Zinc or Copper (II) Salt and Use Thereof as a Biocide

Abstract

Zinc and copper (II) salts of the general formula CH.sub.2═C(R.sup.1)COO-M-OCOR.sup.2 are disclosed, wherein M-Zn or Cu, R.sup.1—H or CH.sub.3, R.sup.2—C.sub.2-C.sub.25 alkyl, or R.sup.2—CO—O— group is crotonate, or sorbate, or linoleate, excluding the compounds: CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—C.sub.2H.sub.5, CH.sub.2═CH—COO—Zn—O—CO—C.sub.2H.sub.5, CH.sub.2═CH—COO—Cu—O—CO—C.sub.2H.sub.5, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.4—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.4—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═CH—COO—Cu—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.14—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.16—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO-iso-C.sub.17H.sub.35, CH.sub.2═CH—COO—Zn—O—CO-iso-C.sub.17H.sub.35, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.17—CH.sub.3. Salts of the general formula wherein R.sup.2—C.sub.2-C.sub.25 alkyl, or R.sup.2—CO—O— group is crotonate, or sorbate, or linoleate, are applicable as biocides.

Claims

1. A zinc or copper salt of the general formula: ##STR00004## wherein M is Zn or Cu, R.sup.1 is H or CH.sub.3, R.sup.2 is a C.sub.2-C.sub.25 alkyl, excluding CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—C.sub.2H.sub.5, CH.sub.2═CH—COO—Zn—O—CO—C.sub.2H.sub.5, CH.sub.2═CH—COO—Cu—O—CO—C.sub.2H.sub.5, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.4—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.4—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═CH—COO—Cu—O—CO—(CH.sub.2).sub.6—CH.sub.3, CH.sub.2═CH—COO—Zn—O—CO—(CH.sub.2).sub.14—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.16—CH.sub.3, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO-iso-C.sub.17H.sub.35, CH.sub.2═CH—COO—Zn—O—CO-iso-C.sub.17H.sub.35, CH.sub.2═C(CH.sub.3)—COO—Zn—O—CO—(CH.sub.2).sub.17—CH.sub.3, or R.sup.2—CO—O— group is selected from the group consisting of crotonate, sorbate, and linoleate.

2. A method of using a zinc or copper (II) salt of the general formula: ##STR00005## as a virucide, the method comprising dissolving the zinc or copper (II) salt in an aqueous medium to form a solution having a salt concentration in a range from 0.01% to 0.1%, and treating a material with the solution, wherein in the general formula M is Zn or Cu, R.sup.1 is H or CH.sub.3, R.sup.2 is a C.sub.2-C.sub.25 alkyl, or R.sup.2—CO—O— is selected from the group consisting of crotonate, sorbate, and linoleate.

3. A method of using a zinc or copper (II) salt of the general formula: ##STR00006## as a bactericide, the method comprising dissolving the zinc or copper (II) salt in an aqueous medium to form a solution having a salt concentration in a range from 2% to 4%, and treating a material with the solution, wherein in the general formula M is Zn or Cu, R.sup.1 is H or CH.sub.3, R.sup.2 is a C.sub.2-C.sub.25 alkyl, or R.sup.2—CO—O— is selected from the group consisting of crotonate, sorbate, and linoleate.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The essence of the invention is illustrated by examples given below. Examples 1-13 describe the preparation and properties of certain representatives of the proposed series of substances, examples 14-31 and 38-49—their virucidal activity. Examples 32-37 and 50 are comparative and illustrate substantial absence of virucidal activity of ZMA in conditions described in examples 14-31 and 38-49. Example 51 illustrates bactericidal activity and examples 52-66—fungicidal activity of representatives of the proposed series of substances.

