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-dimethylpyridine, 2,4,6-trimethylpyridine, 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; 1-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 . The method according to  claim 58 , wherein said antimicrobial material is effective against bacteria selected from the group consisting of  Bordetella, Neisseria, Legionella, Pseudomonas, Salmonella, Shigella, Erwinia, Enterobacter, Escherichia, Vibrio, Haemophilus, Actinobacillus, Klebsiella, Staphylococcus, Streptococcus, Enterococcus, Corynebacterium, Listeria, Bacillus, Mycobacterium, Enterococcus, Leptospira, Serpulina, Mycoplasma, Bacteroides, Yersinia, Chlamydia, Porphyromonas, Pasteurella, Peptostreptococcus, Propionibacterium, Dermatophilus, Campylobacter  and  Erysipelothrix.    
     
     
         66 . The method according to  claim 58 , wherein said antimicrobial material is effective against fungal genera selected from the group consisting of  Aspergillus, Blastomyces, Candida, Coccidioides, Cryptococcus, Epidermophyton, Histoplasma, Microsporum, Mucor, Rhizopus, Sporothrix, Trichophyton, Paracoccidioides, Absidia, Fusarium, Penicillium, Torulopsis, Trichosporon, Rhodotorula, Malassezia, Cladosporium, Fonsecea  and  Phialophora.    
     
     
         67 . The method according to  claim 58 , wherein said antimicrobial material is effective against DNA and RNA viruses belonging to families selected from the group consisting of Parvoviridae, Papillomaviridae, Polyomaviridae, Adenoviridae, Hepadnaviridae, Herpesviridae, Poxviridae, Picornaviridae, Caliciviridae, Reoviridae, Togaviridae, Flaviviridae, Coronaviridae, Orthomyxoviridae, Paramyxoviridae, Rhabdoviridae, Filoviridae, Bunyaviridae, Arenaviridae and Retroviridae. 
     
     
         68 . The method according to  claim 58 , wherein said object is employed in the health industry, food industry, packaging industry, water industry, textile industry, plastic industry, glass industry, paper industry, rubber industry, ceramic industry, paint industry, wood industry, poultry industry, seafood industry, sports industry and agricultural industry. 
     
     
         69 . The method according to  claim 58 , wherein said object is selected from the group comprising medical dressings, urine catheters, endoscopes, medical instruments, hospital furniture, masks, floors, food packets, food processing surfaces and apparatus, pipettes, computer keyboards and mouses, plastic film wraps, cosmetics, handles, water tanks, membranes for water purification, toilets, door handles, drainage pipes, water pipes, ear pieces, shoe insoles, pools, bags for urine or feces or blood platelets, air-conditioning units, filtration equipment, pasteurization equipment and furniture. 
     
     
         70 . 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. 
     
     
         71 . The process according to  claim 70 , wherein the compound of formula (I) is an aminobenzoic acid or aminobenzoate ester. 
     
     
         72 . The process according to  claim 70 , wherein the compound of formula (I) is a sulfanilic acid, and the copolymer is in emeraldine salt form. 
     
     
         73 . An aniline random copolymer prepared by the process of  claim 70 . 
     
     
         74 . A process according to  claim 70 , wherein said oxidizing agent is selected from the group consisting of ammonium persulphate, potassium ferricyanide, an iodate salt and hydrogen peroxide. 
     
     
         75 . The process according to  claim 70 , wherein the iodate salt is potassium iodate and the mineral acid is hydrochloric acid. 
     
     
         76 . The process according to  claim 70 , wherein the ratio of said aniline to said compound of formula (I) is 1:2 to 2:1. 
     
     
         77 . The process according to  claim 70 , 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. 
     
     
         78 . 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, phenyl; 
 x is a number between 1 and 0 and m indicates the degree of polymerisation, 
 
       wherein said copolymer is not polyaniline. 
     
     
         79 . An antimicrobial composite material according to  claim 78 , in the form of a blend or powder. 
     
     
         80 . An antimicrobial composite material according to  claim 78 , wherein the aniline random copolymer is present as a coating on the at least one other substance. 
     
     
         81 . An antimicrobial composite material according  claim 78 , 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, poly(ethylene 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. 
     
     
         82 . An antimicrobial composite material according to  claim 78 , synthesised by in situ polymerisation or surface coating.