Room temperature crosslinkable ion conductive polymer system

Abstract

A room temperature crosslinkable polymer system comprising an anhydride containing polymer and an oxyalkylene amine and a polymer electrolyte derived therefrom are prepared and employed as ion conducting materials for batteries such as lithium ion battery, solar cells and electrochromic devices is disclosed.

1 ) A grafted or crosslinked ion conducting polymer comprising in the backbone of the polymer one or more amic acid or maleimide moieties selected from 
       
         
           
           
               
               
           
         
       
       wherein
 * designates connection to the rest of the polymer backbone, 
 G is H, C 1-12  alkyl, metal cation or amino cation, 
 A, A′ and A″ are independently of the others C 1-24  alkylene, 
 each of x, y and z is a number from 0 to about 125, 
 E is H, C 1-12  alkyl, or C 1-12  alkyl carbonyl, 
 R′ is H or C 1-12  alkyl, 
 R″ is H, C 1-12  alkyl, C 1-12  alkyl carbonyl, C 6-10  aryl, C 6-10  aryl substituted by 1 or more C 1-12  alkyl, C 7-12  aralkyl, C 7-12  aralkyl substituted by 1 or more C 1-12  alkyl, or a group 
 
       
         
           
           
               
               
           
         
         wherein each E′ is independently H, C 1-12  alkyl, or C 1-12  alkyl carbonyl, 
         or one E′ is H, C 1-12  alkyl, or C 1-12  alkyl carbonyl and the other is a carbonyl linking group which forms a crosslink to same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II, 
         or the two E′ groups together form a maleimide group which is fused to the same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II and thus forming a crosslink. 
       
     
     
         2 ) A grafted or crosslinked ion conducting polymer according to  claim 1  comprising in the backbone of the polymer one or more amic acid or maleimide moieties selected from 
       
         
           
           
               
               
           
         
       
       wherein
 each R independently of the others is H or C 1-12  alkyl and at least one of x, y or z is 1 or higher. 
 
     
     
         3 ) A grafted or crosslinked ion conducting polymer according to  claim 1  wherein
 G is H, C 1-12  alkyl or a metal cation selected from Li, Na, K, Mg and Ca,   E is H,   each R independently of the others is H or C 1-12  alkyl,   R′ is H or methyl   and R″ is H or a group   
       
         
           
           
               
               
           
         
         wherein each E′ is H or one E′ is H, and the other is a carbonyl linking group which forms a crosslink to same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II, or the two E′ groups together form a maleimide group which is fused to the same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II and thus forming a crosslink. 
       
     
     
         4 ) A grafted or crosslinked ion conducting polymer according to  claim 2  comprising in the backbone of the polymer one or more amic acid or maleimide moieties selected from 
       
         
           
           
               
               
           
         
       
       Wherein
 * designate the position of attachment the polymer, 
 G is H, C 1-12  alkyl or a metal cation, 
 E is H, C 1-12  alkyl, or C 1-12  alkylcarbonyl, 
 R′ and each R independently are H or C 1-12  alkyl, 
 R″ is H, C 1-12  alkyl, or C 1-12  alkylcarbonyl or a group 
 
       
         
           
           
               
               
           
         
         wherein each E′ is independently H, C 1-12  alkyl, or C 1-12  alkyl carbonyl, 
         or one E′ is H, C 1-12  alkyl, or C 1-12  alkyl carbonyl and the other is a carbonyl linking group which forms a crosslink to same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II, 
         or the two E′ groups together form a maleimide group which is fused to the same polymer backbone or to the backbone of another polymer chain which comprises in the backbone of the polymer chain one or more amic acid or maleimide moieties of Formula I or Formula II and thus forming a crosslink. 
       
     
     
         5 ) A polymer according to  claim 2 , wherein the polymer contains in the backbone crosslinked aminic acid or maleimide acid moieties selected from 
       
         
           
           
               
               
           
         
       
       wherein
 G is H, C 1-12  alkyl, metal cation or amino cation, 
 R′ and each R independently are H or C 1-12  alkyl. 
 
