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CN-121991354-A - Acrylic ester modified fluorosilicone oil and preparation method and application thereof

CN121991354ACN 121991354 ACN121991354 ACN 121991354ACN-121991354-A

Abstract

The invention belongs to the technical field of silicone oil, and particularly relates to acrylate modified fluorosilicone oil and a preparation method and application thereof. The acrylic ester modified fluorosilicone oil has a structure shown in a formula I, wherein n is any integer of 0-6, a is any integer of 1-100, b is any integer of 1-100, and c is any integer of 1-100. The acrylate modified fluorosilicone oil provided by the invention has good stability, and can be rapidly subjected to photocuring (3-20 s) under the ultraviolet irradiation condition when the acrylate modified fluorosilicone oil provided by the invention is used as a raw material for preparing the release film, so that the curing time is shortened compared with the commercially available addition type fluorine release agents (such as the fluorine release agent 7785 or the fluorine release agent 7795), and the production efficiency of the release film is greatly improved. Formula I.

Inventors

  • WU JIRONG
  • HU YINGQIAN
  • ZHANG PENGFEI
  • WU DI

Assignees

  • 杭州师范大学

Dates

Publication Date
20260508
Application Date
20260409

Claims (10)

  1. 1. The acrylic ester modified fluorosilicone oil is characterized by having a structure shown in a formula I: A formula I; wherein n is any integer from 0 to 6, a is any integer from 1 to 100, b is any integer from 1 to 100, and c is any integer from 1 to 100.
  2. 2. The acrylate modified fluorosilicone oil according to claim 1, wherein n is 0,1, 2, 3, 4, 5 or 6, and c/(a+b+c+2) is 1 to 45%.
  3. 3. The method for preparing the acrylate modified fluorosilicone oil according to claim 1 or 2, which is characterized by comprising the following steps: Mixing the compound 1, trimethylolpropane monoallyl ether and a platinum catalyst, and heating to perform an addition reaction to obtain a compound 2; The compound 2, acrylic acid, an acid catalyst, a water carrying agent and a polymerization inhibitor are mixed for the second time and then subjected to esterification reaction to obtain the acrylic ester modified fluorosilicone oil; Compound 1; Compound 2.
  4. 4. The preparation method of the compound 1 according to claim 3, wherein the compound 1 comprises hydrogen-containing methyl trifluoropropyl fluorosilicone oil or hydrogen-containing methyl nonafluorohexyl fluorosilicone oil, and the hydrogen content of the compound 1 is 0.01-0.36wt%; The platinum catalyst comprises a Karstedt catalyst or a Speier catalyst.
  5. 5. The preparation method according to claim 3 or 4, wherein the molar ratio of the trimethylolpropane monoallyl ether to the Si-H-containing group in the compound 1 is 0.8-1.5:1; The weight ratio of the platinum element in the platinum catalyst in the total weight of the compound 1 and the trimethylolpropane monoallyl ether is 1-200 ppm.
  6. 6. The method according to claim 3 or 4, wherein the temperature of the addition reaction is 60 to 120 ℃ and the time is 0.2 to 12 hours.
  7. 7. The preparation method according to claim 3, wherein the acidic catalyst comprises one or more of toluene sulfonic acid, p-toluene sulfonic acid monohydrate and trifluoroacetic acid, the water-carrying agent comprises one or more of toluene, xylene, cyclohexane, n-heptane and n-octane, and the polymerization inhibitor comprises one or more of hydroquinone, p-benzoquinone, o-methyl hydroquinone, p-hydroxyanisole 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone, phenothiazine, 1-diphenyl-2-picrylhydrazine and p-methoxyphenol; the molar ratio of the acrylic acid to the trimethylolpropane monoallyl ether is 2-5:1.
  8. 8. The method according to claim 3, wherein the esterification reaction is carried out under reflux conditions, and the reflux time is 3 to 12 hours.
  9. 9. The application of the acrylate modified fluorosilicone oil prepared by the preparation method of claim 1 or 2 or any one of claims 3-8 in preparing release films.
  10. 10. The use according to claim 9, wherein the method for preparing a release film using acrylate modified fluorosilicone oil comprises the steps of: mixing acrylic ester modified fluorosilicone oil, a photoinitiator and an anchoring agent, coating the mixture on the surface of a substrate, and performing ultraviolet light curing to obtain the release film; the ultraviolet curing time is 3-30 s.

