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

Abstract

Zinc or copper (II) salt which can be used as a biocide, having the general formula CH.sub.2C(R.sup.1)COMOCOR.sup.2(OH).sub.m(COOH).sub.n wherein M is Zn or Cu, R.sup.1 is selected from the group comprising hydrogen and methyl, R.sup.2 is substituted C.sub.1-C.sub.5 alkyl, m=0-5, n=0-2, m+n=1-5.

Claims

1. 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 substituted C.sub.1-C.sub.5 alkyl, m=0-5 n=0-2 m+n=1-5.

2. The salt according to claim 1, wherein the zinc or copper salt is used as a biocide.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) The essence of the invention is illustrated by examples given below. Examples 1-11 describe the preparation and properties of certain representatives of the proposed series of substances, examples 12-28 various types of their biocidal activity,

EXAMPLE 1

(2) 10 g of glycolic acid, 100 ml of distilled water are placed into a 500 ml round-bottom flask, and the solution is stirred until glycolic acid is completely dissolved. Then a suspension of 10.6 g of copper (II) oxide in 50 ml of distilled water is gradually added to the solution under constant stirring, whereupon 11.32 g of methacrylic acid is added, and the suspension is stirred until completely dissolving solids. 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, 28 g of water-soluble powdered copper methacrylate-glycolate is obtained which corresponds to the above general formula wherein R.sup.1CH.sub.3, R.sup.2CH.sub.2, m=1, n=0 (95% 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) Copper methacrylate-alutamate (R.sup.1CH.sub.3, R.sup.2CH(NH.sub.2)(CH.sub.2).sub.2, m=0, n=1) with melting point of 200 C. is obtained in 75% yield of the stoichiometric by analogy with Example 1 using glutamic acid instead of glycolic one.

EXAMPLE 3

(4) Copper acrylate-asparaginate (R.sup.1H, R.sup.2CH(NH.sub.2)CH.sub.2, m=0, n=1) with melting point of 185 C. is obtained in 82% yield of the stoichiometric by analogy with Example 1 using acrylic and asparaginic acids instead of methacrylic and glycolic ones (respectively).

EXAMPLE 4

(5) Zinc methacrylate-succinate (R.sup.1CH.sub.3, R.sup.2(CH.sub.2).sub.2, m=0, n=1) with melting point of 195 C. is obtained in 74% yield of the stoichiometric by analogy with Example 1 using succinic acid instead of alycolic one and zinc oxide instead of copper one.

EXAMPLE 5

(6) Zinc acrylate-malonate (R.sup.1H, R.sup.2CH.sub.2, m=0, n=1) with melting point of 175 C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using acrylic and malonic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one.

EXAMPLE 6

(7) Zinc methacrylate-malate (R.sup.1CH.sub.3, R.sup.2CH.sub.2CH, m=1, n=1) with melting point of 215 C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using malic acid instead of glycolic one and zinc oxide instead of copper one.

EXAMPLE 7

(8) Zinc acrylate-citrate(R.sup.1H, R.sup.2C(CH.sub.2).sub.2, m=1, n=2) with melting point of 155 C. is obtained in 87% yield of the stoichiometric by analogy with Example 1 using acrylic and citric acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one.

EXAMPLE 8

(9) Zinc acrylate-amygdalate (R.sup.1R.sup.2CHC.sub.6H.sub.5, m=1, n=0) with melting point of 180 C. is obtained in 65% yield of the stoichiometric by analogy with Example 1 using acrylic and amygdalic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one.

EXAMPLE 9

(10) Copper acrylate-tartrate (R.sup.1H, R.sup.2CHCH, m=2, n=1) with melting point of 165 C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using acrylic and tartaric acids instead of methacrylic and glycolic ones (respectively).

EXAMPLE 10

(11) Zinc acrylate-lactate (R.sup.1H, R.sup.2CHCH.sub.3, m=1, n=0) with melting point of 175 C. is obtained in 65% yield of the stoichiometric by analogy with Example 1 using acrylic and lactic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one.

