CN102711460A - 协同抗微生物组合物 - Google Patents

协同抗微生物组合物 Download PDF

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CN102711460A
CN102711460A CN2010800479459A CN201080047945A CN102711460A CN 102711460 A CN102711460 A CN 102711460A CN 2010800479459 A CN2010800479459 A CN 2010800479459A CN 201080047945 A CN201080047945 A CN 201080047945A CN 102711460 A CN102711460 A CN 102711460A
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biocide
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thps
methylol
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尹蓓
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Dow Global Technologies LLC
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Abstract

一种包含两种组分的协同抗微生物组合物。第一组分是羟甲基取代的磷化合物。第二组分是以下杀生物剂之一：六氢-1，3，5-三(2-羟乙基)-s-三嗪，2，6-二甲基-1，3-二噁烷-4-基乙酸酯或邻苯基苯酚或其碱金属盐或铵盐。

Description

协同抗微生物组合物
本发明涉及杀生物剂的组合，该组合具有比单独的抗微生物化合物所观察到的活性更高的活性。
使用至少两种抗微生物化合物的组合能拓宽潜在的市场，减小使用浓度和成本，并减少废物。在一些情况下，由于市售的抗微生物化合物对某些种类的微生物的活性很差，或者较慢的抗微生物作用，或者在某些条件如高温和高pH条件下不稳定，所以即使采用高使用浓度，所述市售的抗微生物化合物也无法提供有效的微生物控制。有时人们使用不同抗微生物化合物的组合在具体最终应用环境中提供微生物的总体控制，或者以较低使用率提供相同水平的微生物控制。例如，美国专利第5,385,896号揭示了磷鎓盐和醛的组合，但是该参考文献没有暗示本发明要求保护的任何组合。而且，目前需要其它的抗微生物化合物的组合，这些组合具有增强的活性，从而能有效控制微生物。本发明所解决的问题是提供这些其它的抗微生物化合物的组合。
发明内容
本发明涉及一种协同抗微生物组合物，其包含：(a)选自下组的羟甲基取代的磷化合物：四(羟甲基)磷鎓盐和三(羟甲基)膦；(b)选自下组的第二杀生物剂：(i)四氢-1，3，5-三(2-羟乙基)-s-三嗪(HHT)，(ii)2，6-二甲基-1，3-二噁烷-4-基乙酸酯(DXN)，和(iii)邻苯基苯酚或其碱金属盐或铵盐；其中羟甲基取代的磷化合物与六氢-1，3，5-三(2-羟乙基)-s-三嗪的重量比为15∶1-1∶15，羟甲基取代的磷化合物与2，6-二甲基-1，3-二噁烷-4-基乙酸酯的重量比为15∶1-1∶15，羟甲基取代的磷化合物与邻苯基苯酚或其碱金属盐或铵盐的重量比为15∶1-1∶5。
发明详述
在本文中，除非上下文明确有不同的说明，以下术语具有所限定的含义。根据所用的剂量，体系条件，以及所需微生物控制水平，术语″抗微生物化合物″表示能够抑制微生物生长或繁殖和/或杀伤微生物的化合物；抗微生物化合物包括杀细菌剂、细菌抑制剂(bacteristats)、杀真菌剂、真菌抑制剂、杀藻剂和藻抑制剂。术语″微生物″包括例如真菌(例如酵母菌和霉菌)、细菌和藻类。在本说明书中使用以下缩写：ppm＝百万分之一重量份(重量/重量)，mL＝毫升。除非另外说明，温度的单位是摄氏度(℃)，百分数以重量计(重量％)。本发明组合物中抗微生物化合物的百分含量是基于组合物中活性成分的总重量计，即是基于抗微生物化合物本身，而排除任何可能存在的溶剂、载体、分散剂、稳定剂或其它材料的量。羟甲基取代的磷化合物选自下组：四(羟甲基)磷鎓盐(例如硫酸四(羟甲基)磷鎓(THPS)和氯化四(羟甲基)磷鎓)和三(羟甲基)膦。可以存在不止一种羟甲基取代的磷化合物，在此情况下，由这些化合物的总含量计算杀生物剂比例。邻苯基苯酚或其碱金属盐或铵盐包括锂、钠、钾、铷、铯和铵盐。如果存在不止一种形式的邻苯基苯酚，可以由这些化合物的总含量计算杀生物剂比例。在本发明的一些实施方式中，使用邻苯基苯酚钠(NaOPP)。2，6-二甲基-1，3-二噁烷-4-基乙酸酯(DXN)与早期参考文献中报导的名为6-乙酰氧基-2，4-二甲基-间-二噁烷所指的化合物是相同的化合物。
