Zinc or Copper (II) salt and use thereof as a biocide

Abstract

There is provided as a biocide zinc or copper (II) salt having the general formula CH.sub.2C(R.sup.1)COO-M-OCOC.sub.6H.sub.3R.sup.2R.sup.4, wherein M is Zn or Cu, R.sup.1 is selected from the group comprising hydrogen and methyl, R.sup.2 is selected from the group comprising hydrogen and OH, R.sup.4 is selected from the group comprising hydrogen, alkyl and SO.sub.2OH group.

Claims

1. A biocide comprised of a zinc or copper (II) salt having a general formula: ##STR00003## wherein M is Zn or Cu, R.sup.1 is selected from the group consisting of hydrogen and methyl; R.sup.2 is selected from the group consisting of hydrogen and OH; R.sup.3 is selected from the group consisting of C.sub.1-C.sub.3 alkyl and a SO.sub.2OH group.

2. A method of using the biocide according to claim 1 as a bactericide, the method comprising dissolving said biocide in an aqueous medium to form a solution having a concentration in a range from 0.5% to 2%, and treating an object with the solution.

3. A method of using the biocide according to claim 1 as a fungicide, the method comprising treating a material to be preserved from fungi or spores of fungi with said biocide.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) The essence of the invention is illustrated by examples given below. Examples 1-8 describe the preparation and properties of certain representatives of the proposed series of substances, examples 9-23their bactericidal and fungicidal activity.

Example 1

(2) 10 g of sulfosalicylic acid, 100 ml of distilled water are placed into a 500 ml round-bottom flask and the solution is stirred until sulfosalicylic acid is completely dissolved. Then a suspension of 3.64 g of zinc oxide in 50 ml of distilled water is gradually added to the solution under constant stirring and whereupon 3.2 g of acrylic acid is added and stirred until the suspension is completely dissolved. The obtained solution is evaporated to dryness at a temperature of not more than 70 C., and the resulted solid product is subjected to recrystallization from distilled water, 12.1 g of water-soluble powdered zinc acrylate-sulfosalicylate is obtained which corresponds to the above general formula wherein R.sup.1H, R.sup.2SO.sub.2OH, R.sup.3OH (79% yield of the stoichiometric). The results of elemental analysis of salts obtained as described in this and subsequent examples are given in Table 1.

Example 2

(3) Zinc methacrylate-benzoate (R.sup.1CH.sub.3, R.sup.2H, R.sup.3H) with melting point of 283 C. is obtained in 68% yield of the stoichiometric by analogy with Example 1 using benzoic and methacrylic acids instead of sulfosalicylic and acrylic ones (respectively).

Example 3

(4) Zinc methacrylate-salicylate (R.sup.1CH.sub.3, R.sup.2OH) with melting point of 250 C. is obtained in 80% yield of the stoichiometric by analogy with Example 1 using salicylic and methacrylic acids instead of sulfosalicylic and acrylic ones (respectively).

Example 4

(5) Zinc methacrylate-sulfosalicylate (R.sup.1CH.sub.3, R.sup.2SO.sub.2OH, R.sup.3OH) with melting point of 238 C. is obtained in 82% yield of the stoichiometric by analogy with Example 1 using methacrylic acid instead of acrylic one.

Example 5

(6) Zinc methacrylate-toluylate (R.sup.1CH.sub.3, R.sup.2CH.sub.3, R.sup.3H) is obtained in 80% yield of the stoichiometric by analogy with Example 1 using toluylic and methacrylic acids instead of sulfosalicylic and acrylic ones respectively).

Example 6

(7) Zinc acrylate-benzoate (R.sup.1H, R.sup.2H, R.sup.3H) with melting point of 238 C. is obtained in 55% yield of the stoichiometric by analogy with Example 1 using benzoic acid instead of sulfosalicylic one. The structure of the obtained individual compound is verified by NMR spectra analysis, in NMR spectrum .sup.1H, multiplets in the regions 5.625.72 and 6.156.30 ppm belong to protons of H.sub.2CCHC(O)O acrylate group. Benzoic group displays signals at .sub.H 7.38 (triplet), 7.48 (triplet) and 8.06 ppm (doublet). In NMR spectrum .sup.13C, benzoic group displays signals at .sub.C 129.0 (m-CH), 131.0 (o-CH), 132.8 (p-CH), 135.2 (C.sub.1), 175.4 ppm (OC(O)), and acrylate group displays signals at .sub.C 129.0 and 133.2 (H.sub.2CCH), 175.1 ppm (OC(O)).

