E.i. Dupont De Nemours and Company

Dupont Dow Elastomers Inc.

Centre National De La Recherche Scientifique

Dupont Performance Elastomers LLC

Le Centre National De La Recherche Scien

Le Centre National De La Recherche Science

Other

Le Centre National De La Recherche Scientifique

Ming-Hong Hung

Bruno Ameduri

Paul R Resnick

Shlomo Rozen

William Brown Farnham

Paul Douglas Brothers

Phan Linh Tang

Georgi Kostov

Walter Werner Schmiegel

Michael Joseph Michalczyk

Michael Cregg Coughlin

Sheng Peng

Douglas Robert Anton

Ronald James McKinney

Anestis L Logothetis

Dewey Lynn Kerbow

Mureo Kaku

Tatsuhiro Takahashi

Guillaume Tillet

Andrew Edward Feiring

Robert Clayton Wheland

Carl G Krespan

Bernard Boutevin

Christopher P Junk

Lech Wilczek

Zhen-Yu Yang

Hasan Dindi

Jose Manuel Rodriguez-Parada

Paul Raphael Resnick

Donald Frederick Lyons

Xudong Chen

Vinayakam Subramanyam

Hsu-Nan Huang

Aaron C Su

John Joseph Hagedorn

Roger John Zipfel

Keith W Palmer

Aurelien Soules

Wei-Yuan Huang

Yuanfa Zhang

Cyrille Andre Jean-Marie Boyer

Baishen Liang

Donald F Lyons

Phan L Tang

Provided herein are copolymers that comprise copolymerized residues of a perfluorotrivinyltriazine monomer of Formula 1.  Preferred Rgroups include, without limitation, &#x2014;(CF)&#x2014; (n=1-6); &#x2014;(CF)&#x2014;[OCF(CF)CF]&#x2014; (m=1-4, p=1-4); and &#x2014;[(CF(CF)&#x2014;O)&#x2014;(CF)]&#x2014; (x=1-3, k=1-5). Preferred comonomers for copolymerization with the perfluorotrivinyltriazine monomer (1) include, without limitation, tetrafluoroethylene (TFE); vinylidene fluoride (VF2); hexafluoropropylene (HFP); vinyl fluoride (VF); EVE; PSEPVE; perfluoro-(long chain vinyl ethers); E; P; PFBE; PEVE; EVE-OH; EVE-P; PDD; and the cure-site monomers BTFB, ITFB, 8-CNVE, 8-SAVE, and the like. Also provided are methods of synthesizing the copolymers and articles comprising the copolymers.

Copolymers of perfluorotrivinyltriazine compounds and methods for synthesizing the copolymers

Compositions comprising fluoroelastomers having copolymerized units of a cyano-containing cure site monomer are cured (i.e. crosslinked) with a fluoropolymer having pendant sulfonyl azide groups. The latter fluoropolymer comprises copolymerized units of a fluoroalkanesulfonyl azide of formula CF&#x2550;CF&#x2014;(O)&#x2014;R&#x2014;(CH)&#x2014;SON, wherein p=0 or 1; n=0-4; and Ris a C-Cperfluoroalkyl or perfluoroalkoxy group. The crosslinks are tetrazole rings formed by the reaction of the pendant sulfonyl azide groups on the fluoropolymer with pendant cyano groups on the fluoroelastomer.

Curable fluoroelastomer composition

Disclosed herein is a crosslinked fluoropolymer network formed by the free radical initiated crosslinking of a diacrylate fluoropolymer. The diacrylate copolymer is of formula CH&#x2550;CR'COO&#x2014;(CH)&#x2014;R&#x2014;(CH)&#x2014;OOCR&#x2032;&#x2550;CH, wherein R is selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and iv) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin, R&#x2032; is H or &#x2014;CH, n is 1-4 and wherein said oligomer has a number average molecular weight of 1000 to 25,000 daltons. The source of the free radicals may be a photoinitiator or an organic peroxide.

Crosslinked fluoropolymer networks

Disclosed herein is a telechelic diacrylate fluoropolymer and a process for manufacture of the fluoropolymer. The diacrylate copolymer is of formula CH&#x2550;CR'COO&#x2014;(CH)&#x2014;R&#x2014;(CH)&#x2014;OOCCR&#x2032;&#x2550;CH, wherein R is selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and iv) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin, R&#x2032; is H or&#x2014;CH, n is 1-4 and wherein said oligomer has a number average molecular weight of 1000 to 25,000 daltons.

Fluoropolymers having diacrylate ends

A process for manufacturing a polyfluroalkanoyl phosphorodichloridate comprising reacting a polyfluoroalkanol having the general formula R&#x2014;CH&#x2014;OH, wherein Ris a linear or branched C-Cperfluoroalkyl group optionally interrupted by O, with at least 4 moles of POClper mole of R&#x2014;CH&#x2014;OH in the presence of 0.1 to 0.2 moles of LiCl catalyst per mole of R&#x2014;CH&#x2014;OH at a temperature between 95&#xb0; C. and 110&#xb0; C. to form a phosphorodichloridate of the general formula R&#x2014;CH&#x2014;O&#x2014;P(O)Cl.

Catalytic process for phospho-halogenation of fluorinated alcohols

This invention relates to curable fluoroelastomer compositions comprising a) fluoroelastomers having either nitrile, alkyne or azide cure sites and b) fluorinated curatives containing diazide, dinitrile or dialkyne groups for reacting with cure sites on the fluoroelastomer. Fluoroelastomers having azide cure sites form crosslinks with curatives having dinitrile or dialkyne groups. Fluoroelastomers having nitrile or alkyne cure sites form crosslinks with curatives having diazide groups.

