# US 5,710,345 A · Floorinated polymers and copolymers containing cyclic structures > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,710,345 A - Document ID: US5710345A - Status: Granted - Kind: A - Application number: 08/749,504 - Filed: 1996-11-15 - Granted: 1998-01-20 - Earliest claimed: 1994-05-19 - Assignees: Ausimont S.p.A. - Inventors: Walter Navarrini; Vito Tortelli; Alessandro Zedda - Web page: https://patentgrep.com/patent/US5710345A ## CPC - C08F 16/32: Monomers containing two or more unsaturated aliphatic radicals - C07C 43/313: containing halogen - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Polymers and copolymers of one or more fluorinated dienes of structure CFX.sup.1 .dbd.CX.sup.2 --O--CX.sup.3 X.sup.4 --O--CX.sup.2 .dbd.CX.sup.1 F, wherein X.sup.1 and X.sup.2 are F, Cl or H, and X.sup.3 and X.sup.4 are F or CF.sub.3, wherein said dienes essentially form cyclic repetitive units, the comonomers used for preparing copolymers being ethylene unsaturated fluorinated compounds. Processes for preparing the fluorinated dienes having said structure which comprise the reaction in solution between one halogenated olefin and one hypofluorite CX.sup.3 X.sup.4 (OF).sub.2, wherein X.sup.3 and X.sup.4 are F or CF.sub.3, and the dehalogenation or dehydrohalogenation of the linear adduct between one hypofluorite molecule and two olefin molecules. The polymers and copolymers of the invention are particularly suitable for preparing coatings for applications at high temperatures. ## Claims ### Claim 1 Fluorinated derivatives of bisvinyloxymethane of structure CFX.sup.1 .dbd.CX.sup.2 --O--CX.sup.3 X.sup.4 --O--CX.sup.2' .dbd.CX.sup.1' F, wherein X.sup.1 and X.sup.2, equal to or different from each other, are F, Cl or H; X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3 ; X.sup.1' and X.sup.2', equal to or different from each other, are X.sup.1 or X.sup.2, with the proviso that when X.sup.1 is different from X.sup.2 then X.sup.1' is different from X.sup.2'. ### Claim 2 Fluorinated derivatives of bisvinyloxymethane of structure CFX.sup.1 .dbd.CX.sup.1 --O--CX.sup.3 X.sup.4 --O--CX.sup.1 .dbd.CX.sup.1 F wherein X.sup.1 is F, Cl or H; X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3. ### Claim 3 Fluorinated derivatives of bisvinyloxymethane of structure CF.sub.2 .dbd.CF--O--CX.sup.3 X.sup.4 --O--CF.dbd.CF.sub.2, wherein X.sup.3 and X.sub.4, equal to or different from each other, are F or CF.sub.3. ### Claim 4 Perfluorobisvinyloxymethane CF.sub.2 .dbd.CF--O--CF.sub.2 --O--CF.dbd.CF.sub.2. ### Claim 5 Process for the preparation of bisvinyloxymethane derivatives having the structure CFX.sup.1 .dbd.CX.sup.2 --O--CX.sup.3 X.sup.4 --O--CX.sup.2' .dbd.CX.sup.1' F, wherein X.sup.1 and X.sup.2, equal to or different from each other, are F, Cl or H; X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3 ; X.sup.1' and X.sup.2', equal to or different from each other, are X.sup.1 or X.sup.2, with the proviso that if X.sup.1 is different from X.sup.2 also X.sup.1' is to be different from X.sup.2', comprising: i) addition of an olefin of formula CX.sup.1 X.sup.5 .dbd.CX.sup.2 X.sup.6, wherein X.sup.1, X.sup.2, X.sup.5 and X.sup.6 equal to or different from each other are F, Cl, H or Br, the Br atoms being 2 at most and in such a case being bound to different carbon atoms, X.sup.1 and X.sup.5 not being both F, X.sup.2 and X.sup.6 not being both F, X.sup.1 and X.sup.2 being F only if X.sup.5 and X.sup.6 are different from F and not being both H, in a reactor where an hypofluorite of general formula CX.sup.3 X.sup.4 (OF).sub.2 is essentially always present, where X.sup.3 and X.sup.4 equal to or different from each other, are F or CF.sub.3, dissolved in an inert solvent and having a concentration between 0.001M and 10M, at a temperature from -140.degree. C. to +60.degree. C.; ii) separation of the