EXAMPLE 1

[0026] 50 g of crotonic (2-butenoic) acid and 200 ml of distilled water are placed into a 500 ml round-bottom flask. Then a suspension of 46.76 g of zinc oxide in 100 ml of distilled water is gradually added to the solution under constant stirring, whereupon 41.86 g of acrylic acid is added, and the suspension is stirred until completely dissolving solids. The obtained solution is evaporated to dryness at temperature of not more than 70° C. and the resulted solid product is subjected to recrystallization from distilled water. 127 g of water-soluble powdered zinc acrylate-crotonate with melting point of 180° C. is obtained which corresponds to the above general formula wherein R.sup.1═H, R.sup.2═C.sub.3H.sub.5 (98.7% 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

[0027] Zinc methacrylate-butyrate (R.sup.1═CH.sub.3, R.sup.2═C.sub.3H.sub.7) with melting point of 202° C. is obtained in 99% yield of the stoichiometric by analogy with Example 1 using methacrylic acid instead of acrylic one and butyric (butanoic) acid instead of crotonic one.

EXAMPLE 3

[0028] Zinc acrylate-capronate (R.sup.1═H, R.sup.2═C.sub.5H.sub.11) with melting point of 185° C. is obtained in 98.4% yield of the stoichiometric by analogy with Example 1 using capronic (hexanoic) acid instead of crotonic one and heating acid suspension in water up to 175° C. until capronic acid is completely dissolved whereupon zinc oxide and subsequently acrylic acid are added.

EXAMPLE 4

[0029] Copper acrylate-propionate (R.sup.1═H, R.sup.2═C.sub.2H.sub.5) with melting point of 185° C. is obtained in 99% yield of the stoichiometric by analogy with Example 1 using propionic (propanoic) acid instead of crotonic one and copper (II) oxide instead of zinc oxide.

EXAMPLE 5

[0030] Copper methacrylate-valerate (R.sup.1═CH.sub.3, R.sup.2═C.sub.4H.sub.9) with melting point of 185° C. is obtained in 95% yield of the stoichiometric by analogy with Example 3 using methacrylic acid instead of acrylic one, valerianic (pentanoic) acid instead of capronic one and copper (II) oxide instead of zinc oxide.

EXAMPLE 6

[0031] Copper methacrylate-sorbate (R.sup.1═CH.sub.3, R.sup.2═C.sub.5H.sub.7) with melting point of 220° C. is obtained in 93% yield of the stoichiometric by analogy with Example 3 using methacrylic acid instead of acrylic one, sorbic (2,4-hexadienoic) acid instead of capronic one and copper (II) oxide instead of zinc oxide.

EXAMPLE 7

[0032] Copper acrylate-caprinate (R.sup.1═H, R.sup.2═C.sub.9H.sub.19) with melting point of 187° C. is obtained in 97.8% yield of the stoichiometric by analogy with Example 3 using capric (decanoic) acid instead of capronic one and copper (II) oxide instead of zinc oxide.

EXAMPLE 8

[0033] Copper methacrylate-laurate (R.sup.1═CH.sub.3, R.sup.2═C.sub.11H.sub.23) with melting point of 210° C. is obtained in 97% yield of the stoichiometric by analogy with Example 1 with the difference that the process is carried out in ether medium using methacrylic acid instead of acrylic one, lauric (dodecanoic) acid instead of capronic one and copper (II) oxide instead of zinc oxide.

EXAMPLE 9

[0034] Zinc acrylate-undecylate (R.sup.1═H, R.sup.2═C.sub.10H.sub.21) with melting point of 177° C. is obtained in 95% yield of the stoichiometric by analogy with Example 8 using undecylic (undecanoic) acid instead of lauric one.

EXAMPLE 10

[0035] Copper acrylate-stearate (R.sup.1═H, R.sup.2═C.sub.17H.sub.35) with melting point of 198° C. is obtained in 96% yield of the stoichiometric by analogy with Example 8 using stearic (octadecanoic) acid instead of lauric one and copper (II) oxide instead of zinc oxide.

EXAMPLE 11

[0036] Zinc methacrylate-myristate (R.sup.1═CH.sub.3, R.sup.2═C.sub.13H.sub.27) with melting point of 215° C. is obtained in 98% yield of the stoichiometric by analogy with Example 8 using methacrylic acid instead of acrylic one and myristic (tetradecanoic) acid instead of lauric one.