Curable fluoroelastomer compositions

Disclosed herein is a crosslinked fluoropolymer network formed by the free radical initiated crosslinking of a diacrylate fluoropolymer The diacrylate copolymer is of formula CH&#x2550;CR'COO&#x2014;(CH)&#x2014;R&#x2014;(CH)&#x2014;OOCR&#x2032;&#x2550;CH, wherein R is selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and iv) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin, R&#x2032; is H or &#x2014;CH, n is 1-4 and wherein said oligomer has a number average molecular weight of 1000 to 25,000 daltons. The source of the free radicals may be a photoinitiator or an organic peroxide.

Disclosed herein is a telechelic diacrylate fluoropolymer and a process for manufacture of the fluoropolymer. The diacrylate copolymer is of formula CH&#x2550;CR'COO&#x2014;(CH)&#x2014;R&#x2014;(CH)&#x2014;OOCCR&#x2032;&#x2550;CH, wherein R is selected from the group consisting of i) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), ii) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, iii) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and iv) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin, R&#x2032; is H or &#x2014;CH, n is 1-4 and wherein said oligomer has a number average molecular weight of 1000 to 25,000 daltons.

Oligomers of perfluoro(methyl vinyl ether) with vinylidene fluoride or tetrafluoroethylene are disclosed that contain 40-90 mole percent copolymerized units of vinylidene fluoride or tetrafluoroethylene and 10-60 mole percent copolymerized units of perfluoro(methyl vinyl ether), said oligomers having two functional endgroups and having a number average molecular weight between 1000 and 25,000.

Difunctional oligomers of perfluoro(methyl vinyl ether)

Fluorinated copolymers are prepared via copolycondensation polymerization in a process comprising reacting A) a telechelic fluoroazido compound of formula N(Y)&#x2014;(CH)&#x2014;R&#x2014;(CH)&#x2014;(Y)N, wherein Y is SO, SO, CH, or CO, p=0 or 1, n and m are independently 1 to 4, and R is selected from the group consisting of i) a C-Cfluoroalkylene group, ii) a C-Cfluoroalkoxylene group, iii) a substituted aryl group, iv) an oligomer comprising copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), v) an oligomer comprising copolymerized units of vinylidene fluoride and hexafluoropropylene, vi) an oligomer comprising copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and vii) an oligomer comprising copolymerized units of tetrafluoroethylene and a hydrocarbon olefin with B) a telechelic diyne or dinitrile compound in the presence of copper halide catalyst.

Copolycondensation polymerization of fluoropolymers

Disclosed herein are novel fluoroolefins of formula Rf&#x2014;O&#x2014;(CFCF)(CHCF)&#x2014;CH&#x2550;CH, wherein n is 1 or 2, m is 0 or 1 and Rf is a C-Cfluoroalkyl or fluoroalkoxy group. The fluoroolefins may be oxidized to manufacture fluorinated carboxylic acids. Also disclosed are fluoropolymers comprising copolymerized units of the fluoroolefins of the invention and at least one other fluoromonomer.

Fluoroolefin monomers and copolymers thereof

Fluorosilicon polymers are disclosed that are prepared by a process comprising reacting a) iodinated oligomers having copolymerized units of perfluoro(methyl vinyl ether) and vinylidene fluoride or tetrafluoroethylene that contain 40-90 mole percent copolymerized units of vinylidene fluoride or tetrafluoroethylene and 10-60 mole percent copolymerized units of perfluoro(methyl vinyl ether), said oligomers having two functional endgroups and having a number average molecular weight between 1000 and 25,000 with b) a methoxyvinyl silane or an ethoxyvinyl silane to form a silicon-containing polymeric adduct that is further reacted with an acid to form a crosslinked fluorinated polymer.

Process for preparation of fluorosilicon polymer

An emulsion polymerization process for the production of fluoroelastomers is disclosed wherein at least one fluorosurfactant is employed as dispersant, said fluorosurfactant being a fluoroalkylphosphoric acid ester of the formula X&#x2014;Rf-(CH)&#x2014;O&#x2014;P(O)(OM), wherein n=1 or 2, X=H or F, M=a univalent cation, and Rf is a C-Cfluoroalkyl or fluoroalkoxy group. Optionally, a second dispersing agent may be employed in the polymerization, said second agent being a perfluoropolyether having at least one endgroup selected from the group consisting of carboxylic acid, a salt thereof, sulfonic acid and a salt thereof, phosphoric acid and a salt thereof.

Process for producing fluoroelastomers

An emulsion polymerization process for the production of non-elastomeric fluoropolymers is disclosed wherein at least one fluorosurfactant is employed as dispersant, said fluorosurfactant being a fluoroalkylphosphoric acid ester of the formula X-Rf-(CH)&#x2014;O&#x2014;P(O)(OM), wherein n is 1 or 2, X&#x2550;H or F, M=a univalent cation, and Rf is a C-Cfluoroalkyl or fluoroalkoxy group. Optionally, a second dispersing agent may be employed in the polymerization, said second agent being a perfluoropolyether having at least one endgroup selected from the group consisting of carboxylic acid, a salt thereof, sulfonic acid and a salt thereof, phosphoric acid and a salt thereof.

Process for producing fluoropolymers

Growing community of inventors

Wilmington, DE, United States of America

Ming-Hong Hung