在本发明的一些实施方式中，羟甲基取代的磷化合物与DXN的重量比为12∶1-1∶15，或者12∶1-1∶12，或者10∶1-1∶12，或者10∶1-1∶10，或者9∶1-1∶12，或者9∶1-1∶10，或者9∶1-1∶9，或者8.2∶1-1∶9，或者8.2∶1-1∶8.2。
在本发明的一些实施方式中，羟甲基取代的磷化合物与邻苯基苯酚或其碱金属盐或铵盐的重量比为12∶1-1∶5，或者12∶1-1∶4，或者10∶1-1∶5，或者10∶1-1∶4，或者10∶1-1∶3，或者9∶1-1∶4，或者9∶1-1∶3，或者8∶1-1∶3。
在本发明的一些实施方式中，抗微生物组合物基本不含噁唑烷化合物，也即是说，相对于杀生物剂活性组分总含量，噁唑烷的含量小于5％，或者小于2％，或者小于1％，或者小于0.5％，或者小于0.1％。
在本发明的一些实施方式中，本发明的抗微生物组合可用于油气田注水，产出流体，压裂液和其它功能流体，油气井，油气操作、分离、储存和传输系统，油气管道，油气容器和燃料中。该组合特别可用于加入油气井中的水性流体或由油气井产生的水性流体中。该组合物还可用于控制其它工业用水和含水基质或水污染基质中的微生物，所述工业用水和含水基质或水污染基质的例子包括冷却水，空气洗涤器，热交换器，锅炉水，纸浆和造纸用水，其它工业处理水，压舱水，废水，金属加工流体，胶乳，漆，涂料，粘合剂，油墨，带条接缝配混物，颜料，水基浆料，个人护理产品和居家产品，例如清洁剂，过滤体系(包括反渗透和超滤体系)，抽水马桶(toilet bowel)，织物，皮革和皮革生产体系，或与之一起使用的体系。
通常，为控制微生物生长，本发明杀生物剂组合的量应为10ppm-5,000ppm活性成分。在本发明的一些实施方式中，组合物中活性成分的含量至少为20ppm，或者至少为50ppm，或者至少为100ppm，或者至少为150ppm，或者至少为200ppm。在一些实施方式中，组合物中活性成分的含量不超过2,000ppm，或者不超过1,000ppm，或者不超过500ppm，或者不超过400ppm，或者不超过300ppm，或者不超过250ppm，或者不超过200ppm，或者不超过100ppm，或者不超过50ppm。上述浓度是在含杀生物剂组合的液体组合物中的浓度。在高硫化物和高温环境中的杀生物剂浓度通常高于在其它环境中的浓度。在本发明的一些实施方式中，油井中井下的活性成分的浓度为30-500ppm，或者50-250ppm。在本发明的一些实施方式中，用于油井顶部处理的活性成分浓度为10-300ppm，或者30-100ppm。
本发明还包括防止上述使用区域、特别是石油或天然气生产操作中微生物生长的方法，该方法是将所述的杀生物剂组合引入所述材料中。
实施例
实施例1.THPS和HHT抵抗硫酸盐还原细菌(SRB)的协同效应
在厌氧培养室(Bactron厌氧培养室)中，脱气的无菌盐溶液(3.1183克NaCl，1.3082毫克NaHCO3，47.70毫克KCl，72.00毫克CaCl2，54.49毫克MgSO4，172.28毫克Na2SO4，43.92毫克Na2CO3溶解在1升水中)被油田分离出的厌氧聚生体污染，所述厌氧聚生体主要是SRB，最终细菌浓度为106-107CFU/mL。然后用不同活性浓度的THPS和六氢-1，3，5-三(2-羟乙基)-s-三嗪(HHT)或THPS/HHT组合处理该被污染的水的等分样。在将混合物于40℃培育24小时后，用完全杀死等分样中细菌的最小测得杀生物剂浓度(MBC)确定杀生物效力。表1总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数*1。
表1.THPS、六氢-1，3，5-三(2-羟乙基)-s-三嗪(HHT)、THPS/HHT组合的杀生物效力，以及协同指数
*1协同指数＝Ca/CA+Cb/CB
Ca：当与杀生物剂B组合使用时，完全杀死细菌所需的杀生物剂A的浓度
CA：单独使用时，完全杀死细菌所需的杀生物剂A的浓度
Cb：当与杀生物剂A组合使用时，完全杀死细菌所需的杀生物剂B的浓度
CB：单独使用时，完全杀死细菌所需的杀生物剂B的浓度
如果协同指数小于1，表明有协同效应。
*2P值＜0.05表示平均协同指数与1.00之间存在明显差值
实施例2.评价THPS/HHT组合在高温和富含硫化物环境下抵抗厌氧细菌的杀生物效力
在厌氧培养室(BACTRON IV)中，杀生物剂溶液被104-105CFU/mL的油田SRB聚生体和10ppm二价硫离子(以硫化钠形式加入)污染。然后，将杀生物剂溶液在厌氧条件下于80℃培育7天，每天被SRB聚生体(104-105CFU/mL)和二价硫离子(10ppm)攻击。通过选择在受热、接触SRB和硫化物2小时和7天后杀死99.999％或全部细菌所需的最低测试杀生物剂剂量来确定杀生物效力。然后计算协同指数。表2总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数。
表2.评价THPS、HHT和THPS/HHT组合在高温和富含硫化物环境下的杀生物效力，以及协同指数
Figure BPA00001545841200051
