Functionalized poly(diallylpiperidinium) and its copolymers for use in ion conducting applications

Abstract

The invention relates to membranes, monomers and polymers. The monomers can form polymers, which can be used for membranes. The membranes can be used in alkaline fuel cells, for water purification, for electrolysis, for flow batteries, and for anti-bacterial membranes and materials, as well as membrane electrode assemblies for fuel cells. In addition to the membranes, polymers and monomers and methods of using the membranes, the present invention also relates to methods of making the membranes, monomers and polymers.

1 . A method of forming a poly(diallylammonium) multiblock copolymer, comprising:
 mixing a diallylammonium polymer functionalized on a first end and a second end with a first group, a first difunctional monomer functionalized with a second group and a second difunctional monomer functionalized with a third group form a first mixture; and   reacting the first mixture to form the poly(diallylammonium) multiblock copolymer.   
     
     
         2 . The method of  claim 1 , wherein the second group of the second difunctional monomer functional group is the same as the first group. 
     
     
         3 . The method of  claim 1 , wherein the first group is a halophenyl sulfone. 
     
     
         4 . The method of  claim 1 , wherein the reacting comprises:
 heating the first mixture in an inert environment at a temperature between about 100° C. and about 175° C. for between about 1.5 hours and about 24 hours to form a heated first mixture, wherein the first difunctional monomer is a halophenyl sulfone and wherein the second difunctional monomer is a bisphenol to form a heated mixture;   precipitating the heated mixture with an alcohol to form a precipitate in solution; and   separating the poly(allyl ammonium) multiblock copolymer, wherein the poly(allyl ammonium) multiblock copolymer is a polysulfone-poly(diallylammonium) multiblock copolymer.   
     
     
         5 . The method of  claim 1 , wherein the diallylammonium polymer comprises diallylammonium monomers. 
     
     
         6 . The method of  claim 1 , further comprising an anion, wherein the anion is selected from the group consisting of PF 6   − , BF 4   − , a halide, a hydroxide, a carbonate, a bicarbonate, a tosylate, an aryl sulfonate, and an alkyl sulfonate. 
     
     
         7 . The method of  claim 6 , further comprising exchanging the anion with a second anion selected from the group consisting of PF 6   − , BF 4   − , a halide, a hydroxide, a carbonate, a bicarbonate, a tosylate, an aryl sulfonate, and a alkyl sulfonate, wherein the anion and the second anion are different. 
     
     
         8 . The method of  claim 5 , wherein the diallylammonium monomer is selected from the group consisting of a diallyldimethyl, a diallyldiethyl, a diallyldipropyl, a diallyldibutyl, a diallyldipentyl, a diallyldihexyl, a cyclic diallyl, a diallylpiperidinium, or a diallylpyrrolidinium. 
     
     
         9 . The method of  claim 1 , wherein the iniferter is a disulfide and wherein a functional group of the iniferter is a halophenyl, a carboxylic acid, carboxylic acid chloride, an amine, an acid chloride, an alcohol, a phenol, an alkyl, a alkyl halide, an ester, an ether and combinations thereof. 
     
     
         10 . A poly(diallylammonium) multiblock copolymer. 
     
     
         11 . The copolymer of  claim 10 , wherein the copolymer comprises a first difunctional-monomer and a second difunctional-monomer. 
     
     
         12 . The copolymer of  claim 11 , wherein the first difunctional monomer is selected from the group consisting of a halophenyl sulfone, a halophenyl, a carboxylic acid, an amine, an acid chloride, an alcohol, a phenol, an alkyl, a alkyl halide, an aryl halide, and combinations thereof. 
     
     
         13 . The copolymer of  claim 10 , wherein a functional group of the second difunctional monomer is selected from the group consisting of a phenol, an alcohol, an amine alkyl halide, an aryl halide, a carboxylic acid, a halophenyl, a carboxylic acid, carboxylic acid chloride, an acid chloride, an alkyl, and combinations thereof. 
     
     
         14 . The copolymer of  claim 10 , further comprising an anion selected from the group consisting of PF6 − , BF4 − , tosylates, aryl sulfonates, and alkyl sulfonates. 
     
     
         15 . The copolymer of  claim 14 , wherein the copolymer is soluble in a non-aqueous solvent or solution. 
     
     
         16 . The copolymer of  claim 10 , wherein the copolymer comprises between 10 wt. % and about 80 wt. % of a diallyl ammonium polymer, up to about 5 wt. % of incidental materials, and the balance being the polymer resulting from the polymerization of the first and second di-functional monomers. 
     
     
         17 . A membrane comprising a poly(diallyl ammonium) multiblock copolymer. 
     
     
         18 . The membrane of  claim 17 , further comprising a first anion. 
     
     
         19 . The membrane of  claim 17 , wherein a percentage water uptake of the membrane is between about 10 weight percent and about 40 weight percent at room temperature. 
     
     
         20 . The membrane of  claim 17 , wherein the membrane is colorless and transparent.