reaction product of two olefin molecules and one hypofluorite molecule from the reaction mixture obtained in i) by fractional distillation iii) dehalogenation or dehydrohalogenation of the product obtained in ii), wherein the eliminated halogen atoms are Cl or Br. ### Claim 6 Process for preparing bisvinyloxymethane derivatives having the structure CFX.sup.1 .dbd.CX.sup.1 --O--CX.sup.3 X.sup.4 --O--CX.sup.1 .dbd.CX.sup.1 F, wherein X.sup.1 is F, Cl or H; X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3, which comprises: i) addition of an olefin of formula CX.sup.1 X.sup.5 .dbd.CX.sup.1 X.sup.6, wherein X.sup.1, X.sup.5 and X.sup.6 equal to or different from each other, are F, Cl, Br or H, X.sup.1 and X.sup.5 not being both F, X.sup.1 and X.sup.6 not being both F, X.sup.1 being Br only if X.sup.5 and X.sup.6 equal to each other are different from Br, X.sup.1 being F only if X.sup.5 and X.sup.6 are different from F and not both H, to an hypofluorite of general formula CX.sup.3 X.sup.4 (OF).sub.2 wherein X.sup.3 and X.sup.4 equal to or different from each other, are F or CF.sub.3, dissolved in an inert solvent having a concentration between 0.001M and 10M, at a temperature from -140.degree. C. to +60.degree. C.; ii) separation of the reaction product of two olefin molecules and one hypofluorite molecule from the reaction mixture obtained in i) by fractional distillation iii) dehalogenation or dehydrohalogenation of the product obtained in ii), wherein the eliminated halogen atoms are Cl or Br. ### Claim 7 Process for preparing bisvinyloxymethane derivatives having the structure CF.sub.2 .dbd.CF--O--CX.sup.3 X.sup.4 --O--CF.dbd.CF.sub.2, wherein X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3, which comprises: i) addition of an olefin of formula CFX.sup.5 .dbd.CFX.sup.6, wherein X.sup.5 is Cl, Br or H, and X.sup.6 is Cl or Br, to an hypofluorite of general formula CX.sup.3 X.sup.4 (OF).sub.2 wherein X.sup.3 and X.sup.4, equal to or different from each other, are F or CF.sub.3, dissolved in an inert solvent having a concentration between 0.001M and 10M, at a temperature from -140.degree. C. to +60.degree. C.; ii) separation of the reaction product of two olefin molecules and one hypofluorite molecule from the reaction mixture obtained in i) by fractional distillation iii) dehalogenation or dehydrohalogenation of the product obtained in ii), wherein the eliminated halogen atoms are Cl or Br. ### Claim 8 (depends on 5, 6, 7) Process according to anyone of the claims 5, 6 or 7 wherein the solution of the hypofluorite has a concentration from 0.1M to 4M. ### Claim 9 (depends on 5, 6, 7) Process according to anyone of the claims 5, 6 or 7 wherein the reaction temperature is from -120.degree. C. to 0.degree. C. ### Claim 10 (depends on 5, 6, 7, 8, 9) Process according to anyone of the claims 5, 6, 7, 8 or 9, characterized in that the solution of hypofluorite is prepared using an inert solvent of polar type. ### Claim 11 (depends on 10) Process according to claim 10 characterized in that the solvent is selected from hydrogenfluorocarbons, hydrogenchlorocarbons, fluorochlorocarbons, hydrogenfluorocarbons, trifluoroacetic acid, trifluoroacetic anhydride, acetic nitrile, hydrofluoric acid, sulphur dioxide, trifluoromethanesulphonic acid, CF.sub.2 Cl--CFCl--SO.sub.2 F, mixtures thereof and mixtures of one or more of the same with a solvent having low polarity. ### Claim 12 (depends on 5) Process according to claim 5 wherein the olefin is selected from: CFCl.dbd.CFCl, CHCl.dbd.CHCl, CHCl.dbd.CCl.sub.2, CCl.sub.2 .dbd.CCl.sub.2, CH.sub.2 .dbd.CF.sub.2, CF.sub.2 .dbd.CF.sub.2, CFH.dbd.CFCl, CFCl.dbd.CHCl, CH.sub.2 .dbd.CCl.sub.2, CH.sub.2 .dbd.CFCl. ### Claim 13 (depends on 5) Fluorinated derivatives of bisethoxymethane obtained as intermediates after the steps i) and ii) of the processes of claims 5.