*3协同指数＝Ca/CA+Cb/CB
Ca：当与杀生物剂B组合使用时，杀死99.999％细菌所需的杀生物剂A的浓度
CA：单独使用时，杀死99.999％细菌所需的杀生物剂A的浓度
Cb：当与杀生物剂A组合使用时，杀死99.999％细菌所需的杀生物剂B的浓度
CB：单独使用时，杀死99.999％细菌所需的杀生物剂B的浓度
如果协同指数小于1，表明有协同效应。
上述数据表明THPS和HHT的组合对于高温且富含硫化物的环境有协同效应。
实施例3.THPS和DXN抵抗硫酸盐还原细菌(SRB)的协同效应
在厌氧培养室(Bactron III)中，脱气的无菌盐溶液(3.1183克NaCl，1.3082毫克NaHCO3，47.70毫克KCl，72.00毫克CaCl2，54.49毫克MgSO4，172.28毫克Na2SO4，43.92毫克Na2CO3，溶解在1升水中)被油田分离出的厌氧SRB聚生体污染，所述厌氧SRB聚生体的最终细菌浓度为106-107CFU/mL。然后用不同活性浓度的THPS、DXN或THPS/DXN组合处理该被污染的水的等分样。在将混合物于40℃培育24小时后，使用连续稀释法计数活细菌的数目，通过24小时内减少99.99％细菌所需的杀生物剂剂量来确定杀生物效力。然后计算协同指数。表3总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数。
表3.THPS、DXN、THPS/DXN组合的杀生物效力，以及协同指数
Figure BPA00001545841200061
*4协同指数＝Ca/CA+Cb/CB
Ca：当与杀生物剂B组合使用时，杀死99.99％细菌所需的杀生物剂A的浓度
CA：单独使用时，杀死99.99％细菌所需的杀生物剂A的浓度
Cb：当与杀生物剂A组合使用时，杀死99.99％细菌所需的杀生物剂B的浓度
CB：单独使用时，杀死99.99％细菌所需的杀生物剂B的浓度
如果协同指数小于1，表明有协同效应。
实施例4.THPS和NaOPP抵抗硫酸盐还原细菌(SRB)的协同效应
在厌氧培养室(Bactron厌氧室)中，脱气的无菌盐溶液(3.1183克NaCl，1.3082毫克NaHCO3，47.70毫克KCl，72.00毫克CaCl2，54.49毫克MgSO4，172.28毫克Na2SO4，43.92毫克Na2CO3，溶解在1升水中)被油田分离出的SRB聚生体污染，所述SRB聚生体的最终细菌浓度为106-107CFU/mL。然后用不同活性浓度的THPS、NaOPP或THPS/NaOPP组合处理该被污染的水的等分样。混合物在40℃培育24小时后，在培养基中检测等分样中的活细菌。通过完全杀死等分样中细菌的最小测得杀生物剂浓度(MBC)来确定杀生物效力。表4总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数。
表4.THPS、NaOPP、THPS/NaOPP组合抵抗厌氧细菌的杀生物效力
Figure BPA00001545841200071
实施例5.THPS和NaOPP抵抗硫酸盐还原细菌(SRB)的协同效应
在厌氧培养室(BACTRON厌氧培养室)中，脱气的无菌盐溶液(3.1183克NaCl，1.3082毫克NaHCO3，47.70毫克KCl，72.00毫克CaCl2，54.49毫克MgSO4，172.28毫克Na2SO4，43.92毫克Na2CO3，溶解在1升水中)被油田分离出的厌氧聚生体污染，所述厌氧聚生体主要是SRB，最终细菌浓度为107CFU/mL。然后用不同活性浓度的THPS、NaOPP或THPS/NaOPP组合处理该被污染的水的等分样。混合物在40℃培育24小时后，使用连续稀释方法计数活细菌。通过杀死等分样中99.999％细菌的最小测试杀生物剂浓度来确定杀生物效力。表5总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数。
表5.THPS、NaOPP、THPS/NaOPP组合抵抗厌氧细菌的杀生物效力
Figure BPA00001545841200081
实施例6.THPS和NaOPP抵抗需氧细菌的协同效应
用铜绿假单胞菌(Psedomonas aeruginosa ATCC 10145)和金黄色葡萄球菌(Staphylococcus aureus ATCC 6538)污染PBS缓冲液(pH7)，最终细菌浓度为～106CFU/ml。然后用不同活性浓度的THPS、NaOPP或THPS/NaOPP组合处理该被污染的水的等分样。混合物在37℃培育24小时后，使用连续稀释方法计数活细菌。通过杀死99.999％等分样中细菌的最小测试杀生物剂浓度来确定杀生物效力。表6总结了各杀生物剂和它们的混合物的效力，以及各种组合的协同指数。
表6.THPS、NaOPP、THPS/NaOPP组合抵抗需氧细菌的杀生物效力
Figure BPA00001545841200091
如表4-6所示，THPS与NaOPP的组合显示协同效应，当它们组合使用时，达到良好的SRB控制所需的剂量明显低得多。

