# Patent

## Title
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 CH2C(R1)CO—M—OCOR2(OH)m(COOH)n wherein M is Zn or Cu, R1 is selected from the group comprising hydrogen and methyl, R2 is substituted C1-C5 alkyl, m=0-5, n=0-2, m+n=1-5.

## Background
RELATED APPLICATIONS
This Application is a Continuation application of International Application PCT/RU2015/000251, filed on Apr. 20, 2015, which in turn claims priority to Russian Patent Applications No. RU 2014121530, tiled May 27, 2014, both of which are incorporated herein by reference in their entirety.


FIELD OF THE INVENTION
The invention relates to new chemical compounds—zinc and copper salts with organic acids, which can find application as biocides.
BACKGROUND OF THE INVENTION
Various zinc and copper compounds exhibiting biocidal activity are known in the art, in particular, zinc and copper oxides and inorganic salts (U.S. Pat. No. 5,540,954, A01N 59/16, A01N 59/20, B27K 3/52, B05D 07/06, A01N 31/08, A01N 31/00, 1996; U.S. Pat. No. 6,858,658, A01N 59/20, A01N 59/16, C09D 5/16, C08K 03/10, C08K 03/18, C08K 03/22, 2005; US 20080219944, C09D 5/16, 2008; US 20090223408, C09D 5/16, C09D 5/14, 2009), zinc and copper naphthenates or resinates (EP 2161316, C09D 133/06, C09D 133/12, C09D 143/04, C09D 5/16, C09D 7/12, 2010; EP 2360214, C09D 143/04, C09D 193/04, C09D 5/16, 2011; U.S. Pat. No. 4,258,090, C04B 41/45, C04B 41/52, C04B 41/60, C04B 41/70, B05D 03/02, 1981), ammonia complexes of zinc salts (U.S. Pat. No. 5,460,644, C08K 3/10, C08K 3/00, C09D 5/14, C09D 5/00, 1995), zinc and copper pyrithionates-bis-(2-pyridylthio)-1,1′-dioxides (U.S. Pat. No. 5,298,061, C09D 5/16, C09D 5/14, 1994; U.S. Pat. No. 5,717,007, C09D 5/16, C08L, 33/10, C08K 05/17, C08K 05/18, 1998; U.S. Pat. No. 6399560, A01N 43/40, A01N 43/34, A61L 2/18, C11D 3/48, 2002; U.S. Pat. No. 7,410,553, D21C 5/02, B32B 27/04, D21G 1/02, 2008). The above mentioned compounds were used with various degrees of efficiency as biocide of different purpose.
Zinc salt with acetic and methacrylic acids, i.e. zinc methacrylate-acetate (hereinafter referred to as ZMA) exhibiting a certain biocidal activity when compounded with aqueous styrene-acrylic dispersion being used as polymer primer for applying paint coatings to various surfaces is also known (RU 2315793, C09D 5/14, C09D 131/02, C09D 133/10, 2008).
The closest analogue of the proposed compounds is zinc or copper (II) salt of the general formula




wherein M—Zn or Cu,
R1 is selected from the group comprising hydrogen and methyl,
R2 is selected from the group comprising hydrogen, alkyl and SO2OH group.
R3 is selected from the group comprising hydrogen and OH (RU 2497857, C09D 5/14, C07C 69/78).
SUMMARY OF THE INVENTION
To provide new means effecting on various biological substrates zinc or copper (II) salt of the general formula is proposed:




wherein M—Zn or Cu,
R1 is selected from the group comprising hydrogen and methyl,
R2 is substituted C1-C5 alkyl,
m=0-5
n=0-2
m+n=1-5
To solve the same problem it is also proposed to use the above compound as biocide.
It was found that zinc and copper (II) salts corresponding to the above formula exhibit high biocidal activity and wide spectrum of effect on biological matters. Thus, they can be used in disinfectant compositions of various purposes, coating compositions, paper and wood treatment compositions, polymer compositions with higher fungus resistance as well as in many processes preventing organisms and materials from adverse effect of biological matters, in particular crustaceans.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
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
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 R1═CH3, R2═CH2, 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
Copper methacrylate-alutamate (R1═CH3, R2═CH(NH2)(CH2)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
Copper acrylate-asparaginate (R1═H, R2═CH(NH2)CH2, 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
Zinc methacrylate-succinate (R1═CH3, R2═(CH2)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
Zinc acrylate-malonate (R1═H, R2═CH2, 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
Zinc methacrylate-malate (R1═CH3, R2═CH2CH, 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
Zinc acrylate-citrate(R1═H, R2═C(CH2)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
Zinc acrylate-amygdalate (R1═R2═CHC6H5, 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
Copper acrylate-tartrate (R1═H, R2═CHCH, 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
Zinc acrylate-lactate (R1═H, R2═CHCH3, 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
Copper acrylate-gluconate (R1═H, R2═(CH)4CH2, 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
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
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
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
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.







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
C6H8O5Cu
0.5
0.1609
0.161
0 0180
0.0179



methacrylate-



0.1609





glycolate








2
Copper
C9H13O6NCu
0.5
0.183
0.18
0.022
0.021



methacrylate-



0.184

0.02



glutamate








3
Copper
C7H9O6NCu
0.5
0.1575
0.157
0.0168
0.016



acrylate-



0.151

0.017



asparginate








4
Zinc
C8H10O6Zn
0.5
0.1795
0.18
0.0187
0.019



methacrylate-



0.178

0.0185



succinate








5
Zinc acrylate-
C6H6O6Zn
0.5
0.15
0.148
0.0125
0.013



malonate



0.151

0.0125


6
Zinc
C8H10O7Zn
0.5
0.1695
0.169
0.0176
0.0179



methacrylate-



0.17

0.0177



malate








7
Zinc acrylate-
C9H10O9Zn
0.5
0.165
0.164
0.0153
0.0153



citrate



0.167

0.0151


8
Zinc acrylate-
C11H10O5Zn
0.5
0.2295
0.23
0.0174
0.0175



amygdalate



0.229




9
Copper 
C7H8O8Cu
0.5
0.148
0.15
0.014
0.014



acrylate-



0.149

0.0145



tartrate








10
Zinc acrylate-
C6H8O5Zn
0.5
0.159
0.16
0.0177
0.018



lactate








11
Copper 
C9H14O9Cu
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


















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













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
















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

## Claims

1. A zinc or copper (II) salt having a general formula



wherein M is Zn or Cu,
R1 is selected from the group consisting of hydrogen and methyl,
R2 is substituted C1-C5 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.