CN100432112C - Preparation process of fluorine-containing emulsion under carboxy fluorocarbon furfactant composition action - Google Patents
Preparation process of fluorine-containing emulsion under carboxy fluorocarbon furfactant composition action Download PDFInfo
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- CN100432112C CN100432112C CNB2006101053497A CN200610105349A CN100432112C CN 100432112 C CN100432112 C CN 100432112C CN B2006101053497 A CNB2006101053497 A CN B2006101053497A CN 200610105349 A CN200610105349 A CN 200610105349A CN 100432112 C CN100432112 C CN 100432112C
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- fluorine
- fluorocarbon
- furfactant
- carboxy
- methyl
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Abstract
The present invention discloses preparation process of fluoric emulsion under the action of carboxyl group containing fluorocarbon surfactant composition, which is obtained with carboxyl group containing fluorocarbon surfactant and proper amount of cationic surfactant and through electrostatic combination. Under the action of carboxyl group containing fluorocarbon surfactant composition, polymerisable monomer is emulsion polymerized to obtain the fluoric emulsion. The preparation process of the present invention has greatly reduced mobilizing performance of small molecular weight emulsifier in coating, raised emulsion polymerization stability, raised solid content in the emulsion, improved application performance and production performance of fluoric emulsion product and no use of organic solvent.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action.
Background technology
Fluorocarbon polymer 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 carbon emulsifying agent 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, reduce the surface property 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.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, the preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action who provide a kind of and can improve the fluorine-containing coat surface property, do not contain organic solvent, the emulsifying agent molecular migration is extremely low.
For achieving the above object, the technical solution used in the present invention is: will contain carboxy fluorocarbon furfactant composition, polymerisable monomer and water by 1: the mass ratio of 1-100: 5-2000 mixes and makes solution A; Then with solution A and initiator by 1: the mass ratio of 0.0005-0.15 mixes, and can obtain fluorine-containing latex in 30-90 ℃ of following polymerization 2-6 hour.
The general structure that contains carboxy fluorocarbon furfactant composition of the present invention is:
In the formula, R
1, R
2And R
3For hydrogen atom or methyl, can be the same or different; M is NH
4 +, Na
+, K
+, N (CH
3)
3, N (CH
2CH
3)
3Or N (CH
2CH
2OH)
3Rf is that carbonatoms is the perfluoroalkyl of 2-9, and wherein the part of fluorine atom can be replaced by hydrogen atom; R
4Be carbonatoms be 1-20 alkyl, phenyl or-OOR
7, R wherein
7Be that carbonatoms is the alkyl of 1-20; R
5Be methyl or benzyl; R
6Be that carbonatoms is the alkyl of 12-18; X, y, z, w are integers, and its total amount is the integer of 5-3000; The scope of x is 2-2970, and the scope of y, z is 1-2000, and x/ (x+y+z) is 0.1-0.99, and the scope of w is 1-450, and x is greater than w; Polymerisable monomer is a 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, hydroxyethyl methylacrylate, the 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, perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide, trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters, methacrylic acid 19 fluorine esters, a kind of monomer or multiple monomeric mixture in perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide; Initiator is ammonium persulphate, Potassium Persulphate or oxidation-reduction trigger system, oxidation-reduction trigger system is ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite, Potassium Persulphate-S-WAT, Potassium Persulphate-sodium bisulfite, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxidized portion and reduction part is 1: 2-0.05.
To contain carboxy fluorocarbon furfactant composition, polymerisable monomer and water by 1: the mass ratio of 1-100: 5-2000 mixes and makes solution A; Solution A and initiator are by 1: the mass ratio of 0.0005-0.15 mixes, and can obtain fluorine-containing latex in 30-90 ℃ of following polymerization 2-6 hour.
Adopt the present invention can increase substantially letex polymerization stability and emulsion solid content, reduce the migration performance of small-molecular emulsifier in coating, thereby help improving the production and the application performance of fluorine-containing latex product, can eliminate the harm of organic solvent fully simultaneously physical environment.And it is very extensive to be suitable for raw material type of the present invention.
