CN105637040B - 锌或铜(ii)盐及其作为杀生剂的应用 - Google Patents

锌或铜(ii)盐及其作为杀生剂的应用 Download PDF

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CN105637040B
CN105637040B CN201380080157.3A CN201380080157A CN105637040B CN 105637040 B CN105637040 B CN 105637040B CN 201380080157 A CN201380080157 A CN 201380080157A CN 105637040 B CN105637040 B CN 105637040B
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拉瑞莎·弗拉基米罗芙娜·卡巴诺娃
伊戈尔·伊万诺维奇·佐特金
娜杰日达·弗拉基米罗芙娜·库兹涅佐娃
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Abstract

本发明提供了作为杀生剂应用的具有通式CH2＝C(R1)COO‑M‑OCOC6H3R2R4的锌或铜(II)盐，其中M为锌或铜；R1选自包含氢和甲基的组；R2选自包含氢和OH的组；R4选自包含氢、烷基和SO2OH基的组。

Description

锌或铜(II)盐及其作为杀生剂的应用
技术领域
本发明涉及一种新的化合物-可作为杀生剂应用的结合有机酸的锌和铜盐。
背景技术
各种锌或铜盐表现出杀菌活性在本技术领域是已知的，特别地，锌和铜的氧化物和无机盐(RU 95102413,C09D 5/14,1997；RU 2162870,C09D 5/02,C09D 5/14,2001；RU2395548,C09D 5/14,B82B 1/00,2010；RU 2398804,C09D 5/14,A01N 59/00,A01N 47/00,B82B 1/00,2010；US 5540954,A01N 59/16,A01N 59/20,B27K 3/52,B05D 07/06,A01N 31/08,A01N 31/00,1996；US 6858658,A01N 59/20,A01N 59/16,C09D 5/16,C08K 03/10,C08K03/18,C08K 03/22,2005；US 20080219944,C09D 5/16,2008；US 20090223408,C09D 5/16,C09D 5/14,2009)，锌和铜的环烷酸盐或树脂酸盐(RU 2377121,B27K 3/50,B27K 3/52,B27K 3/22,2009；EP 2161316,C09D 133/06,C09D 133/12,C09D 143/04,C09D 5/16,C09D7/12,2010；EP 2360214,C09D 143/04,C09D 193/04,C09D 5/16,2011；US 4258090,C04B41/45,C04B 41/52,C04B 41/60,C04B 41/70,B05D 03/02,1981)，锌盐的氨络合物(US5460644,C08K 3/10,C08K 3/00,C09D 5/14,C09D 5/00,1995)，吡啶硫酮锌和吡啶硫酮铜(双-(2-巯基吡啶)-1,1'-二氧化物)(RU 2111993,C09D 5/14,C09D 5/16,1998；RU2415168,C09D 5/16,C09D 5/14,2011；US 5185033,C09D 5/14,C09D 5/16,1993；US5298061,C09D 5/16,C09D 5/14,1994；US 5717007,C09D 5/16,C08L 33/10,C08K 05/17,C08K 05/18,1998；US 6399560,A01N 43/40,A01N 43/34,A61L 2/18,C11D 3/48,2002；US7410553,D21C 5/02,B32B 27/04,D21G 1/02,2008)。不同功效等级的上述化合物作为添加剂用于涂层，以处理建筑结构，预防水下结构和船体免遭污垢，以及用于纸张和木材处理。