     
     
         6 ) A polymer according to  claim 1  which is prepared by reacting a maleic anhydride polymer with at least one amine of the formula 
       
         
           
           
               
               
           
         
       
       wherein
 A, A′ and A″ are independently of the others C 1-24  alkylene, 
 each of x, y and z is a number from 0 to about 125, 
 E is H, C 1-12  alkyl, or C 1-12  alkyl carbonyl, 
 R′ is H or C 1-12  alkyl, 
 R″ is H, C 1-12  alkyl, C 1-12  alkyl carbonyl, C 6-10  aryl, C 6-10  aryl substituted by 1 or more C 1-12  alkyl, C 7-12  aralkyl, C 7-12  aralkyl substituted by 1 or more C 1-12  alkyl, or a group 
 
       
         
           
           
               
               
           
         
          wherein each E′ is independently H, C 1-12  alkyl or C 1-12  alkylcarbonyl, wherein 1-99% of the anhydride units are reacted with amine. 
       
     
     
         7 ) A polymer according to  claim 6  which is prepared by reacting a maleic anhydride polymer with at least one amine of the formula 
       
         
           
           
               
               
           
         
       
       wherein each R independently of the others is H or C 1-12  alkyl. 
     
     
         8 ) A polymer according to  claim 6  which is prepared by reacting a maleic anhydride polymer with at least one amine of the formula 
       
         
           
           
               
               
           
         
       
       wherein
 R is methyl, 
 R′ is H or methyl, 
 R″ is H, C 1-12  alkyl, C 1-12  alkylcarbonyl, phenyl, phenyl substituted by 1 or more C 1-12  alkyl, benzyl, phenethyl, benzyl or phenethyl substituted by 1 or more C 1-12  alkyl, or a group 
 
       
         
           
           
               
               
           
         
         wherein each E′ is independently H, C 1-12  alkyl, or C 1-12  alkylcarbonyl. 
       
     
     
         9 ) A polymer according to  claim 6 , wherein the maleic anhydride polymer is a maleic anhydride copolymer with an ethylenically unsaturated monomer selected from styrenes, olefins, and (meth)acrylic acid esters and amides. 
     
     
         10 ) A copolymer according to  claim 9 , wherein the maleic anhydride copolymer is selected from poly(styrene-alt-maleic anhydride), poly(methyl vinyl ether-alt-maleic anhydride), poly(ethyylene-g-maleic anhydride), poly(isobutylene-alt-maleic anhydride), polyisoprene-g-maleic anhydride, poly(maleic anhydride-alt-1-octadecene), poly(ethylene-co-ethyl acrylate-co-maleic anhydride), polyethylene-graft-maleic anhydride. 
     
     
         11 ) The polymer according to  claim 6  wherein 10-99% of the anhydride units are reacted with amine. 
     
     
         12 ) A process for preparing a polymer according to  claim 1  wherein a maleic anhydride polymer is reacted with at least one amine of the formula 
       
         
           
           
               
               
           
         
       
       wherein
 A, A′ and A″ are independently of the others C 1-24  alkylene, 
 each of x, y and z is a number from 0 to about 125, 
 E is H, C 1-12  alkyl, or C 1-12  alkyl carbonyl, 
 R′ is H or C 1-12  alkyl, 
 R″ is H, C 1-12  alkyl, C 1-12  alkyl carbonyl, C 6-10  aryl, C 6-10  aryl substituted by 1 or more C 1-12  alkyl, C 7-12  aralkyl, C 7-12  aralkyl substituted by 1 or more C 1-12  alkyl, or a group 
 
       
         
           
           
               
               
           
         
          wherein each E′ is independently H, C 1-12  alkyl or C 1-12  alkylcarbonyl. 
       
     
     
         13 ) A process according to  claim 12 , wherein the polymer obtained by reaction of the maleic anhydride polymer with the at least one amine is treated with heat at elevated temperature from about 60 to about 25° C. 
     
     
         14 ) A solid polymer electrolyte or gel electrolyte comprising an ion conductive polymer according to  claim 1 . 
     
     
         15 ) A solid polymer electrolyte or gel electrolyte according to  claim 14  comprising a metal carboxylic acid salt connected to the polymer backbone or complexed electrolyte salt. 
     
     
         16 ) A solid polymer electrolyte or gel electrolyte according to  claim 15 , comprising a lithium carboxylic acid salt connected to the polymer backbone or complexed electrolyte lithium salt. 
     
     
         17 . A battery having a cathode, an anode and a solid polymer electrolyte or gel electrolyte according to  claim 14 . 
     
     
         18 . A molded membrane comprising a polymer according to  claim 1 .