EXAMPLE 11

(12) Copper acrylate-gluconate (R.sup.1H, R.sup.2(CH).sub.4CH.sub.2, m=5, n=0) with melting point of 195 C. is obtained in 68% yield of the stoichiometric by analogy with Example 1 using acrylic and &conic acids instead of methacrylic and glycolic ones (respectively).

EXAMPLE 12

(13) Bactericidal activity of copper methacrylate-glycolate obtained as described in Example 1, copper acrylate-tartrate obtained as described in Example 9 and zinc acrylate-malonate obtained as described in Example 5 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 (CFU colony-forming unit) while growth up to 100 CFU/ml indicates incomplete bactericidal effect, growth up to 100-300 CFU/ml indicates sub-bactericidal effect and growth up to more than 300 CFU/ml indicates resistance of microorganisms to a disinfectant, The determination is performed on E. coli No. 906 and S. aureus No. 1257 test strains conventionally used to study the bactericidal activity of biocides as well as on clinical strain P. aeruginosa at salt concentrations from 1.5 to 3% and time of exposure from 5 to 60 min. Test results are given in Table 2. It follows from Table 2 that copper methacrylate-glycolate, copper acrylate-tartrate and zinc acrylate-malonate at concentration of 2.0% exhibit stable bactericidal effect against investigated strains at time of exposure from 30 min.

EXAMPLES 13-24

(14) 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 3 wherein tolerance time for untreated materials are given for comparison,

EXAMPLES 25-26

(15) The biocidal activity of copper methacrylate-glycolate obtained as described in Example 1 and zinc acrylate-lactate obtained as described in Example 10 against crustaceans (daphnias) is tested according to FR. 1.39.2007,03223 procedure, Test results for salts obtained as described in these and subsequent examples are given in Table 4.

Examples 27-28 (comparative). The biocidal activity of known compounds is tested in conditions described in Examples 25-26,

INDUSTRIAL APPLICABILITY

(16) The present invention can be used for production of biocides intended, for example, for incorporation into polymer compositions, 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.

(17) TABLE-US-00001 TABLE 1 Results of elemental analysis of salts Empirical Sample C, g H, g Example Name formula weight, g calculated determined calculated determined 1 2 3 4 5 6 7 8 1 Copper C.sub.6H.sub.8O.sub.5Cu 0.5 0.1609 0.161 0 0180 0.0179 methacrylate- 0.1609 glycolate 2 Copper C.sub.9H.sub.13O.sub.6NCu 0.5 0.183 0.18 0.022 0.021 methacrylate- 0.184 0.02 glutamate 3 Copper C.sub.7H.sub.9O.sub.6NCu 0.5 0.1575 0.157 0.0168 0.016 acrylate- 0.151 0.017 asparginate 4 Zinc C.sub.8H.sub.10O.sub.6Zn 0.5 0.1795 0.18 0.0187 0.019 methacrylate- 0.178 0.0185 succinate 5 Zinc acrylate- C.sub.6H.sub.6O.sub.6Zn 0.5 0.15 0.148 0.0125 0.013 malonate 0.151 0.0125 6 Zinc C.sub.8H.sub.10O.sub.7Zn 0.5 0.1695 0.169 0.0176 0.0179 methacrylate- 0.17 0.0177 malate 7 Zinc acrylate- C.sub.9H.sub.10O.sub.9Zn 0.5 0.165 0.164 0.0153 0.0153 citrate 0.167 0.0151 8 Zinc acrylate- C.sub.11H.sub.10O.sub.5Zn 0.5 0.2295 0.23 0.0174 0.0175 amygdalate 0.229 9 Copper C.sub.7H.sub.8O.sub.8Cu 0.5 0.148 0.15 0.014 0.014 acrylate- 0.149 0.0145 tartrate 10 Zinc acrylate- C.sub.6H.sub.8O.sub.5Zn 0.5 0.159 0.16 0.0177 0.018 lactate 11 Copper C.sub.9H.sub.14O.sub.9Cu 0.5 0.1638 0.164 0.0212 0.021 acrylate- 0.165 gluconate Zn, g Cu, g N, g Example calculated determined calculated determined calculated determined 1 9 10 11 12 13 14 1 0.1421 0.1420 0.1421 2 0.108 0.11 0.0237 0.024 3 0.1193 0.119 0.0262 0.027 4 0.122 0.12 0.116 5 0.137 0.14 6 0.115 0.115 0.117 7 0.0998 0.1 0.099 8 0.1137 0.1138 9 0.112 0.1125 10 0.145 0.147 11 0.0964 0.0968 0.0962

(18) TABLE-US-00002 TABLE 2 Bactericidal activity of salts Time of Copper methacrylate-glycolate Copper acrylate-tartrate Zinc acrylate-malonate Concentration, exposure, E. coli S. aureus E. coli S. aureus E. coli S. aureus % wt. min. 906 1257 P. aeruginosa 906 1257 P. aeruginosa 906 1257 3.0 30 NG NG NG NG NG NG 15 NG NG NG NG NG NG 5 NG NG NG NG NG NG 2.0 60 NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG 30 NG NG NG NG NG NG NG NG NG NG >300 CFU NG NG NG NG NG NG NG >300 CFU NG NG >300 CFU NG NG NG 15 >300 CFU >300 CFU >300 CFU NG NG >300 CFU NG NG 5 CG CG CG NG NG CG 1 CFU NG 1.5 60 >300 CFU >300 CFU CG NG NG CG 5 CFU 1 CFU NG NG 4 CFU 3 CFU NG NG 30 CG CG CG CG 45 CFU 35 CFU 53 CFU 43 CFU 15 78 CFU 85 CFU 5 >300 CFU >300 CFU Note: NG - no growth; CFU - number of colony-forming units in 1 ml; CG - confluent growth

(19) TABLE-US-00003 TABLE 3 Fungicidal activity of salts Exam- Additive Tolerance ple Content, time, No. Test material Name % wt. days 13 Polyvinyl Copper 5 10 chloride methacrylate- emulsion glycolate 14 Polyvinyl Copper 5 17 chloride acrylate- emulsion tartrate 15 Polyvinyl Zinc 5 9 chloride methacrylate- emulsion malate 16 Polyvinyl Zinc 5 17 chloride acrylate- emulsion citrate 17 Polyvinyl Zinc 5 18 chloride acrylate- emulsion malonate 18 Polyvinyl 6 (com chloride par.) emulsion 19 Paper impregnated Copper 5 8 with latex SKS methacrylate- 65 GP glycolate 20 Paper impregnated Copper 5 16 with latex SKS acrylate- 65 GP tartrate 21 Paper impregnated Zinc 5 20 with latex SKS acrylate- 65 GP malonate 22 Paper impregnated 4 (com with latex SKS par.) 65 GP 23 Paper impregnated Copper 5 8 with petrolatum methacrylate- base glycolate 24 Paper impregnated 5 (com with petrolatum par.) base

(20) TABLE-US-00004 Table 4 Biocidal activity of compounds against crustaceans Number of survived Daphnia daphnias death (the average rate Concen- over in test tration in parallel set of sample, aqueous Test samples) % of Example Com- medium, time, Control Test control No. pound % wt. h sample sample sample 25 Zinc 1 96 10 0 100 acrylate- 0.1 0 100 lactate 0.01 0 100 0.001 0 100 0.0001 1 90 0.001 3 70 26 Copper 1 96 10 0 100 meth- 0.1 0 100 acrylate- 0.01 0 100 glycolate 0.001 0 100 0.0001 0 100 0.00001 1 90 27 Copper 1 96 10 8 20 (compar.) acrylate- 0.1 9 10 benzoate 0.01 10 0 0.001 10 0 0.0001 10 0 0.00001 10 0 28 Zinc 1 96 10 10 0 (compar.) meth- 0.1 10 0 acrylate- 0.01 10 0 salicylate 0.001 10 0 0.0001 10 0 0.00001 10 0