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CN-122011258-A - Application of fluorine-containing polymer as surfactant

CN122011258ACN 122011258 ACN122011258 ACN 122011258ACN-122011258-A

Abstract

The invention discloses an application of a fluorine-containing polymer as a surfactant, wherein the surface tension of a solution with the fluorine-containing polymer content of 1.0wt% is 28-39 mN/m. When the fluorine-containing polymer is used as a surfactant in the fields of photovoltaic backboard coating, lithium battery diaphragm coating, lithium battery anode binder, film, fluorine-containing polymer film, coating, fluorine-containing polymer coating, viscous glue solution and the like, the fluorine-containing polymer has excellent interface regulation performance, and can effectively improve the problems of shrinkage cavity, orange peel, ripple and the like caused by unbalanced surface tension.

Inventors

  • ZENG YANG
  • LU YANGTIAN
  • ZHU WEIWEI

Assignees

  • 浙江省化工研究院有限公司
  • 中化蓝天集团有限公司

Dates

Publication Date
20260512
Application Date
20241105

Claims (12)

  1. 1. The application of the fluoropolymer as the surfactant is characterized in that the surface tension of a solution with the fluoropolymer content of 1.0wt% is 28-39 mN/m.
  2. 2. Use of a fluoropolymer according to claim 1 as a surfactant, characterized in that: the solution with the content of the fluorine-containing polymer of 1.0 weight percent is prepared by dissolving the fluorine-containing polymer in an organic solvent, wherein the organic solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
  3. 3. The method of using a fluoropolymer as a surfactant according to claim 1, wherein said fluoropolymer is prepared by polymerizing vinylidene fluoride, fluoroenyl ether structural monomers and ethylenically unsaturated polar structural monomers.
  4. 4. The use of the fluorine-containing polymer as a surfactant according to claim 3, wherein the fluoroalkenyl ether structural monomer is a compound represented by the structural formula (1), Wherein R 1 、R 2 、R 3 is independently selected from hydrogen, halogen, perfluoroalkyl group having 1-6 carbon atoms, R 1 、R 2 、R 3 is at least one of halogen or perfluoroalkyl group having 1-6 carbon atoms, Rf is selected from perfluoroalkyl groups having 1 to 12 carbon atoms, and perfluorooxyalkyl groups having 1 to 200 carbon atoms and containing one or more ether oxygen atoms.
  5. 5. The method of using a fluoropolymer as surfactant according to claim 4, wherein said fluoroalkenyl ether structural monomer is selected from the group consisting of CH 2 ＝CF-O-CF 3 、CH 2 ＝CF-O-CF 2 -CF 3 、CH 2 ＝CF-O-CF 2 -CF 2 -CF 3 、 CH 2 ＝CF-O-CF(CF 3 )-CF 3 、CH 2 ＝CF-O-CF(CF 3 )-CF 2 -CF 3 、CH 2 ＝CF-O-CF 2 -CF(CF 3 )-CF 3 、 CH 2 ＝CF-O-CF 2 -CF(CF 3 )-O-CF 2 -CF 2 -CF 3 、CH 2 ＝C(CF 3 )-O-CF 3 、CH 2 ＝C(CF 3 )-O-CF 2 -CF 3 、 CH 2 ＝C(CF 3 )-O-CF 2 -CF 2 -CF 3 、CH 2 ＝C(CF 3 )-O-CF(CF 3 )-CF 3 、 CH 2 ＝C(CF 3 )-O-CF(CF 3 )-CF 2 -CF 3 、CH 2 ＝C(CF 3 )-O-CF 2 -CF(CF 3 )-CF 3 、 CH 2 ＝C(CF 3 )-O-CF 2 -CF(CF 3 )-O-CF 2 -CF 2 -CF 3 、CF 2 ＝CF-O-CF 3 、CF 2 ＝CF-O-CF 2 -CF 3 、 CF 2 ＝CF-O-CF 2 -CF 2 -CF 3 、CF 2 ＝CF-O-CF(CF 3 )-CF 3 、CF 2 ＝CF-O-CF(CF 3 )-CF 2 -CF 3 、 CF 2 ＝CF-O-CF 2 -CF(CF 3 )-CF 3 、CF 2 ＝CF-O-CF 2 -CF(CF 3 )-O-CF 2 -CF 2 -CF 3 At least one of them.
  6. 6. The method of claim 5, wherein said fluoroalkenyl ether structural monomer is at least one selected from the group consisting of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether.
  7. 7. The method of claim 3, wherein said ethylenically unsaturated polar monomer is at least one selected from the group consisting of alkenylcarboxylic acids, alkenylcarboxylic esters, alkenylphosphonic acids, alkenylphosphonic esters, and alkenylsulfonic compounds.
  8. 8. The method of claim 3, wherein said ethylenically unsaturated polar monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, itaconic acid, maleate, citraconic acid, 2- (trifluoromethyl) acrylic acid, 2-fluoroacrylic acid, vinylphosphonic acid, dimethyl vinylphosphonate, diethyl vinylphosphonate, and vinylsulfonic acid.
  9. 9. The method of using a fluoropolymer according to claim 3 as a surfactant, wherein said fluoropolymer has a vinylidene fluoride structural unit content of 69 to 99mol%, a fluoroalkenyl ether structural unit content of 0.1 to 30mol%, and an ethylenically unsaturated polar structural unit content of 0.1 to 30mol%.
  10. 10. The method of using the fluoropolymer as surfactant according to claim 1, wherein the fluoropolymer is used as surfactant in photovoltaic back sheet coating, lithium battery separator coating, lithium battery positive electrode binder, film, fluoropolymer film, paint, fluoropolymer paint, adhesive glue.
  11. 11. The method according to claim 10, wherein the fluorine-containing polymer is used as a surfactant for at least one of a photovoltaic back sheet coating, a lithium battery separator coating, a lithium battery positive electrode binder, a film, a fluorine-containing polymer film, a paint, a fluorine-containing polymer paint, and an adhesive glue solution, wherein the fluorine-containing polymer is selected from the group consisting of polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, a vinylidene fluoride-trifluoroethylene copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene copolymer, and an ethylene-chlorotrifluoroethylene copolymer.
  12. 12. The use of the fluoropolymer according to claim 10 or 11 as a surfactant, wherein the amount of the fluoropolymer used as a surfactant is 0.01-10wt%.