Embodiment
Embodiment 1: will contain carboxy fluorocarbon furfactant composition, vinylbenzene and water and mix by 1: 1: 5 mass ratio and make solution A, the structural formula that wherein contains carboxy fluorocarbon furfactant composition is:
R in the formula
1, R
2And R
3Be hydrogen atom, M is NH
4 +, Rf is that carbonatoms is 2 perfluoroalkyl, wherein 2 fluorine atoms are replaced R by hydrogen atom
4For carbonatoms is 1 alkyl, R
5Be methyl, R
6Carbonatoms is 12 alkyl; The value of x, y, z, w is 2,1,1 and 1 respectively, and x/ (x+y+z+w) is 0.4; Solution A and ammonium persulphate mix by 1: 0.0005 mass ratio, can obtain fluorine-containing latex in 2 hours in 90 ℃ of following polymerizations.
Embodiment 2: will contain carboxy fluorocarbon furfactant composition, vinylbenzene, vinylformic acid hexafluoro butyl ester and water by 1: (5: 2): 20 mass ratio mixes and makes solution A, and the structural formula that wherein contains carboxy fluorocarbon furfactant composition is:
R in the formula
1, R
2And R
3Be methyl, M is Na
+, Rf is that carbonatoms is 4 perfluoroalkyl, wherein 4 fluorine atoms are replaced R by hydrogen atom
4Be that carbonatoms is 20 alkyl, R
5Be benzyl, R
6Carbonatoms is 12 alkyl; The value of x, y, z, w is respectively 100,200,670 and 30, and x/ (x+y+z+w) is 0.1; Solution A and Potassium Persulphate mix by 1: 0.01 mass ratio, can obtain fluorine-containing latex in 4 hours in 80 ℃ of following polymerizations.
Embodiment 3: will contain carboxy fluorocarbon furfactant composition, N-Hexyl methacrylate, methacrylic acid ten difluoro heptyl esters and water by 1: (10: 5): 200 mass ratio mixes and makes solution A, and the structural formula that wherein contains carboxy fluorocarbon furfactant composition is:
R in the formula
1Be hydrogen atom, R
2And R
3Be methyl, M is N (CH
3)
3, Rf is that carbonatoms is 8 perfluoroalkyl, wherein 3 fluorine atoms are replaced R by hydrogen atom
4Be phenyl, R
5Be methyl, R
6Carbonatoms is 16 alkyl; The value of x, y, z, w is respectively 900,2000,70 and 30, and x/ (x+y+z+w) is 0.3; Solution A, ammonium persulphate-S-WAT are by 1: the mass ratio of (0.05: 0.1) mixes, and hour can obtain fluorine-containing latex in 50 ℃ of following polyase 13s.
Embodiment 4: will contain carboxy fluorocarbon furfactant composition, stearyl methacrylate, vinylbenzene and water by 1: (10: 30): 1000 mass ratio mixes and makes solution A, and the structural formula that wherein contains carboxy fluorocarbon furfactant composition is:
R in the formula
1Be methyl, R
2And R
3Be hydrogen atom, M is K
+, Rf is that carbonatoms is 9 perfluoroalkyl, R
4Be-OOR
7, R
7Be that carbonatoms is 1 alkyl, R
5Be methyl, R
6Carbonatoms is 18 alkyl; The value of x, y, z, w is respectively 500,50,2000 and 450, and x/ (x+y+z+w) is 0.17; Solution A, Potassium Persulphate-sodium bisulfite are by 1: the mass ratio of (0.1: 0.005) mixes, and can obtain fluorine-containing latex in 5 hours in 40 ℃ of following polymerizations.
Embodiment 5: will contain carboxy fluorocarbon furfactant composition, Hydroxyethyl acrylate, methacrylic acid 19 fluorine esters and water by 1: (90: 10): 2000 mass ratio mixes and makes solution A, and the structural formula that wherein contains carboxy fluorocarbon furfactant composition is:
R in the formula
1Be methyl, R
2And R
3Be hydrogen atom, M is N (CH
2CH
2OH)
3, Rf is that carbonatoms is 9 perfluoroalkyl, R
4Be-OOR
7, R
7Be that carbonatoms is 20 alkyl, R
5Be benzyl, R
6Carbonatoms is 18 alkyl; The value of x, y, z, w is respectively 2970,20,5 and 5, and x/ (x+y+z+w) is 0.99; Solution A, Potassium Persulphate-Sulfothiorine are by 1: the mass ratio of (0.12: 0.03) mixes, and can obtain fluorine-containing latex in 6 hours in 30 ℃ of following polymerizations.
