Bioactive aniline copolymers

Abstract

Aniline copolymers and the synthesis thereof for use as antimicrobial (antibacterial, antifungal or antiviral material) material of for the manufacture of antimicrobial objects, suitable for use in the health, food, packaging, water, paint, wood, textile, poultry, glass, paper, rubber, ceramic, seafood, sports, plastic and agricultural industries. The copolymer may be for example (A): where for example R 3 ═H 5 —CO 2 H, —CO 2 Me, or —CO 2 Et. R is typically H or a C 1 -C 6 alkyl, x is an integer between 1 and 0 and m indicates the degree of polymerisation. Preferred copolymers are copolymers of aniline with 3-aminobenzoic acid, 2-aminobenzoic acid and ethyl 3-aminobenzoate.

1 - 57 . (canceled) 
     
     
         58 . A method for producing an object for inhibiting growth of microbes comprising incorporating the object with an aniline copolymer as an antimicrobial material, wherein the aniline copolymer is not polyaniline. 
     
     
         59 . The method according to  claim 58 , wherein said aniline copolymer is soluble to at least 0.05 mg/mL in a solvent selected from the group consisting of N-methyl-2-pyrrolidone, pyridine, 2,6-dimethyl pyridine, 2,4,6-trimethyl pyridine, dimethyl sulfoxide, N,N-dimethyl acetamide anhydrous, tetrahydrofuran, dimethylformamide, hexafluoro-2-propanol, chloroform and dichloromethane. 
     
     
         60 . The method according to  claim 58 , wherein said copolymer has a leucoemeraldine, emeraldine or pernigraniline structure. 
     
     
         61 . The method according to  claim 58 , wherein said copolymer is formed by reaction of aniline with a compound of formula (I): 
       
         
           
           
               
               
           
         
         wherein R is hydrogen or a C 1 -C 6  alkyl, 
         n=1, 2 or 3 
         R 1  is independently selected from the group consisting of: 
         C 1 -C 6  alkyl, 
         C 1 -C 6  alkoxyl, 
         halo, 
         —CO 2 R 2 , 
         —SO 3 R 2 , 
         —PO 3 HR 2 , 
         —COR 4 , 
         —CH 2 COOR 4 , 
         —CN, 
         —CH 2 OH, 
         —CH 2 NH 2 , 
         —CH 2 CN, 
         —OH, 
         —SO 2 NH 2 ; 
         R 2  is selected from hydrogen, C 1 -C 6 , alkyl, an alkali metal, ammonium and a substituted ammonium salt; 
         R 4  is selected from hydrogen, C 1 -C 6  alkyl, phenyl; and 
         salts thereof. 
       
     
     
         62 . The method according to  claim 61 , wherein R is hydrogen, and R 1  is —CO 2 R 2 , —SO 3 R 2 , —OCH 3 , —CH 3 , or —Cl. 
     
     
         63 . The method according to  claim 58 , wherein the aniline copolymer is a homopolymer of 3-amino benzoic acid or a homopolymer of 3-aminosulfonic acid. 
     
     
         64 . The method according to  claim 61 , wherein the compound of formula I is selected from the group consisting of 3-aminobenzoic acid, 2-aminobenzoic acid, ethyl 3-aminobenzoate, sulfanilic acid, 2-chloroaniline, o-toluidine and o-anisidine; 3-acetylaniline; 2-aminobenzaldehyde; 2-aminobenzenesfonamide; 2-aminophenol; 3-aminophenol; 2-aminophenylacetic acid; 3-aminophenylacetic acid; 2-aminobenzonitrile; 3-aminobenzonitrile; 2-aminobenzophenone; 3-aminobenzophenone; 2-aminobenzyl alcohol; 3-aminobenzyl alcohol; 2-aminobenzylamine; 2-aminobenzyl cyanide; 2-amino-4-bromobenzoic acid; 2-amino-6-chlorobenzoic acid; 2-amino-4-chlorobenzoic acid; 2-amino-4-chlorophenol; 2-amino-4-methylphenol; 2-amino-4,6-dihydroxypyrimidine; 2-amino-1,3-diethylbenzene; amino-3,5-dimethylbenzene; 2-amino-4,6-dimethylpyridine; 2-amino-4-hydroxy-6-methylpyrimidine; 5-aminoisophthalic acid; 3-amino-2-methylbenzoic acid; 2-amino-3-methylphenol; 2-amino-6-methylpyridine; 2-amino-3-picoline; 2-aminopyridine; and 3-aminopyridine. 
     
