Fluoroolefin monomers and copolymers thereof

Abstract

Disclosed herein are novel fluoroolefins of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —CH═CH 2 , wherein n is 1 or 2, m is 0 or 1 and Rf is a C 1 -C 8 fluoroalkyl 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.

1 . A process for the manufacture of a fluorinated carboxylic acid of the formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —COON, wherein n is 1 or 2, m is 0 or 1 and Rf is selected from the group consisting of a C 1 -C 8  fluoroalkyl group and a C 1 -C 8  fluoroalkoxy group, said process comprising:
 A) reacting i) a fluorovinyl ether of formula Rf—O—CF═CF 2 , wherein Rf is selected from the group consisting of a C 1 -C 8  fluoroalkyl group and a C 1 -C 8  fluoroalkoxy group, with ii) iodine monochloride, iii) HF and iv) a Lewis acid catalyst at a temperature of 50°-100° C. for 10 to 48 hours to form a fluoroalkyl iodide of formula Rf—O—CF 2 CF 2 —I wherein Rf is as defined above; 
 B) reacting said fluoroalkyl iodide with an olefin selected from the group consisting of tetrafluoroethylene and vinylidene fluoride to generate a compound of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —I wherein n is 1 or 2, m is 0 or 1 and Rf is as defined above; 
 C) reacting said compound of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —I with ethylene to produce a compound of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —CH 2 CH 2 I wherein Rf, n and m are as defined above; 
 D) reacting said compound of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —CH 2 CH 2 I with base to produce a fluoroolefin of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —CH═CH 2 , wherein Rf, n and m are as defined above; and 
 E) oxidizing said fluoroolefin to a fluorinated carboxylic acid having the formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —COON, wherein n is 1 or 2, m is 0 or 1 and Rf is selected from the group consisting of a C 1 C 8  fluoroalkyl group and a C 1 -C 8  fluoroalkoxy group. 
 
     
     
         2 . A process for the manufacture of a fluorinated carboxylic acid of  claim 1  wherein said Lewis acid catalyst is selected from the group consisting of BF 3 , SbF 3 , Ta F 5 , NbF 5 , SbCl 5  and TiCl 4 . 
     
     
         3 . A process for the manufacture of a fluorinated carboxylic acid of  claim 1  wherein step C) is run at 190° to 230° C. for 6 to 24 hours in the absence of a radical initiator. 
     
     
         4 . A process for the manufacture of a fluorinated carboxylic acid of  claim 1  wherein step C) is run at 60° to 90° C. in the presence of radical initiator. 
     
     
         5 . A process for the manufacture of a fluorinated carboxylic acid of  claim 1  wherein an oxidizing agent selected from the group consisting of KMnO 4  and CrO 3  is employed in step E). 
     
     
         6 . A process for the manufacture of a fluorinated carboxylic acid of  claim 1  further comprising F) neutralizing said fluorinated carboxylic acid with base to form an anionic fluorosurfactant of formula Rf—O—(CF 2 CF 2 ) n (CH 2 CF 2 ) m —COOM, wherein M is a univalent cation.