Claims (4)
1, contain the preparation method of fluorine-containing latex under the carboxy fluorocarbon furfactant composition action, it is characterized in that:
1) will contain carboxy fluorocarbon furfactant composition, polymerisable monomer and water by 1: the mass ratio of 1-100: 5-2000 mixes and makes solution A;
2) then with solution A and initiator by 1: the mass ratio of 0.0005-0.15 mixes, and can obtain fluorine-containing latex in 30-90 ℃ of following polymerization 2-6 hour.
2, the preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action according to claim 1 is characterized in that: the said general structure that contains carboxy fluorocarbon furfactant composition is:
In the formula, R
1, R
2And R
3For hydrogen atom or methyl, can be the same or different; M is NH
4 +, Na
+, K
+, N (CH
3)
3, N (CH
2CH
3)
3Or N (CH
2CH
2OH)
3Rf is that carbonatoms is the perfluoroalkyl of 2-9, and wherein the part of fluorine atom can be replaced by hydrogen atom; R
4Be carbonatoms be 1-20 alkyl, phenyl or-OOR
7, R wherein
7Be that carbonatoms is the alkyl of 1-20; R
5Be methyl or benzyl; R
6Be that carbonatoms is the alkyl of 12-18; X, y, z, w are integers, and its total amount is the integer of 5-3000; The scope of x is 2-2970, and the scope of y, z is 1-2000, and x/ (x+y+z) is 0.1-0.99, and the scope of w is 1-450, and x is greater than w.
3, the preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action according to claim 1 is characterized in that: said polymerisable monomer is a 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, hydroxyethyl methylacrylate, the 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, perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide, trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters, methacrylic acid 19 fluorine esters, a kind of monomer or multiple monomeric mixture in perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide.
4, the preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action according to claim 1, it is characterized in that: said initiator is ammonium persulphate, Potassium Persulphate or oxidation-reduction trigger system, oxidation-reduction trigger system is ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite, Potassium Persulphate-S-WAT, Potassium Persulphate-sodium bisulfite, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxidized portion and reduction part is 1: 2-0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101053497A CN100432112C (en) | 2006-12-29 | 2006-12-29 | Preparation process of fluorine-containing emulsion under carboxy fluorocarbon furfactant composition action |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101053497A CN100432112C (en) | 2006-12-29 | 2006-12-29 | Preparation process of fluorine-containing emulsion under carboxy fluorocarbon furfactant composition action |
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| Publication Number | Publication Date |
|---|---|
| CN100999556A CN100999556A (en) | 2007-07-18 |
| CN100432112C true CN100432112C (en) | 2008-11-12 |
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5346949A (en) * | 1992-05-29 | 1994-09-13 | Hoechst Gosei K.K. | Fluorine containing aqueous composition having water repellent and oil repellent properties |
| CN1206721A (en) * | 1997-07-11 | 1999-02-03 | 罗姆和哈斯公司 | Preparation of fluorated polymer |
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
-
2006
- 2006-12-29 CN CNB2006101053497A patent/CN100432112C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5346949A (en) * | 1992-05-29 | 1994-09-13 | Hoechst Gosei K.K. | Fluorine containing aqueous composition having water repellent and oil repellent properties |
| CN1206721A (en) * | 1997-07-11 | 1999-02-03 | 罗姆和哈斯公司 | Preparation of fluorated polymer |
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
Non-Patent Citations (1)
| Title |
|---|
| 含氟聚合物乳液的研制及应用. 徐祖顺，陈中华，涂伟萍，杨卓如，陈焕钦.功能高分子学报，第13期. 2000 * |
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| CN100999556A (en) | 2007-07-18 |
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Granted publication date: 20081112 Termination date: 20111229 |