     
         65 . A process for preparing an aniline random copolymer, said process comprising the step of reacting aniline with a compound of formula (I) in a mineral acid solution containing an oxidizing agent 
       
         
           
           
               
               
           
         
         wherein R is hydrogen or a C 1 -C 6  alkyl, 
         R 1  is independently selected from the group consisting of: 
         C 1 -C 6  alkyl, 
         C 1 -C 6  alkoxyl, 
         halo or 
         —CO 2 R 2 , 
         —PO 3 HR 2 , 
         —COR 4 , 
         —CH 2 COOR 4 , 
         —CN, 
         —CH 2 OH, 
         —CH 2 NH 2 , 
         —CH 2 CN, 
         —OH, 
         —SO 2 NH 2 ; 
         R 2  is selected from hydrogen, C 1 -C 6  alkyl, an alkali metal, ammonium and a substituted ammonium salt; 
         R 4  is selected from hydrogen, C 1 -C 6  alkyl, phenyl and 
         n is 1, 2 or 3; and 
         wherein said copolymer is not polyaniline. 
       
     
     
         66 . The process according to  claim 65 , wherein the compound of formula (I) is an aminobenzoic acid or aminobenzoate ester. 
     
     
         67 . The process according to  claim 65 , wherein the compound of formula (I) is a sulfanilic acid, and the copolymer is in emeraldine salt form. 
     
     
         68 . An aniline random copolymer prepared by the process of  claim 65 . 
     
     
         69 . A process according to  claim 65 , wherein said oxidizing agent is selected from the group consisting of ammonium persulphate, potassium ferricyanide, an iodate salt and hydrogen peroxide. 
     
     
         70 . The process according to  claim 65 , wherein the iodate salt is potassium iodate and the mineral acid is hydrochloric acid. 
     
     
         71 . The process according to  claim 65 , wherein the ratio of said aniline to said compound of formula (I) is 1:2 to 2:1. 
     
     
         72 . The process according to  claim 65 , further including a purification step which includes treating the aniline copolymer with a compound in which the aniline copolymer is largely insoluble, but which acts as a solvent to remove, where present, starting monomers, intermediate oligomers or other impurities. 
     
     
         73 . An antibacterial and/or antifungal and/or antiviral object comprising an aniline random copolymer, wherein the aniline copolymer has the following formula: 
       
         
           
           
               
               
           
         
         wherein R is hydrogen or a C 1 -C 6  alkyl, R 3 ═H or R 1    
         R 1  is independently selected from the group consisting of: 
         C 1 -C 6  alkyl, 
         C 1 -C 6  alkoxyl, 
         halo, 
         —CO 2 R 2 , 
         —SO 3 R 2 , 
         —PO 3 HR 2 , 
         —COR 4 , 
         —CH 2 COOR 4 , 
         —CN, 
         —CH 2 OH, 
         —CH 2 NH 2 , 
         —CH 2 CN, 
         —OH, 
         —SO 2 NH 2 ; 
         R 2  is selected from hydrogen, C 1 -C 6  alkyl, an alkali metal, ammonium and a substituted ammonium salt; 
         R 4  is selected from hydrogen, C 1 -C 6  alkyl, and phenyl; 
         x is a number between 1 and 0 and m indicates the degree of polymerisation, 
         wherein said copolymer is not polyaniline. 
       
     
     
         74 . An antimicrobial composite material according to  claim 73 , in the form of a blend or powder. 
     
     
         75 . An antimicrobial composite material according to  claim 73 , wherein the aniline random copolymer is present as a coating on the at least one other substance. 
     
     
         76 . An antimicrobial composite material according to  claim 73 , wherein the at least one other substance is selected from the group consisting of poly(vinyl alcohol), poly(vinyl acetate), poly(methyl methacrylate), acrylic polymers, polyethylene terephthalate), polyesters, polyamides, polyethylene and polypropylene, polyvinylidene fluoride, ethylene vinyl acetate copolymers, methyl acrylate copolymers, butane copolymers, hexane copolymers, rubber, natural rubber latex, acrylic latexes, epoxy latexes, ethyl cellulose, cellulose, polysaccharides, and proteins. 
     
     
         77 . An antimicrobial composite material according to  claim 73 , synthesized by in situ polymerization or surface coating.