CN101503496A - Preparation of fluorocarbon soap-free emulsion - Google Patents
Preparation of fluorocarbon soap-free emulsion Download PDFInfo
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- CN101503496A CN101503496A CNA2009100213793A CN200910021379A CN101503496A CN 101503496 A CN101503496 A CN 101503496A CN A2009100213793 A CNA2009100213793 A CN A2009100213793A CN 200910021379 A CN200910021379 A CN 200910021379A CN 101503496 A CN101503496 A CN 101503496A
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- fluorine
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- emulsion
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Abstract
The invention discloses a preparation method of soap-free fluorocarbon emulsion. In the preparation method, a fluorine-containing amphipathic polymer is taken as a dispersing emulsifying agent to pre-emulsify polymer monomers such as fluorine-containing monomers and (or) non-fluorine monomers and the like, and then novel soap-free fluorocarbon emulsion is obtained by soap-free polymerization, wherein, hydrophilicity of the fluorine-containing amphipathic polymer is provided by carboxyl, hydrophobicity is provided by fluorine-containing ester group and alkyl or phenyl, and structure of the polymer monomers and a hydrophobic structural unit of the fluorine-containing amphipathic polymer can be same or different. The preparation method can help fully eliminate adverse effects of micromolecular emulsifying agents and organic solvents on application performance of products and environmental protection.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of soap-free fluorocarbon emulsion
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 conventional emulsifier or (with) organic solvent, this is 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, a kind of preparation method of soap-free fluorocarbon emulsion that does not contain conventional emulsifier and organic solvent is provided.
For achieving the above object, the technical solution used in the present invention is: 1) with fluorine-containing amphipathic nature polyalcohol, polymerization single polymerization monomer and water by 1: the mass ratio of 1-80: 5-1000 mixes and makes pre-emulsion A;
2) pre-emulsion A and initiator are by 1: the mass ratio of 0.001-0.1 mixes, and hour can obtain fluorocarbon soap-free emulsion in 50-90 ℃ of following polyase 13-6.
The general structure of fluorine-containing amphipathic nature polyalcohol of the present invention is:
In the formula, R
1, R
2And R
3Be hydrogen atom or methyl; M is NH
4 +, Na
+, N (CH
2CH
3)
3Rf is that carbonatoms is the perfluoroalkyl of 2-9, and wherein the part of fluorine atom is replaced by hydrogen atom; R
4Be carbonatoms be 1-10 alkyl, phenyl or-OOR
5, R wherein
5Be that carbonatoms is the alkyl of 1-20; X, y, z are integers, and its total amount is the integer of 4-1000; The scope of x is 2-900, and the scope of y, z is 1-800, and x/ (x+y+z) is 0.1-0.9.
Non-fluorine monomer in the polymerization single polymerization monomer is a kind of monomer or the multiple monomeric mixture in methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, vinylbenzene, vinyl toluene, Hydroxyethyl acrylate, the hydroxyethyl methylacrylate;
Fluorochemical monomer in the polymerization single polymerization monomer is 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 ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium bisulfite, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxidized portion and reduction part is 1: 2-0.1.
Adopt the present invention can produce many kinds, multi-series fluorine-containing latex, can eliminate small-molecular emulsifier and organic solvent disadvantageous effect simultaneously fully product application performance and environment protection.
Embodiment
Embodiment 1: with fluorine-containing amphipathic nature polyalcohol, vinylbenzene, methyl acrylate and water by 1: (0.5: 0.5): 5 mass ratio mixes and makes pre-emulsion A, and wherein the structural formula of fluorine-containing amphipathic nature polyalcohol 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, the value of x, y, z is respectively 2,1 and 1, and x/ (x+y+z) is 0.5; Pre-emulsion A and ammonium persulphate mix by 1: 0.001 mass ratio, hour can obtain the novel fluoro-carbon soap-free emulsion in 90 ℃ of following polyase 13s.
Embodiment 2: with fluorine-containing amphipathic nature polyalcohol, hydroxyethyl methylacrylate, vinylformic acid trifluoro ethyl ester and water by 1: (5: 2): 20 mass ratio mixes and makes emulsion A, and wherein the structural formula of fluorine-containing amphipathic nature polyalcohol 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 10 alkyl, the value of x, y, z is respectively 100,200 and 700, and x/ (x+y+z) is 0.1; Pre-emulsion A and Potassium Persulphate mix by 1: 0.01 mass ratio, can obtain the novel fluoro-carbon soap-free emulsion in 4 hours in 80 ℃ of following polymerizations.
Embodiment 3: with fluorine-containing amphipathic nature polyalcohol, N-Hexyl methacrylate, methacrylic acid ten difluoro heptyl esters and water by 1: (10: 5): 200 mass ratio mixes and makes pre-emulsion A, and wherein the structural formula of fluorine-containing amphipathic nature polyalcohol is:
R in the formula
1Be hydrogen atom, R
2And R
3Be methyl, M is N (CH
2CH
3)
3, Rf is that carbonatoms is 8 perfluoroalkyl, wherein 3 fluorine atoms are replaced R by hydrogen atom
4Be phenyl, the value of x, y, z is respectively 100,800 and 100, and x/ (x+y+z) is 0.1; Pre-emulsion A, ammonium persulphate and sodium bisulfite are by 1: the mass ratio of (0.03: 0.06) mixes, and can obtain the novel fluoro-carbon soap-free emulsion in 5 hours in 70 ℃ of following polymerizations.