Description

Acrylic ester modified fluorosilicone oil and preparation method and application thereof Technical Field The invention belongs to the technical field of organic silicon, and particularly relates to acrylate modified fluorosilicone oil and a preparation method and application thereof. Background The fluorosilicone oil is usually formed by introducing fluorine-containing organic groups into the side chains of common silicone oil (polydimethylsiloxane), and as a large class of special organosilicon compounds, the fluorosilicone oil combines the advantages of fluorine element and silicon element, and therefore has a plurality of unique properties, and is widely used in the manufacture of industrial products such as waterproof/oil-proof finishing agents, lubricants, defoamers, release agents, paint additives, release agents and the like. At present, commercially available addition type fluorine release agents such as Dow 7785 and 7795 take linear polysiloxane containing vinyl and methyl nine-fluorohexyl as base gum, hydrogen-containing silicone oil as a crosslinking agent and a large amount of organic solvent as a dispersing agent, and realize crosslinking and film formation under the action of a platinum-series catalyst, and the curing and practical application of the release agents are seriously affected because the platinum-series catalyst is easy to react with N, P, S-containing compounds in application scenes and is deactivated (commonly called as catalyst poisoning). Disclosure of Invention In order to solve the defects in the prior art, the invention provides the acrylate modified fluorosilicone oil, and the preparation method and the application thereof, wherein the acrylate modified fluorosilicone oil can be rapidly cured under ultraviolet radiation, can avoid the generation of catalyst poisoning without adding extra catalyst, and can improve the production efficiency and the environmental friendliness of the release film. In order to solve the technical problems, the invention provides acrylic ester modified fluorosilicone oil which has a structure shown in a formula I: A formula I; wherein n is any integer from 0 to 6, a is any integer from 1 to 100, b is any integer from 1 to 100, and c is any integer from 1 to 100. Preferably, n is 0,1, 2, 3, 4, 5 or 6, and c/(a+b+c+2) is 1 to 45%. The invention also provides a preparation method of the acrylic ester modified fluorosilicone oil, which comprises the following steps: Mixing the compound 1, trimethylolpropane monoallyl ether and a platinum catalyst, and heating to perform an addition reaction to obtain a compound 2; The compound 2, acrylic acid, an acid catalyst, a water carrying agent and a polymerization inhibitor are mixed for the second time and then subjected to esterification reaction to obtain the acrylic ester modified fluorosilicone oil; Compound 1; Compound 2. Preferably, the compound 1 comprises hydrogen-containing methyl trifluoropropyl fluorosilicone oil or hydrogen-containing methyl nonafluorohexyl fluorosilicone oil, wherein the hydrogen content of the compound 1 is 0.01-0.36wt%; The platinum catalyst comprises a Karstedt catalyst or a Speier catalyst. Preferably, the molar ratio of the trimethylolpropane monoallyl ether to the Si-H-containing group in the compound 1 is 0.8-1.5:1; The weight ratio of the platinum element in the platinum catalyst in the total weight of the compound 1 and the trimethylolpropane monoallyl ether is 1-200 ppm. Preferably, the temperature of the addition reaction is 60-120 ℃ and the time is 0.2-12 h. Preferably, the acid catalyst comprises one or more of toluene sulfonic acid, p-toluene sulfonic acid monohydrate and trifluoroacetic acid, the water carrying agent comprises one or more of toluene, xylene, cyclohexane, n-heptane and n-octane, and the polymerization inhibitor comprises one or more of hydroquinone, p-benzoquinone, o-methyl hydroquinone, p-hydroxyanisole 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone, phenothiazine, 1-diphenyl-2-picrylhydrazine and p-methoxyphenol; the molar ratio of the acrylic acid to the trimethylolpropane monoallyl ether is 2-5:1. Preferably, the esterification reaction is carried out under a reflux condition, and the reflux time is 3-12 hours. The invention also provides application of the acrylic ester modified fluorosilicone oil prepared by the technical scheme or the preparation method of the acrylic ester modified fluorosilicone oil in preparation of release films. Preferably, the method for preparing the release film by utilizing the acrylate modified fluorosilicone oil comprises the following steps: mixing acrylic ester modified fluorosilicone oil, a photoinitiator and an anchoring agent, coating the mixture on the surface of a substrate, and performing ultraviolet light curing to obtain the release film; the ultraviolet curing time is 3-30 s. The invention provides acrylic ester modified fluorosilicone oil, which has a structure shown in a formula I: