Anti-microbial polymer incorporating a quaternary ammonium group

Abstract

The present disclosure relates to anti-microbial polymers comprising a polymerizable cyclic moiety which forms part of the backbone of the polymer.

1 . An anti-microbial polymer, comprising polymerizable units of
 i) at least one monomer comprising a polymerizable aromatic moiety containing an aromatic group, wherein the aromatic group is covalently incorporated into the polymer backbone through loss of aromaticity, and wherein the aromatic group comprises a quaternary aromatic ammonium or phosphonium salt, a quaternary aromatic ammonium or phosphonium salt, or quinone or quinone derivative; and   wherein the monomer further comprises an anti-microbial moiety, wherein the anti-microbial moiety is a quaternary ammonium moiety or a quaternary phosphonium moiety.   
     
     
         2 . The anti-microbial polymer of  claim 1 , further comprising polymerizable units of at least one unsaturated monomer having an ethylenically unsaturated double or triple bond. 
     
     
         3 . The anti-microbial polymer of  claim 1 , wherein the quaternary aromatic ammonium salt comprises a monomer of the formula 
       
         
           
           
               
               
           
         
         wherein 
         Ar is optionally substituted (C 6 -C 14 )-aryl or optionally substituted (C 5 -C 14 )-heteroaryl, 
         Y is absent, (C 1 -C 10 )-alkylene, (C 2 -C 10 )-alkenylene, or (C 2 -C 10 )-alkynylene, wherein 1 or 2 carbon atoms are optionally replaced with N, S or O; 
         R 1 , R 2  and R 3  are independently or simultaneously optionally substituted H, (C 1 -C 24 )-alkyl, (C 2 -C 24 )-alkenyl, (C 2 -C 24 )-alkynyl, (C 6 -C 14 )-aryl, (C 5 -C 14 )-heteroaryl or (C 1 -C 10 )-alkylene-(C 6 -C 14 )-aryl, 
         wherein the optional substituents are chosen from one or more of halogen, hydroxyl, (C 1 -C 6 )-alkoxy, thionyl, nitro, amino (—NH 2 ), (C 6 -C 14 )-aryl or (C 5 -C 14 )-heteroaryl, and 
         X is any suitable counteranion. 
       
     
     
         4 . The anti-microbial polymer of  claim 3 , wherein Ar is optionally substituted phenyl, naphthyl, anthracenyl, 1,2-dihydronaphthyl, 1,2,3,4-tetrahydronaphthyl, fluorenyl, indanyl, indenyl, thienyl, furyl, pyrrolyl, pyrididyl, indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, or benzothienyl. 
     
     
         5 . The anti-microbial polymer of  claim 4 , wherein Ar is optionally substituted phenyl. 
     
     
         6 . The anti-microbial polymer of  claim 3 , wherein Y is (C 1 -C 6 )-alkylene, (C 2 -C 6 )-alkenylene, or (C 2 -C 6 )-alkynylene, wherein 1 or 2 carbon atoms are optionally replaced with O. 
     
     
         7 . The anti-microbial polymer of  claim 3 , wherein R 1 , R 2  and R 3  are independently or simultaneously (C 1 -C 24 )-alkyl, (C 2 -C 24 )-alkenyl, (C 2 -C 24 )-alkynyl, or (C 1 -C 10 )-alkylene-(C 6 -C 14 )-aryl. 
     
     
         8 . The anti-microbial polymer of  claim 3 , wherein the quaternary aromatic ammonium salt comprises a monomer of the formula 
       
         
           
           
               
               
           
         
         wherein 
         Y′ is (C 1 -C 3 )-alkylene, wherein 1 carbon atom is optionally replaced with O; 
         R 1 ′ and R 2 ′ are independently or simultaneously (C 1 -C 4 )-alkyl optionally substituted with —OH; 
         R 3 ′ is (C 1 -C 24 )-alkyl or (C 1 -C 10 )-alkylene-(C 6 -C 14 )-aryl, and 
         R is one or more optional substituents chosen from halogen, (C 1 -C 6 )-alkyl, thionyl, nitro, (C 6 -C 14 )-aryl or (C 5 -C 14 )-heteroaryl, and 
         X is halo. 
       