与上述化合物最接近的相似物是含乙酸和甲基丙烯酸的锌盐，如甲基丙烯酸-乙酸锌(后文称之为ZMA)，ZMA与水性苯乙烯-丙烯酸分散体复合作为聚合物底漆用于各种表面的涂层时，表现出一定的杀菌活性(RU 2315793,C09D 5/14,C09D 131/02,C09D 133/10,2008)。
发明内容
为了提供作用在不同生物基底上的新途径，本发明提供了具有如下通式的锌或铜(II)盐：
其中，M为锌或铜；
R1选自包含氢和甲基的组；
R2选自包含氢和OH的组；
R3选自包含烷基和SO2OH基的组。
为了解决相同的问题，本发明提供了用作杀生剂的具有以下通式的锌或铜(II)盐：
其中M为锌或铜；
R1选自包含氢和甲基的组；
R2选自包含氢和OH的组；
R4选自包含氢、烷基和SO2OH基的组。
令人惊奇地发现，符合通式(2)的锌和铜(II)盐涵盖了式(1)的新化合物，以及以前已知的丙烯酸-安息香酸锌和甲基丙烯酸-安息香酸铜(CN 102167775,2011)，其杀菌活性以前并未被知晓，它们具有比ZMA高得多的杀菌活性，且对生物物质具有宽光谱影响。因此，它们不仅可以用于涂层组合物中，而且可以用于不同目的的消毒剂组合物中、纸张和木材处理组合物中、具有高抗霉性聚合物组合物中，以及一些预防生物和材料免遭生物物质不利影响的方法中。
具体实施方式
本发明的本质将通过下面的实施例进行阐明。实施例1-8描述了本发明涉及的系列物质中的某些代表物质的制备和性质，实施例9-23描述了--它们的杀菌和杀真菌活性。
实施例1：10g磺基水杨酸、100ml蒸馏水被置于一个500ml圆底烧瓶中，溶液被搅拌直至磺基水杨酸完全溶解。然后，将3.64g氧化锌加入50ml蒸馏水中形成的悬浮液在不停搅拌下逐渐加入到上述溶液中，同时加入3.2g丙烯酸且搅拌，直至悬浮液完全溶解。在不超过70℃的温度下将获得的溶液蒸发干燥，然后将所得固态产物从蒸馏水中再结晶。获得12.1g水溶性粉状丙烯酸-磺基水杨酸锌，该产物对应上述通式中R1＝H，R2＝SO2OH，R3＝OH(化学计量的产率为79％)。表1给出了本实施例和后续实施例中所得盐的元素分析结果。
实施例2：通过实施例1类似的方法，用安息香酸和甲基丙烯酸替代磺基水杨酸和丙烯酸(分别替代)，获得了化学计量的产率为68％、熔点为283℃的甲基丙烯酸-安息香酸锌(R1＝CH3，R2＝H，R3＝H)。
实施例3：通过实施例1类似的方法，用水杨酸和甲基丙烯酸替代磺基水杨酸和丙烯酸(分别替代)，获得了化学计量的产率为80％、熔点为250℃的甲基丙烯酸-水杨酸锌(R1＝CH3，R2＝H，R3＝OH)。
实施例4：通过实施例1类似的方法，用甲基丙烯酸替代丙烯酸，获得了化学计量的产率为82％、熔点为238℃的甲基丙烯酸-磺基水杨酸锌(R1＝CH3，R2＝SO2OH，R3＝OH)。
实施例5：通过实施例1类似的方法，用苯乙酸和甲基丙烯酸替代磺基水杨酸和丙烯酸(分别替代)，获得了化学计量产率为80％的甲基丙烯酸-甲苯甲酸锌(R1＝CH3，R2＝CH3，R3＝H)。
实施例6.通过实施例1类似的方法，用安息香酸替代磺基水杨酸，获得了化学计量的产率为55％、熔点238℃的丙烯酸-安息香酸锌(R1＝H，R2＝H，R3＝H)。获得的化合物的结构通过NMR光谱分析检验。在1Н的NMR谱中，在5.62÷5.72和6.15÷6.30ppm区域的多重谱线属于H2C＝CH–C(O)O丙烯酸盐基团的质子。安息香基团在δН为7.38(三重线)、7.48(三重线)和8.06ppm(双重线)处显示信号。在13С的NMR谱中，安息香基团在δС为129.0(m-СН)、131.0(о-СН)、132.8(p-СН)、135.2(С1)、175.4ppm(ОС(＝О))处显示信号，丙烯酸盐基团在δС为129.0和133.2(Н2С＝СH-)、175.1ppm(ОС(＝О))处显示信号。