Example 7

(8) Copper acrylate-benzoate (R.sup.1H, R.sup.2H, R.sup.3H) is obtained in 55% yield of the stoichiometric by analogy with Example 1 using benzoic acid instead of sulfosalicylic one and copper oxide instead of zinc oxide.

Example 8

(9) Copper methacrylate-salicylate (R.sup.1CH.sub.3, R.sup.2H, R.sup.3OH) is obtained in 85% yield of the stoichiometric by analogy with Example 1 using salicylic and methacrylic acids instead of sulfosalicylic and acrylic ones (respectively) and copper oxide instead of zinc oxide.

Example 9

(10) Bactericidal activity of zinc methacrylate-salicylate obtained as described in Example 3 and zinc methacrylate-sulfosalicylate obtained as described in Example 4 is determined according to the known method (RU 2378363, C12N 1/00, C12Q 1/00, 2010) based on the exposure of a bacterial culture in a solution of bactericidal substance for a certain period of time followed by its neutralization and inoculation of the culture on a solid nutrient medium. The sensitivity of microorganisms to a disinfectant is judged by microorganism growth on the nutrient medium up to 300 CFU/ml (CFUcolony-forming unit): in particular, growth up to 100 CFU/ml exhibits incomplete bactericidal effect, growth up to 100-300 CFU/mlsub-bactericidal effect and growth up to more than 300 CFU/ml exhibits resistance of microorganisms to a disinfectant. The determination is performed on E. coli No. 906 and S. aureus No. 1257 test strains being usually used to study the bactericidal activity of biocides as well as on clinical strainsP. aeruginosa and methicillin-resistant strain S. aureusat salt concentrations from 0.5 to 2% and time of exposure from 5 to 60 min. Test results are given in Table 2. It follows from Table 2 that zinc methacrylate-salicylate at concentration of 1.0% exhibits stable bactericidal effect against all strains at time of exposure from 30 min. At concentration of 2.0%, it exhibits the same bactericidal effect at time of exposure from 5 min. Zinc methacrylate-sulfosalicylate at concentration of 1.0% also exhibits stable bactericidal effect against three of four investigated strains at time of exposure from 30 min.

Example 10 (Comparative)

(11) The same method as described in Example 9 is used to determine the bactericidal activity of ZMA against three of four strains studied in Example 9. Test results are given in Table 3. From Table 3 it follows that the bactericidal activity of ZMA is substantially lower than that of the proposed salts: it exhibits stable bactericidal activity against E. coli No. 906 at time of exposure of 30 min. and concentration from 1.0 to 2.5%, not completely stable bactericidal activity against P. aeruginosaonly at concentration from 2.5%, and sub-bactericidal activity against S. aureus No. 1257only at concentration of 2.5% and time of exposure of 60 min.

Examples 11-23

(12) The fungicidal activity of the proposed salts is determined according to GOST 30028.4-2006 by testing samples of various materials treated with these salts for resistance to fungal spores. Test results in terms of tolerance time (in days) are given in Table 4 wherein tolerance time for untreated and ZMA-treated materials are given for comparison. It follows from Table 4 that the fungicidal activity of the proposed salts exceeds the fungicidal activity of ZMA.

INDUSTRIAL APPLICABILITY

(13) The present invention can be used for production of biocides intended, for example, for incorporation into polymer materials, disinfectant and antiseptic compositions, treatment of wood, paper, building structures and other materials to prevent their damage caused by biological matters (microorganisms, fungi, algae), manufacture of various articles with biocidal properties, etc.