Embodiment 4: with fluorine-containing amphipathic nature polyalcohol thing, stearyl methacrylate, vinylbenzene and water by 1: (10: 30): 600 mass ratio mixes and makes pre-emulsion A, and wherein the structural formula of fluorine-containing amphipathic nature polyalcohol is:
R in the formula
1Be methyl, R
2And R
3Be hydrogen atom, M is Na
+, Rf is that carbonatoms is 9 perfluoroalkyl, R
4Be-00R
5, R
5Be that carbonatoms is 1 alkyl, the value of x, y, z is respectively 100,100 and 800, and x/ (x+y+z) is 0.1; Pre-emulsion A, Potassium Persulphate and sodium bisulfite are by 1: the mass ratio of (0.08: 0.008) mixes, and can obtain the novel fluoro-carbon soap-free emulsion in 5.5 hours in 60 ℃ of following polymerizations.
Embodiment 5: with fluorine-containing amphipathic nature polyalcohol, Hydroxyethyl acrylate, perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide and water by 1: (70: 10): 1000 mass ratio mixes and makes pre-emulsion A, and wherein the structural formula of fluorine-containing amphipathic nature polyalcohol is:
R in the formula
1Be methyl, R
2And R
3Be hydrogen atom, M is N (CH
2CH
3)
3, Rf is that carbonatoms is 9 perfluoroalkyl, R
4Be-OOR
5, R
5Be that carbonatoms is 20 alkyl, the value of x, y, z is respectively 900,50 and 50, and x/ (x+y+z) is 0.9; Pre-emulsion A, Potassium Persulphate, Sulfothiorine are by 1: the mass ratio of (0.05: 0.05) mixes, and can obtain the novel fluoro-carbon soap-free emulsion in 6 hours in 50 ℃ of following polymerizations.
Claims (5)
1, a kind of preparation method of soap-free fluorocarbon emulsion is characterized in that:
1) with fluorine-containing amphipathic nature polyalcohol, polymerization single polymerization monomer and water by 1: the mass ratio of 1-80: 5-1000 mixes and makes pre-emulsion A;
2) pre-emulsion A and initiator are by 1: the mass ratio of 0.001-0.1 mixes, and hour can obtain fluorocarbon soap-free emulsion in 50-90 ℃ of following polyase 13-6.
2, preparation method of soap-free fluorocarbon emulsion according to claim 1 is characterized in that: the general structure of said fluorine-containing amphipathic nature polyalcohol is:
In the formula, R
1, R
2And R
3Be hydrogen atom or methyl; M is NH
4 +, Na
+, N (CH
2CH
3)
3Rf is that carbonatoms is the perfluoroalkyl of 2-9, and wherein the part of fluorine atom is replaced by hydrogen atom; R
4Be carbonatoms be 1-10 alkyl, phenyl or-OOR
5, R wherein
5Be that carbonatoms is the alkyl of 1-20; X, y, z are integers, and its total amount is the integer of 4-1000; The scope of x is 2-900, and the scope of y, z is 1-800, and x/ (x+y+z) is 0.1-0.9.
3, preparation method of soap-free fluorocarbon emulsion according to claim 1 is characterized in that: the non-fluorine monomer in the said polymerization single polymerization monomer is a kind of monomer or the multiple monomeric mixture in methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, octadecyl acrylate, vinylbenzene, vinyl toluene, Hydroxyethyl acrylate, the hydroxyethyl methylacrylate.
4, preparation method of soap-free fluorocarbon emulsion according to claim 1 is characterized in that: the fluorochemical monomer in the said polymerization single polymerization monomer is 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.
5, preparation method of soap-free fluorocarbon emulsion according to claim 1, it is characterized in that: said initiator is ammonium persulphate, Potassium Persulphate or oxidation-reduction trigger system ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium bisulfite, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxidized portion and reduction part is 1: 2-0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100213793A CN101503496A (en) | 2009-03-04 | 2009-03-04 | Preparation of fluorocarbon soap-free emulsion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100213793A CN101503496A (en) | 2009-03-04 | 2009-03-04 | Preparation of fluorocarbon soap-free emulsion |
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| CN101503496A true CN101503496A (en) | 2009-08-12 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061668A (en) * | 2015-07-22 | 2015-11-18 | 陕西科技大学 | Cationic fluorine-containing emulsion and preparation method therefor |
| CN110804138A (en) * | 2019-11-19 | 2020-02-18 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer prepared by soap-free emulsion polymerization method and method |
| CN110922539A (en) * | 2019-11-19 | 2020-03-27 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer prepared by ultra-concentrated emulsion method and preparation method thereof |
| CN110951009A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer and method for preparing same by core-shell emulsion method |
| CN110951010A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylic slump retaining agent and method for preparing same by using ultra-concentrated emulsion method |
-
2009
- 2009-03-04 CN CNA2009100213793A patent/CN101503496A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061668A (en) * | 2015-07-22 | 2015-11-18 | 陕西科技大学 | Cationic fluorine-containing emulsion and preparation method therefor |
| CN105061668B (en) * | 2015-07-22 | 2017-03-08 | 陕西科技大学 | A kind of cation fluoride emulsion and preparation method thereof |
| CN110804138A (en) * | 2019-11-19 | 2020-02-18 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer prepared by soap-free emulsion polymerization method and method |
| CN110922539A (en) * | 2019-11-19 | 2020-03-27 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer prepared by ultra-concentrated emulsion method and preparation method thereof |
| CN110951009A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylate superplasticizer and method for preparing same by core-shell emulsion method |
| CN110951010A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylic slump retaining agent and method for preparing same by using ultra-concentrated emulsion method |
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Open date: 20090812 |