实施例7：通过实施例1类似的方法，用安息香酸替代磺基水杨酸、用氧化铜替代氧化锌，获得了化学计量的产率为55％的丙烯酸-安息香酸铜(R1＝H，R2＝H，R3＝H)。
实施例8.通过实施例1类似的方法，用水杨酸和甲基丙烯酸替代磺基水杨酸和丙烯酸(分别替代)、用氧化铜替代氧化锌，获得了化学计量产率为85％的甲基丙烯酸-水杨酸铜(R1＝CH3，R2＝H，R3＝OH)。
实施例9：按照已知方法(RU 2378363,C12N 1/00,C12Q 1/00,2010)，所述已知方法基于在杀菌物质溶液中进行细菌培养暴露一定时间，然后在固体营养培养基上进行培养的中和和接种，测定了实施例3中所得的甲基丙烯酸-水杨酸锌和实施例4中所得的甲基丙烯酸-磺基水杨酸锌的杀菌活性。微生物对消毒剂的敏感性通过微生物在营养培养基中生长至300CFU/ml(CFU–菌落形成单位)判定：具体地，生长至100CFU/ml表现出不完全的杀菌效果，生长至100–300CFU/m表现出亚杀菌效果，生长至超过300CFU/ml表现出微生物对消毒剂的抗性。测定在大肠杆菌906号实验菌株(E.coli No.906)和金黄色葡萄球菌1257号实验菌株(S.aureus No.1257)上进行，所述两种实验菌株常用于研究杀生剂的杀菌活性，测定也在临床菌株–铜绿假单胞菌和耐甲氧西林金黄色葡萄球菌菌株(P.aeruginosa andmethicillin-resistant strain S.aureus)上进行–盐浓度从0.5至2％和暴露时间从5至60分钟。测试结果示于表2中。从表2可以看出，甲基丙烯酸-水杨酸锌在浓度1.0％时对所有菌株在30分钟暴露时间表现稳定杀菌效果。在浓度2.0％时，它表现出与暴露时间5分钟相同的杀菌效果。甲基丙烯酸-磺基水杨酸锌在浓度1.0％时对四分之三的被研究均菌株在30分钟暴露时间也表现稳定的杀菌效果。
实施例10(对比实施例)：用与实施例9中相同的方法测定ZMA对实施例9中四分之三的被研究菌株的杀菌活性。测试结果示于表3中，从表3可以看出，ZMA的杀菌活性明显地低于本发明涉及的盐：它在30分钟暴露时间和从1.0至2.5％的浓度下对大肠杆菌906号(E.coli No.906)实验菌株表现出稳定的杀菌活性，仅在2.5％的浓度下对铜绿假单胞菌(P.aeruginosa)表现不完全稳定杀菌活性，仅在2.5％浓度和60分钟暴露时间下对金黄色葡萄球菌1257号菌株(S.aureus No.1257)表现亚杀菌活性。
实施例11-23：按照GOST 30028.4-2006，通过测试用本发明涉及的盐处理的不同材料对真菌孢子的抗性，测定了用本发明涉及的盐的杀霉菌活性。测试结果用耐受时间(天)示于表4中，其中，未处理过和用ZMA处理过材料的耐受时间用于比较。从表4中可以看出，本发明涉及的盐的杀霉菌活性胜过ZMA的杀真菌活性。
工业实用性
本发明可用于生产杀生剂，例如，结合到聚合物材料、消毒剂和杀菌剂的组合物中，处理木材、纸张、建筑结构和其他物质以预防上述各种物质因生物物质(微生物、霉菌、藻类)引起的损坏，制造具有生物杀灭特性的各种物品等。
表3.甲基丙烯酸-乙酸锌的杀菌活性
注：NG–未生长；CFU–1ml中的菌落形成个数；CG–汇合生长
表4.本发明涉及的盐的杀真菌活性

Claims (2)

1.具有下列通式的锌或铜(II)盐：
其中，M为锌或铜；
R1选自包含氢和甲基的组；
R2选自包含氢和SO2OH基的组；
R3选自包含OH的组。
2.具有下列通式的锌或铜(II)盐作为杀生剂的应用：
其中M为锌或铜；
R1选自包含氢和甲基的组；
R2选自包含氢和SO2OH基的组；
R4选自包含氢和OH的组。
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