then, wherein the mass ratio of solution B and organic solvent is 100: 10-2000, the dropping time is 0.5-3 hour, continues to obtain after polymerase 10 .5-3 hour the organic solvent solution C of fluorinated copolymer then;
3) interpolation water and alkali stir in solution C, wherein the mass ratio of solution C, water and alkali is 100: 80-5000: 0.3-80, organic solvent and water are removed in distillation then, obtain water-soluble fluorinated copolymer or the solution C straight run distillation removed organic solvent obtaining fluorinated copolymer, add water and alkali in fluorinated copolymer, wherein the mass ratio of fluorinated copolymer, water and alkali is 100: 80-5000: 5-80; Dephlegmate obtains water-soluble fluorinated copolymer then;
4) water-soluble fluorinated copolymer, cats product and water are pressed 1: the quality of 0.0001-1: 0.5-5000 makes tensio-active agent complex solution D than mixing and stirring;
5) with vinyl monomer, solution D and water soluble starter by 1: the mass ratio of 0.5-100: 0.002-0.02 joins in the water soluble starter after with vinyl monomer, solution D mixing and stirring, and can obtain the tensio-active agent low migration in 30-90 ℃ of following polymerization 2-6 hour can fluorine-containing latex.
2, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said vinyl monomer is methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate, vinylbenzene, vinyl toluene, Hydroxyethyl acrylate or hydroxyethyl methylacrylate.
3, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said fluorinated acrylate is vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, vinylformic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-ethyl propenoate base) sulphonamide or perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide; Said fluorine-containing methacrylate is trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters, methacrylic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide.
4, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said oil-soluble initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
5, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said organic solvent is acetone, methylethylketone, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, isopropyl acetate, N, dinethylformamide, N,N-dimethylacetamide, normal hexane, hexanaphthene, octane-iso, acetonitrile, sherwood oil or N-Methyl pyrrolidone.
6, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said alkali is ammonia, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, Trimethylamine 99, triethylamine or trolamine.
7, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said cats product is dodecylbenzyl alkyl dimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl benzyl dimethyl ammonium chloride or octadecyl benzyl dimethyl brometo de amonio.
8, the preparation method of the fluorine-containing latex of tensio-active agent low migration energy according to claim 1, it is characterized in that: said water soluble starter is ammonium persulphate, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508755B (en) * | 2009-03-11 | 2011-07-20 | 陕西科技大学 | Crosslinking self-emulsifying cation full fluorine copolymer soap-free emulsion and preparation thereof |
| CN102675534A (en) * | 2012-05-17 | 2012-09-19 | 陕西科技大学 | Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method |
| CN104947099A (en) * | 2015-05-14 | 2015-09-30 | 重庆大学 | Preparation method of metal surface film with quick self-repairing capability |
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| US5344903A (en) * | 1993-04-14 | 1994-09-06 | E. I. Du Pont De Nemours And Company | Water- and oil-repellent fluoro(meth)acrylate copolymers |
| US6180740B1 (en) * | 1998-02-27 | 2001-01-30 | E. I. Du Pont De Nemours And Company | Stabilization of fluorochemical copolymer emulsions |
| JP2001233906A (en) * | 2000-02-22 | 2001-08-28 | Nicca Chemical Co Ltd | Method for manufacturing copolymer composition, and water/oil-repellent agent |
| KR100427261B1 (en) * | 2001-12-04 | 2004-04-14 | 한국화학연구원 | Preparation of fluorinated core-shell particles for water and oil repellent |
| CN1300192C (en) * | 2004-09-17 | 2007-02-14 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508755B (en) * | 2009-03-11 | 2011-07-20 | 陕西科技大学 | Crosslinking self-emulsifying cation full fluorine copolymer soap-free emulsion and preparation thereof |
| CN102675534A (en) * | 2012-05-17 | 2012-09-19 | 陕西科技大学 | Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method |
| CN104947099A (en) * | 2015-05-14 | 2015-09-30 | 重庆大学 | Preparation method of metal surface film with quick self-repairing capability |
| CN104947099B (en) * | 2015-05-14 | 2017-04-26 | 重庆大学 | Preparation method of metal surface film with quick self-repairing capability |
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