EXAMPLE 12

[0037] Copper acrylate-linolenoate (R.sup.1═H, R.sup.2═C.sub.17H.sub.29) with melting point of 178° C. is obtained in 97% yield of the stoichiometric by analogy with Example 8 using linolenic (3,6,9-octadecatrienoic) acid instead of lauric one and copper (II) oxide instead of zinc oxide.

EXAMPLE 13

[0038] Zinc acrylate-cerotinoate (R.sup.1═H, R.sup.2═C.sub.25H.sub.51) with melting point of 181° C. is obtained in 98% yield of the stoichiometric by analogy with Example 8 using cerotinic (hexacosanoic) acid instead of lauric one.

EXAMPLES 14-19

[0039] Virucidal activity of zinc acrylate-capronate obtained as described in Example 3 against human immunodeficience virus (HIV) was investigated in suspension test in vitro according to the reference document “Guidelines for investigating and evaluating the virucidal activity of disinfectants” MU 3.52431-08 (approved on Dec. 13, 2008 by Service for Consumer Rights Protection and Human Health Control of the Russian Federation) at a concentration of biocide in an aqueous solution from 0.01 to 0.1 mass % and time of exposure from 30 to 60 min. The activity specified in the above document was estimated by the degree of inhibition of infectious virus titre measured as lg TCID.sub.50 (TCID.sub.50—50% tissue cytopathic infectious dose) which should not be less than 4 for a disinfectant. Test results for salts obtained as described in these and subsequent examples are given in Table 2.

EXAMPLES 20-25

[0040] Virucidal activity of copper acrylate-propionate obtained as described in example 4 was investigated by analogy with examples 14-19.

EXAMPLES 26-31

[0041] Virucidal activity of zinc methacrylate-myristate obtained as described in example 11 was investigated by analogy with examples 14-19.

EXAMPLES 32-37 (COMPARATIVE)

[0042] For comparison, virucidal activity of known biocide—zinc methacrylate-acetate (ZMA) against HIV was investigated by analogy with examples 14-19.

EXAMPLES 38-41

[0043] Virucidal activity of zinc methacrylate-butyrate obtained as described in example 2 against influenza A virus was investigated by analogy with examples 16-19 at a concentration of biocide in an aqueous solution from 0.05 to 0.1 mass %.

EXAMPLES 42-45

[0044] Virucidal activity of zinc acrylate-crotonate obtained as described in example 1 was investigated by analogy with examples 38-41.

EXAMPLE 46-49

[0045] Virucidal activity of copper methacrylate-sorbate obtained as described in example 6 was investigated by analogy with examples 38-41.

EXAMPLE 50 (COMPARATIVE)

[0046] For comparison, virucidal activity of known biocide—zinc methacrylate-acetate (ZMA) against influenza A virus was investigated by analogy with example 41 at a concentration of biocide in an aqueous solution of 0.1 mass % and time of exposure of 60 min.

[0047] As it follows from Table 2, the claimed compounds meet the criterion specified in the reference document for disinfectants in respect of two investigated test viruses while their closest structural analogue—ZMA—does not substantially exhibit virucidal activity against these viruses.

EXAMPLE 51

[0048] Bactericidal activity of zinc acrylate-crotonate obtained as described in Example 1, copper acrylate-stearate obtained as described in Example 10 and copper methacrylate-sorbate obtained as described in Example 6 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 estimated by microorganism growth on the nutrient medium up to 300 CFU/ml (CFU—colony-forming unit) wherein 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 2 to 4% and time of exposure from 5 to 60 min. Test results are given in Table 3. It follows from Table 3 that zinc acrylate-crotonate and copper methacrylate-sorbate at concentration of 4.0% exhibit sustained bactericidal effect against all investigated strains at time of exposure from 15 min. Copper acrylate-stearate shows sustained bactericidal effect against two first strains at concentration of 2.0% and time of exposure of 60 min. as well as at concentration of 4.0% and time of exposure from 5 min. while its bactericidal effect against the third strain is exhibited at concentration of 4.0% and time of exposure of more than 30 min.

