Use of polymers as biocides

Details Use of polymers as biocides Use of polymers as biocides

1998-09-03

2001-07-17

Harrison, Robert H. (Department: 1619)

Drug, bio-affecting and body treating compositions

Preparations characterized by special physical form

Biocides; animal or insect repellents or attractants

C424S078080, C424S078350

Reexamination Certificate

active

06261581

ABSTRACT:

This is a 371 of application Ser. No. PCT/EP 97/01082, filed Mar. 4, 1997.
The invention relates to the use of polymers which contain
(a) 0.1 to 100 mol % of vinylamine or ethyleneimine units,
(b) 0 to 99.9 mol % of units of at least one monomer from the group consisting of N-vinylcarboxamides, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, C
1
- to C
6
-alkyl vinyl ethers, monoethylenically unsaturated C
3
- to C
8
-carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines and
(c) 0 to 5 mol % of units of monomers having at least two ethylenically unsaturated double bonds,
in copolymerized form as biocide.
Specifically functionalized polyvinyl alcohols, polyacrylates and polyethyleneimines for the immobilization of antimicrobially active substances are known from Z. Chem., Volume 27, 1 (1987). The active compounds are released in a controlled manner during the use of such systems. According to the information in the publication, the antimicrobial activity is based, however, on the release of the biocidal active compounds.
SU-A-1 071 630 discloses that copolymers of diallyldimethyl-ammonium chloride and sodium acrylate have a bactericidal activity. EP-A-0 331 528 discloses copolymers of ethylene and dialkylaminoalkylacrylamides having biocidal activity. Antimicrobially active polymers which contain vinylphosphonium and vinylsulfonium groups were reported in J. Polym. Sci. Part A: Polym. Chem., Volume 31, 335, 1441, 1467 and 2873 (1993) and also in Arch. Pharm. (Weinheim) 321, 89 (1988). Biocidally active copolymers of N-vinylpyrrolidone and vinylamines are known from Makromol. Chem., Suppl. Volume 9, 25 (1985).
It is an object of the present invention to make available novel biocidal agents.
We have found that this object is achieved according to the invention by the use of polymers which contain
(a) 0.1 to 100 mol % of vinylamine or ethyleneimine units,
(b) 0 to 99.9 mol % of units of at least one monomer from the group consisting of N-vinylcarboxamides of the formula
in which R
1
, R
2
=H or C
1
- to C
6
-alkyl,
vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, C
1
- to C
6
-alkyl vinyl ethers, monoethylenically unsaturated C
3
- to C
8
-carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines and
(c) 0 to 5 mol % of units of monomers having at least two ethylenically unsaturated double bonds,
in copolymerized form, the sum of (a), (b) and (c) in mol % always being 100, as biocide.
The polymers described above are known from the prior art, cf. EP-B-0 071 050 and EP-B-0 216 387. The polymers comprising vinylamine units are obtainable, for example, by polymerizing mixtures which comprise
(a) 0.1 to 100 mol % of open-chain N-vinylcarboxamides of the formula I indicated above,
(b) 0 to 99.9 mol % of at least one monomer from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, C
1
- to C
6
-alkyl vinyl ethers, monoethylenically unsaturated C
3
- to C
8
-carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylimidazoles and N-vinylimidazolines and
(c) 0 to 5 mol % of at least one monomer having at least two ethylenically unsaturated double bonds,
and then partially or completely removing the group
in which R
2
has the meaning indicated in formula I, from the copolymerized monomers of the formula I.
Open-chain N-vinylcarboxamides of the formula I are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide. The open-chain vinylcarboxamides can be employed in the polymerization on their own or as a mixture. Preferably, N-vinylformamide is used from this group of monomers.
The polymers comprising ethyleneimine units are polyethyleneimines which are obtainable by polymerization of ethyleneimine in the presence of acids, Lewis acids or acid-eliminating catalysts such as alkyl halides, e.g. methyl chloride, ethyl chloride, propyl chloride, methylene chloride, trichloromethane, carbon tetrachloride or tetrabromomethane. The polyethyleneimines, for example, have molecular weights Mw of 300 to 1,000,000. Polymers comprising ethyleneimine units of this type, which are obtainable by grafting polyamidoamines with ethyleneimine or by grafting polymers of open-chain N-vinylcarboxamides of the formula I with ethyleneimine, are additionally suitable. Grafted polyamidoamines are disclosed, for example, in U.S. Pat. No. 4,144,123.
As component (a), the polymers to be used according to the invention contain 0.1 to 100, preferably 10 to 90, mol % of vinylamine or ethyleneimine units. Of the polymers comprising ethyleneimine units, polyethyleneimine having molecular masses from 500 to 500,000 is preferably used.
Polymers comprising vinylamine units can be modified by copolymerizing monomers of the formula I with other monomers during the preparation. Suitable monomers include vinyl formate, vinyl acetate, vinyl propionate, C
1
- to C
6
-alkyl vinyl ethers, monoethylenically unsaturated C
3
- to C
8
-carboxylic acids, their esters, nitrites, amides and, if available, also the anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines. Examples of the mentioned monomers of group (b) are vinyl esters of saturated carboxylic acids having 1 to 6 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate, monoethylenically unsaturated C
3
- to C
8
-carboxylic acids, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, crotonic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, citraconic acid and itaconic acid as well as their esters, anhydrides, amides and nitriles. Preferably employed anhydrides are, for example, maleic anhydride, citraconic anhydride and itaconic anhydride.
Suitable esters which are derived, for example, from alcohols having 1 to 6 C atoms are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, hexyl acrylate or glycols or polyalkylene glycols, where in each case only one OH group of the glycols or polyglycols is esterified with a monoethylenically unsaturated carboxylic acid, e.g. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. Acrylic acid monoesters and methacrylic acid monoesters of polyalkylene glycols of a molecular weight of up to 10,000, preferably 1500 to 9000, and esters of the mentioned carboxylic acids with aminoalcohols are, additionally suitable, e.g. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate and dimethylaminopropyl methacrylate. Suitable amides are, for example, acrylamide and methacrylamide. The basic acrylates can be employed in the form of the free bases, the salts with mineral acids or carboxylic acids or alternatively in quaternized form. Comonomers which are additionally suitable are acrylonitrile, methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole and N-vinyl-2-ethylimidazole, N-vinylimidazoline and substituted N-vinylimidazolines, e.g. N-vinyl-2-methylimidazoline. Apart from the monomers mentioned, it is also possible to employ monomers comprising sulfo groups, such as, for example, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid and 3-sulfopropyl acrylates as other monoethylenically unsaturated monomers.
The polymers comprising vinylamine units preferably contain
(a) 1 to 99 mol % of vinylamine units and
(b) 1 to 99 mol % of units of monomers from the group consisting of open-chain N-vinylcarboxamides, vinyl formate, vinyl acetate, vinyl propionate, C
1
- to C
6
-alkyl vinyl ethers, N-vinylurea, acrylic acid, methacrylic acid, maleic acid and also the anhydrides, esters, nitriles and amides of the carboxylic acids mentioned, N-vinylimidazoles

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