# US 11,299,593 B2 · Fluorosilicone resin and preparation method thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,593 B2 - Document ID: US11299593B2 - Status: Granted - Kind: B2 - Application number: 17/032,436 - Filed: 2020-09-25 - Published: 2021-01-14 - Granted: 2022-04-12 - Earliest claimed: 2018-03-23 - Assignees: Soochow University - Applicants: Soochow University - Inventors: Zhanxiong Li; Yakun Zong; Wulong Li - Web page: https://patentgrep.com/patent/US11299593B2 ## CPC - C08G 77/24: halogen-containing groups - C09J 183/04: Polysiloxanes - C08G 77/06: Preparatory processes - C08G 77/08: characterised by the catalysts used - C08G 77/20: containing silicon bound to unsaturated aliphatic groups - C08G 77/80: {Siloxanes having aromatic substituents, e.g. phenyl side groups} - C08K 5/44: Sulfenamides - C08K 5/5415: containing at least one Si—O bond - C09J 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen - C07F 7/16: Preparation thereof from silicon and halogenated hydrocarbons {direct synthesis} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) ## Abstract Provided is a fluorosilicone resin and a preparation method thereof. Using pentafluorostyrene as raw material, pentafluorophenethyldimethylchlorosilane is prepared by a hydrosilylation reaction. By means of a polycondensation reaction of the pentafluorophenethyldimethylchlorosilane, trimethylchlorosilane and tetraethyl orthosilicate, a pentafluorophenyl silicone resin is prepared. The preparation method adopts a two-step polycondensation process, which overcomes the disadvantages of a large difference in hydrolysis reactivity between pentafluorophenyldimethylchlorosilane and a copolymerized trialkyl-chlorosilane, and achieves a high yield. The obtained pentafluorophenyl silicone resin has the advantages of superior heat resistance, simple preparation process, low equipment requirements, high availability of raw material, and suitability for mass production. The heat-resistant fluorosilicone resin can be applied in a polymer material, such as a heat-resistant adhesive. ## Claims ### Claim 1 A fluorosilicone resin having the following chemical structural formula: wherein R=methyl, phenyl, vinyl or hydrogen; m=2 to 20; n=1 to 5; and p=1 to 8. ### Claim 2 (depends on 1) A method of preparing the fluorosilicone resin according to claim 1, comprising the following steps: (1) reacting a pentafluorostyrene with a dimethylchlorosilane in the presence of a noble metal salt as a catalyst to prepare a pentafluorophenethyldimethylchlorosilane; (2) reacting the pentafluorophenethyldimethylchlorosilane and a tetraethyl orthosilicate in a mixture of water, an inorganic acid and an organic solvent to form a polycondensation product, and reacting the polycondensation product with a mixture of a trimethyl chlorosilane and a tetraethyl orthosilicate to form the fluorosilicone resin. ### Claim 3 (depends on 2) The method according to claim 2, wherein a mass ratio of the pentafluorostyrene, the noble metal salt, and the dimethylchlorosilane is 1:(0.003 to 0.006):(0.5 to 2); a mass ratio of the pentafluorophenethyldimethylchlorosilane to the tetraethyl orthosilicate is (1 to 6):(1 to 10); a mass ratio of trimethyl chlorosilane to tetraethyl orthosilicate is (1 to 3):(1 to 10). ### Claim 4 (depends on 2) The method according to claim 2, further comprising: step (1): dissolving the pentafluorostyrene into an aromatic hydrocarbon solvent, adding the noble metal salt with protection of N2; adding the dimethylchlorosilane dropwise at 50 to 140° C., and conducting a reaction at 50 to 140° C. for 1 to 10 hours, to form the pentafluorophenethyldimethylchlorosilane; step (2): dispersing water and the inorganic acid in the organic solvent; adding the mixture of the pentafluorophenethyldimethylchlorosilane and the tetraethyl orthosilicated dropwise to the organic solvent at 60 to 80° C.; carrying out a first polycondensation for 0.5 to 1 hour to form the polycondensation product; adding the mixture of the trihydrocarbylmonochlorosilane and the tetraethyl orthosilicate to the polycondensation product; carrying out a second polycondensation for 1 to 6 hours to form the fluorosilicone resin. ### Claim 5 (depends on 4) The method according to claim 4, wherein the aromatic hydrocarbon solvent is selected from the group consisting of toluene, xylene, benzotrifluoride, 1,3-bis(trifluoro-methyl)benzene, the noble metal salt is chloroplatinic acid; the trihydrocarbylmonochlorosilane is selected from the group consisting of trimethyl chlorosilane, dimethylhydrochlorosilane, dimethylhydrogen monochlorosilane, phenyldimethylmonochlorosilane; the inorganic acid is concentrated sulfuric acid or concentrated hydrochloric acid; and the organic solvent is tetrahydrofuran. ### Claim 6 (depends on 4) The method according to claim 4, wherein, in the step (1), the dimethylchlorosilane is added dropwise over a period of 0.5 to 5 hours; in the step (2), the mixture of the trihydrocarbylmonochlorosilane and the tetraethyl orthosilicate is added over a period of 0.5 to 1 hour. ### Claim 7 (depends on 4) The method according to claim 4, further comprising: in the step (1), removing the aromatic hydrocarbon solvent under vacuum to obtain the pentafluorophenethyldimethylchlorosilane after completing the reaction; and in step (2), after the second polycondensation, cooling, distilling under vacuum, separating, extracting, washing with distilled water, drying, filtering, and distilling to form the fluorosilicone resin.