EXAMPLES 52-66

[0049] 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 materials are given for comparison.

INDUSTRIAL APPLICABILITY

[0050] The present invention can be used for production of biocides intended for combating pathogenic microorganisms, for example, for incorporation into disinfecting and antiseptic compositions, polymer materials, for 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.

TABLE-US-00001 TABLE 1 Results of elemental analysis of salts Sample C, g H, g Zn, g Cu, g Empirical weight, calcu- deter- calcu- deter- calcu- deter- calcu- deter- Example Name formula g lated mined lated mined lated mined lated mined 1 2 3 4 5 6 7 8 9 10 11 12 1 Zinc acrylate-crotonate C.sub.7H.sub.8O.sub.4Zn 0.5 0.1903 0.2 0.0204 0.02 0.148 0.149 0.1899 0.148 2 Zinc methacrylate-butyrate C.sub.8H.sub.12O.sub.4Zn 0.5 0.2029 0.203 0.0254 0.025 0.1364 0.137 0.202 0.026 3 Zinc acrylate-capronate C.sub.9H.sub.14O.sub.4Zn 0.5 0.2138 0.2137 0.0277 0.0278 0.129 0.129 0.2139 0.0276 4 Copper acrylate-propionate C.sub.6H.sub.8O.sub.4Cu 0.5 0.1726 0.1726 0.0192 0.019 0.1524 0.1525 0.1728 0.02 5 Copper methacrylate- C.sub.9H.sub.14O.sub.4Cu 0.5 0.216 0.218 0.028 0.029 0.127 0.128 valerate 0.216 0.027 6 Copper methacrylate- C.sub.10H.sub.12O.sub.4Cu 0.5 0.231 0.229 0.023 0.024 0.122 0.123 sorbate 0.23 0.023 7 Copper acrylate-caprinate C.sub.13H.sub.22O.sub.4Cu 0.5 0.255 0.256 0.0376 0.0377 0.104 0.105 0.255 8 Copper methacrylate- C.sub.16H.sub.28O.sub.4Cu 0.5 0.1558 0.156 0.013 0.0129 0.0913 0.092 laurate 0.155 0.0133 9 Zinc acrylate-undecylate C.sub.14H.sub.24O.sub.4Zn 0.5 0.2618 0.262 0.0374 0.0375 0.1005 0.1 0.2617 0.0374 0.1006 10 Copper acrylate-stearate C.sub.21H.sub.38O.sub.4Cu 0.5 0.302 0.303 0.046 0.045 0.076 0.077 0.046 11 Zinc methacrylate- C.sub.18H.sub.32O.sub.4Zn 0.5 0.271 0.27 0.042 0.043 0.0856 0.0855 myristate 12 Copper acrylate-linolenoate C.sub.21H.sub.32O.sub.4Cu 0.5 0.306 0.31 0.0389 0.039 0.077 0.078 0.305 13 Zinc acrylate-cerotinoate C.sub.29H.sub.54O.sub.4Zn 0.5 0.327 0.328 0.051 0.05 0.061 0.06 0.327 0.062