     
     
         9 . The anti-microbial polymer of  claim 8 , wherein the quaternary aromatic ammonium salt comprises 
       
         
           
           
               
               
           
         
       
     
     
         10 . The anti-microbial polymer of  claim 1 , wherein the quaternary aromatic ammonium salt comprises a monomer of the formula 
       
         
           
           
               
               
           
         
         wherein 
         Ring B is an optionally substituted aromatic moiety containing from 5 to 18 carbon atoms, in which from 0 to 4 carbon atoms are replaced with a heteroatom selected from N, O and S, 
         R 4  is H, (C 1 -C 24 )-alkyl, (C 2 -C 24 )-alkenyl, (C 2 -C 24 )-alkynyl, (C 6 -C 14 )-aryl or (C 5 -C 14 )-heteroaryl, 
         wherein the optional substituents are chosen from one or more of halogen, —OH, (C 1 -C 6 )-alkoxy, thionyl, nitro, amino (—NH 2 ), (C 6 -C 14 )-aryl, (C 6 -C 14 )-heteroaryl, or two adjacent substituents are joined to form a methylene dioxy moiety, and 
         X is any suitable counteranion. 
       
     
     
         11 . The anti-microbial polymer of  claim 10 , wherein Ring B is an optionally substituted aromatic moiety containing from 5 to 14 carbon atoms, in which from 0 to 2 carbon atoms are replaced with a heteroatom selected from N, O and S. 
     
     
         12 . The anti-microbial polymer of  claim 11 , wherein the monomer is 
       
         
           
           
               
               
           
         
         wherein 
         R 4  is H, (C 1 -C 24 )-alkyl, (C 2 -C 24 )-alkenyl, (C 2 -C 24 )-alkynyl, (C 6 -C 14 )-aryl or (C 5 -C 14 )-heteroaryl, 
         R is one or more optional substituents chosen from halogen, —OH, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkoxy, thionyl, nitro, amino (—NH 2 ), (C 6 -C 14 )-aryl, (C 5 -C 14 )-heteroaryl, or two adjacent substituents are joined to form a methylene dioxy moiety, and 
         X is any suitable counteranion. 
       
     
     
         13 . The anti-microbial polymer of 12, wherein the monomer is 
       
         
           
           
               
               
           
         
         wherein 
         R 4  is H or (C 1 -C 24 )-alkyl, and 
         X is any suitable counteranion. 
       
     
     
         14 . The anti-microbial polymer of  claim 1 , wherein the quinone or quinone derivative is a monomer of the formula 
       
         
           
           
               
               
           
         
         R is one or more optional substituents chosen from halogen, OH, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkenyl, (C 1 -C 6 )-alkoxy, thionyl, nitro, (C 6 -C 14 )-aryl, (C 5 -C 14 )-heteroaryl, or 
         two or more adjacent substituents are joined together to form an optionally substituted aromatic or non-aromatic monocyclic or polycyclic ring. 
       
     
     
         15 . The anti-microbial polymer of  claim 14 , wherein the quinone or quinone derivative is a monomer of the formula 
       
         
           
           
               
               
           
         
       
     
     
         16 . The anti-microbial polymer of  claim 1 , wherein the at least one monomer having an ethylenically unsaturated double or triple bond comprises acrylic acid, acrylates, styrene, a vinylpyridine, 2-butyne-1,4-diol, cis-2-butene-1,4-diol, vinyl acetate, pentaerythritol allyl ether, linalool or acrylated epoxidized soybean oil. 
     
     
         17 . The anti-microbial polymer of  claim 16 , wherein the monomer comprises 
       
         
           
           
               
               
           
         
       
       wherein M +  is any suitable counter-cation. 
     
     
         18 . The anti-microbial polymer of, wherein the polymer comprises 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  are as defined in  claim 3 ; 
         X is any suitable counteranion, and 
         m, n and p are independently or simultaneously integers between 1 and 1,000,000. 
       
     
     
         19 . The anti-microbial polymer of  claim 1 , wherein the polymer comprises 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  are as defined in  claim 3 , 
         X is any suitable counteranion, and 
         m, n and p are independently or simultaneously integers between 1 and 1,000,000. 
       
     
     
         20 . The anti-microbial polymer of any one of  claims 1  to  28 , wherein the polymer is conjugated to cellulose or a cellulose derivative.