Description

Application of fluorine-containing polymer as surfactant Technical Field The invention relates to the field of polymers, in particular to an application of a fluorine-containing polymer as a surfactant. Background Fluorine-containing polymer materials are of great interest because of their unique chemical stability and mechanical properties. Among them, polyvinylidene fluoride (PVDF) is a partially fluorinated, semi-crystalline polymer having excellent chemical resistance, heat resistance, weather resistance, and dielectric properties, making it the second most productive fluoropolymer on the market at present. As a main member of the family of fluorine-containing high molecular materials, the specificity of the PVDF resin is that the polymer chain segment not only provides C-F bonds with framework structure stability, but also contains C-H bonds with solubility, so that the PVDF resin is easy to process, and therefore, the PVDF resin is particularly suitable for being dissolved by a solvent to prepare a paint and a viscous glue solution, such as a paint, a photovoltaic back plate coating, a lithium battery diaphragm coating, a lithium battery positive electrode binder and the like. When PVDF resin is dissolved by solvent to prepare paint or glue solution, there is a process of solvent evaporation and film drying at solid-liquid interface, which may occur shrinkage cavity caused by unbalanced surface tension, orange peel caused by unbalanced surface tension of the surface layer and the lower layer of film volatilized by solvent, and uneven film drying speed, the surface tension of fast drying place is higher than that of slow drying place, at this time, the surface tension will push the paint at slow drying place to move to fast drying place, and left and right direction waves are generated. In order to ensure that the coating or the adhesive glue solution forms a flat, smooth and uniform film in the drying film forming process and prevent shrinkage cavity, orange peel, ripple and other phenomena, an additional surfactant or a leveling agent is required to be added into the coating or the glue solution. However, the addition of these surfactants makes the original system more complex, and may bring about some new problems, such as the fact that the surfactants used in the photovoltaic back sheet coating are not resistant to aging and ultraviolet radiation, the surfactants used in the lithium battery separator coating are not resistant to electrolyte dissolution, and the surfactants used in the lithium battery positive electrode binder are not resistant to electrochemical oxidation, thereby reducing the use effect and the service life of the PVDF resin material. Thus, to avoid the uncertainty effect of the introduction of other components, it is necessary to provide a surfactant with excellent interfacial conditioning properties developed based on fluoropolymers. Disclosure of Invention Technical problem to be solved by the invention In order to solve the problems of shrinkage cavity, orange peel, ripple and the like of the fluorine-containing resin coating or glue solution in the film forming and drying process and avoid the influence caused by additional surfactant components, the inventor of the invention discovers that the surfactant developed based on the fluorine-containing polymer has good interface regulating performance. Technical scheme for solving problems The application of a fluorine-containing polymer as a surfactant, wherein the surface tension of a solution with the fluorine-containing polymer content of 1.0wt% is 28-39 mN/m. Further, the surface tension of the solution with the fluoropolymer content of 1.0wt% is 28-37 mN/m, and preferably, the surface tension is 28-35 mN/m. Further, the solution with the content of the fluorine-containing polymer of 1.0 weight percent is prepared by dissolving the fluorine-containing polymer in an organic solvent, wherein the organic solvent is an organic solvent commonly used in the field of paint or glue solution, preferably, the organic solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and more preferably, the organic solvent is selected from N-methylpyrrolidone. The fluorine-containing polymer is prepared by polymerization reaction of vinylidene fluoride, fluoro alkenyl ether structural monomer and olefinically unsaturated polar structural monomer. The fluoro alkenyl ether structural monomer is a compound shown in a structural formula (1), Wherein R 1、R2、R3 is independently selected from hydrogen, halogen, perfluoroalkyl group having 1-6 carbon atoms, R 1、R2、R3 is at least one of halogen or perfluoroalkyl group having 1-6 carbon atoms, Rf is selected from perfluoroalkyl groups having 1 to 12 carbon atoms, and perfluorooxyalkyl groups having 1 to 200 carbon atoms and containing one or more ether oxygen atoms. Preferably, the fluoroalkenyl ether structural monomer is selected from at