Blocky poly(ether ether ketone) copolymers and corresponding synthesis methods and articles

Abstract

Described here are blocky PEEK copolymers and corresponding synthesis methods. It was surprisingly found that synthesis of blocky PEEK copolymers in a non-solvent environment with respect to PEEK produced blocky PEEK copolymers with high degrees of functionalization and crystallinity. The blocky PEEK copolymers had an increased blocky structure, relative to corresponding PEEK copolymer synthesized with other known methods. Moreover, membranes formed from the blocky PEEK polymers are particularly desirable in fuel cell applications. For example, the membranes formed from the blocky PEEK polymers had surprisingly large ion conductivities as well as significantly improved chemical and thermal resistance, at least in part, to the improved functionalization and crystallinity.

1 - 15 . (canceled) 
     
     
         16 . A blocky PEEK copolymer comprising:
 (i) recurring unit (R PEEK ) represented by the following formula:   
       
         
           
           
               
               
           
         
       
       wherein
 each R 1  to R 6  is independently selected at each instance from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or an alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium; 
 i and j are independently selected integers from 0 to 4; and 
 (ii) recurring unit (R* PEEK ) represented by the following formula: 
 
       
         
           
           
               
               
           
         
         
           wherein 
         
         i, j, R 5 , R 6  and each R 1  and R 2  are identical to those selected for recurring unit (R PEEK ); 
         L 1  is the same as R 3 , −SO 3 M or —Br, 
         L 2  is the same as R 4 , —SO 3 M′ or —Br, 
         M and M′ are independently selected from the group consisting of hydrogen, Group IA elements and alkali earth metal elements; and 
         at least one of L 1  and L 2  is —SO 3 M or Br. 
       
       wherein the PEEK copolymer
 has a degree of functionalization of at least about 20%, as measured by  1 HNMR spectroscopy and 
 a degree of crystallinity of at least about 10%, as measured by Differential Scanning calorimetry (“DSC”) using a ramp rate of 10° C./min and heating from a first temperature of 0° C. to 390° C. 
 
     
     
         17 . The blocky PEEK copolymer of  claim 16 , wherein the PEEK copolymer has a degree of functionalization of at least about 22%, preferably at least about 25%. 
     
     
         18 . The blocky PEEK copolymer of  claim 16 , wherein the PEEK polymer has a crystallinity of at least about 15%, preferably at least about 20%, even more preferably at least about 25%. 
     
     
         19 . The blocky PEEK copolymer of  claim 16 , wherein
 i and j equal 0;   R 3 , R 4 , R 5 , and R 6  are each hydrogen and   recurring unit (R* PEEK ) is represented by a formula selected form the following group of formulae:   
       
         
           
           
               
               
           
         
         wherein 
         L 1  is —SO 3 M or —Br, and 
         L 2  is —SO 3 M′ or —Br. 
       
     
     
         20 . The blocky PEEK copolymer of  claim 16 , wherein i and j are zero and R 3 , R 4 , R 5 , and R 6  are hydrogen. 
     
     
         21 . The blocky PEEK copolymer of  claim 16 , wherein L 1  is —SO 3 M, preferably SO 3 H, and L 2 , is the same as R 4 . 
     
     
         22 . A membrane comprising the blocky PEEK copolymer of  claim 16 , wherein the membrane has an average thickness of about 10 microns to about 200 microns, and a proton conductivity from about 10 milliSiemens per centimeter (“mS/cm”) to about 200 mS/cm, preferably at from about 20 mS/cm to about 200 mS/cm. 
     
     
         23 . A PEEK copolymer gel comprising the blocky PEEK copolymer of  claim 16  and a gel solvent that is a non-solvent for the blocky PEEK copolymer and a solvent for trifluoroacetyl sulfate. 
     
     
         24 . The PEEK copolymer gel of  claim 23  wherein the gel solvent is 1,2-dichloroethane. 
     
     
         25 . A method for forming the blocky PEEK copolymer of  claim 16 , the method comprising:
 contacting, in a reaction mixture, (A) a PEEK gel comprising a PEEK polymer comprising recurring unit (R PEEK ) and (B) a functionalization agent,   wherein,   the contacting forms the blocky PEEK copolymer, and   the reaction mixture comprises a liquid that is a non-solvent for the PEEK polymer and is a solvent for the functionalization agent.   
     
     
         26 . The method of  claim 25 , wherein the PEEK gel comprises a gel solvent that is miscible with the liquid. 
     
     
         27 . The method of  claim 25 , wherein the liquid is a halogenated alkane represented by the formula: C n′ H m′ X 1   p′ , where p′ is an integer from 1 to 6; n′ is an integer from 1 to 8 and m′ is an integer from 1 to 17, such that 4n′−2(n′−1)=m′+p′, preferably CHCl 3  or ClH 3 C—CH 3 Cl, and the gel solvent is selected from dichloroacetic acid, trichloroacetic acid, and a combination thereof, preferably dichloroacetic acid. 
     
     
         28 . The method of  claim 25 , wherein the functionalization agent is represented by a formula selected from the following group of formulae consisting of: 
       
         
           
           
               
               
           
         
         wherein 
         each R 7  and R 8  is independently selected at each instance from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or an alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium; 
         m is an integer from 0 to 2; 
         n is an integer from 1 to 20; 
         p is an integer from 0 to 3, and 
         X 2  is a halogen; and
 wherein L 1  is —SO 3 H. 
 
       
     
     
         29 . The method of  claim 25 , wherein the functionalization agent is selected from the group consisting of trifluoroacetyl sulfate, acetyl sulfate, chlorosulfonic acid or any combination thereof. 
     
     
         30 . The method of  claim 26 , wherein the PEEK gel has a PEEK concentration of at least about 15 w/v %, preferably at least about 20 w/vol %, relative to the amount of gel solvent.