TABLE-US-00002 TABLE 2 Results of investigation of virucidal activity of salts Concentration Time of Degree of virus of biocide in a exposure, inhibition, Example Biocide solution, % Virus min. lg TCID.sub.50 14 Zinc 0.01 HIV 30 0.0 15 acrylate- 0.01 HIV 60 0.0 16 capronate 0.05 HIV 30 2.0 17 0.05 HIV 60 3.5 18 0.1 HIV 30 4.5 19 0.1 HIV 60 5.0 20 Copper 0.01 HIV 30 0.0 21 acrylate- 0.01 HIV 60 1.0 22 propionate 0.05 HIV 30 3.0 23 0.05 HIV 60 3.5 24 0.1 HIV 30 4.0 25 0.1 HIV 60 5.0 26 Zinc 0.01 HIV 30 0.5 27 methacrylate- 0.01 HIV 60 1.5 28 myristate 0.05 HIV 30 3.0 29 0.05 HIV 60 4.5 30 0.1 HIV 30 5.5 31 0.1 HIV 60 6.5 32 (compar.) Zinc 0.01 HIV 30 0.0 33 (compar.) methacrylate- 0.01 HIV 60 0.0 34 (compar.) acetate 0.05 HIV 30 0.0 35 (compar.) 0.05 HIV 60 0.0 36 (compar.) 0.1 HIV 30 1.0 37 (compar.) 0.1 HIV 60 2.5 38 Zinc 0.05 Influenza A 30 4.0 39 methacrylate- 0.05 Influenza A 60 4.8 40 butyrate 0.1 Influenza A 30 4.5 41 0.1 Influenza A 60 5.1 42 Zinc 0.05 Influenza A 30 3.8 43 acrylate- 0.05 Influenza A 60 4.5 44 crotonate 0.1 Influenza A 30 4.2 45 0.1 Influenza A 60 4.9 46 Copper 0.05 Influenza A 30 4.1 47 methacrylate- 0.05 Influenza A 60 4.8 48 sorbate 0.1 Influenza A 30 4.7 49 0.1 Influenza A 60 5.2 50 (compar.) Zinc 0.1 Influenza A 60 0.0 methacrylate- acetate

TABLE-US-00003 TABLE 3 Bactericidal activity of salts Concen- Time of Zinc acrylate-crotonate Copper acrylate-stearate Copper methacrylate-sorbate tration, 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 4.0 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 30 NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG NG >300 CFU NG NG NG 15 NG NG NG NG NG >300 CFU NG NG 5 NG 7 CFU 1 CFU NG NG CG 1 CFU NG 2.0 60 1 CFU >300 CFU NG NG NG CG 5 CFU 1 CFU 3 CFU >300 CFU 3 CFU NG NG 4 CFU 3 CFU NG NG 30 >300 CFU CG 4 CFU 10 CFU 25 CFU CG 45 CFU 35 CFU 53 CFU 43 CFU 15 42 CFU CG 10 CFU 100 CFU >300 CFU CG 78 CFU 85 CFU 5 75 CFU CG >300 CFU CG CG CG >300 CFU >300 CFU Note: NG—no growth; CFU—number of colony-forming units in 1 ml; CG—confluent growth

TABLE-US-00004 TABLE 4 Fungicidal activity of salts Additive Example Content, Tolerance No. Test material Name wt % time, days 52 Emulsion polyvinyl Zinc acrylate-undecylate 5 10 chloride 53 Emulsion polyvinyl Copper methacrylate-valerate 5 16 chloride 54 Emulsion polyvinyl Copper acrylate-stearate 5 12 chloride 55 Emulsion polyvinyl Zinc methacrylate-butyrate 5 11 chloride 56 Emulsion polyvinyl Copper acrylate-caprinate 5 20 chloride 57 Emulsion polyvinyl Zinc methacrylate-myristate 5 12 chloride 58 Emulsion polyvinyl Control test — 6 chloride 59 Paper impregnated Zinc methacrylate-butyrate 5 10 with latex SKS 65 GP 60 Paper impregnated Copper acrylate-stearate 5 16 with latex SKS 65 GP 61 Paper impregnated Zinc acrylate-undecylate 5 12 with latex SKS 65 GP 62 Paper impregnated Copper acrylate-caprinate 5 19 with latex SKS 65 GP 63 Paper impregnated Control test — 4 with latex SKS 65 GP 64 Paper impregnated Zinc acrylate-undecylate   4.7 20 with petrolatum base 65 Paper impregnated Copper acrylate-caprinate 5 21 with petrolatum base 66 Paper impregnated Control test — 15 with petrolatum base