(14) TABLE-US-00001 TABLE 1 Results of elemental analysis of salts Sample C, g H, g Zn, g Cu, g S, g Exam- Empirical weight, calcu- deter- calcu- deter- calcu- deter- calcu- deter- calcu- deter- ple Name formula g lated mined lated mined lated mined lated mined lated mined 1 Zinc C.sub.10H.sub.8O.sub.8SZn 0.5 0.170 0.165 0.011 0.012 0.093 0.093 0.045 0.044 acrylate- sulfo- salicylate 2 Zinc meth- C.sub.11H.sub.10O.sub.4Zn 0.5 0.242 0.25 0.020 0.019 0.120 0.120 acrylate- 0.24 0.021 0.117 benzoate 3 Zinc meth- C.sub.11H.sub.10O.sub.5Zn 0.5 0.230 0.20 0.0175 0.016 0.114 0.100 acrylate- 0.21 0.014 0.091 salicylate 4 Zinc meth- C.sub.11H.sub.10O.sub.8SZn 0.5 0.180 0.182 0.0137 0.013 0.089 0.08 0.045 acrylate- 0.178 0.0135 0.087 0.042 sulfo- salicylate 5 Zinc meth- C.sub.12H.sub.12O.sub.4Zn 0.5 0.252 0.25 0.021 0.015 0.114 0.11 acrylate- 0.265 0.0165 0.116 toluylate 6 Zinc C.sub.10H.sub.8O.sub.4Zn 0.5 0.233 0.24 0.0156 0.015 0.127 0.12 acrylate- 0.238 0.0165 0.126 benzoate 7 Copper C.sub.10H.sub.8O.sub.4Cu 0.5 0.235 0.24 0.0158 0.0156 0.124 0.125 acrylate- 0.235 0.016 0.128 benzoate 8 Copper C.sub.11H.sub.10O.sub.5Cu 0.5 0.231 0.21 0.0176 0.0155 0.111 0.115 meth- 0.205 0.016 0.1 acrylate- salicylate

(15) TABLE-US-00002 TABLE 2 Bactericidal activity of zinc methacrylate-salicylate and zink methacrylate-sulfosalicylate Concen- Time of tration, exposure, Zinc methacrylate-salicylate Zinc methacrylate-sulfosalicylate % wt. min. E. coli 1257 S. aureus 906 P. aeruginosa S. aureus E. coli 906 S. aureus 1257 P. aeruginosa S. aureus 2.0 30 NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG 15 NG NG NG NG NG NG NG NG 5 NG NG NG NG NG NG NG NG 1.0 60 NG NG NG NG NG NG NG 101 CFU NG NG NG NG NG NG 30 CFU NG NG NG NG NG NG 30 NG NG NG NG NG NG NG NG NG NG NG NG NG NG >300 CFU NG 15 NG NG NG 40 CFU NG >300 CFU NG 5 NG 7 CFU 1 CFU >300 CFU NG CG 1 CFU 0.5 60 1 CFU >300 CFU NG 3 CFU >300 CFU 3 CFU 30 >300 CFU CG 4 CFU 15 42 CFU CG 10 CFU 5 75 CFU CG >300 CFU Note: NGno growth; CFUnumber of colony-forming units in 1 ml; CGconfluent growth

(16) TABLE-US-00003 TABLE 3 Bactericidal activity of zinc methacrylate-acetate Concen- Time of tration, exposure, Zinc methacrylate-acetate % wt. min. E. coli 1257 S. aureus 906 P. aeruginosa 5 5 NG >300 CFU 1 CFU NG >300 CFU NG NG >300 CFU NG 2.5 60 NG 1 CFU NG NG 4 CFU NG NG 95 CFU NG 30 NG >300 CFU NG NG >300 CFU 1 CFU NG >300 CFU NG 5 24 CFU CG CG 113 CFU CG CG 180 CFU CG CG 1.0 60 NG CG 3 CFU NG CG 93 CFU NG CG 78 CFU 30 NG CG >300 CFU NG CG >300 CFU NG CG >300 CFU 5 CG CG CG CG CG CG CG CG CG Note: NGno growth; CFUnumber of colony-forming units in 1 ml; CGconfluent growth

(17) TABLE-US-00004 TABLE 4 Fungicidal activity of the proposed salts Additive Example Content, Tolerance No. Test material Name % wt. time, days 11 Polyvinyl chloride emulsion Zinc methacrylate- 0.5 16 salicylate 12 Polyvinyl chloride emulsion Zinc methacrylate- 0.5 16 sulfosalicylate 13 Polyvinyl chloride emulsion Zinc acrylate- 0.5 11 benzoate 14 Polyvinyl chloride emulsion Copper methacrylate- 0.5 17 benzoate 15 Polyvinyl chloride emulsion ZMA 5 22 (compar.) 16 Polyvinyl chloride emulsion 6 (compar.) 17 Paper impregnated with Zinc methaerylate- 0.5 8 latex SKS 65 GP salicylate 18 Paper impregnated with Zinc methacrylate- 0.5 16 latex SKS 65 GP sulfosalicylate 19 Paper impregnated with ZMA 0.5 12 (compar.) latex SKS 65 GP 20 Paper impregnated with 4 (compar.) latex SKS 65 GP 21 Paper impregnated with Zinc methacrylate- 4.7 20 petrolatum base sulfosalicylate 22 Paper impregnated with ZMA 4.7 16 (compar.) petrolatum base 23 Paper impregnated with 15 (compar.) petrolatum base