Claims (7)

1.一种协同抗微生物组合物，其包含：(a)选自下组的羟甲基取代的磷化合物：四(羟甲基)磷鎓盐和三(羟甲基)膦；(b)选自下组的第二杀生物剂：(i)四氢-1，3，5-三(2-羟乙基)-s-三嗪，(ii)2，6-二甲基-1，3-二噁烷-4-基乙酸酯，和(iii)邻苯基苯酚或其碱金属盐或铵盐；其中羟甲基取代的磷化合物与六氢-1，3，5-三(2-羟乙基)-s-三嗪的重量比为15∶1-1∶15，羟甲基取代的磷化合物与2，6-二甲基-1，3-二噁烷-4-基乙酸酯的重量比为15∶1-1∶15，羟甲基取代的磷化合物与邻苯基苯酚或其碱金属盐或铵盐的重量比为15∶1-1∶5。
2.如权利要求1所述的组合物，其特征在于，第二杀生物剂是六氢-1，3，5-三(2-羟乙基)-s-三嗪。
3.如权利要求2所述的组合物，其特征在于，所述重量比为12∶1-1∶12。
4.如权利要求1所述的组合物，其特征在于，第二杀生物剂是2，6-二甲基-1，3-二噁烷-4-基乙酸酯。
5.如权利要求4所述的组合物，其特征在于，所述重量比为10∶1-1∶10。
6.如权利要求1所述的组合物，其特征在于，第二杀生物剂是邻苯基苯酚或其碱金属盐或铵盐。
7.如权利要求6所述的方法，其特征在于，所述重量比为10∶1至1∶4。
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