CN116940657A - 金属加工流体杀生物剂 - Google Patents

金属加工流体杀生物剂 Download PDF

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CN116940657A
CN116940657A CN202180092587.1A CN202180092587A CN116940657A CN 116940657 A CN116940657 A CN 116940657A CN 202180092587 A CN202180092587 A CN 202180092587A CN 116940657 A CN116940657 A CN 116940657A
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microbial growth
glycol ether
control agent
propylamine
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赵超
陈雪
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Dow Global Technologies LLC
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Abstract

本发明公开了一种微生物生长控制剂和控制金属工作流体中的微生物生长的方法，其中所述试剂至少包含二醇醚胺。

Description

金属加工流体杀生物剂
实施方案涉及微生物生长控制剂和控制金属加工流体中微生物生长的方法，其中该试剂至少包含二醇醚胺。
背景技术
金属加工流体(MWF)用于金属切削和工具成形的润滑。这些流体为金属工件工具提供冷却，从工具/工件界面去除切削碎屑，并且帮助提供可接受的后加工完成表面。胺是广泛用于各种应用中的流行MWF，这是由于它们的抗腐蚀、中和和pH调节特性。有机胺通常被用作缓蚀剂，因为MWF由于微生物生长而随着时间的推移降解，这对流体性能产生了负面影响，并且微生物以流体中的活性成分为食。
MWF中的这种微生物生长可能会在金属加工处理中以多种形式引起严重问题，这些形式包括：MWF普遍酸化、MWF粘度变化、MWF保质期缩短以及工具和材料的腐蚀。另外，设备和工艺诸如进料喷嘴、储存罐、管线和再循环系统设施的功能也可能受到MWF中微生物生长的影响。这种酸化增加了MWF的成本，加速了腐蚀速率并且降低了金属加工的效率。
因此，在MWF工业中对于不支持微生物生长并且长时间保持性能的组分存在未满足的需求。最常见的解决方案是向给定的MWF中连续地或作为分批处理添加杀生物剂和胺醇。然而，杀生物剂和一些仲胺醇受到监管限制的局限，并且大多数杀生物剂化学品会随着时间的推移释放甲醛，这对人类健康有害。
由于所有这些原因以及其他原因，需要微生物生长控制剂和控制金属加工流体中微生物生长的方法。
发明内容
实施方案涉及微生物生长控制剂和控制金属加工流体中微生物生长的方法，其中该试剂至少包含二醇醚胺。
具体实施方式
根据它们的组成，金属加工流体被分类为纯油、可溶性油、半合成流体或合成流体。可溶性油MWF包含50-70重量％的油，其余为抗磨/极压添加剂和乳化剂。半合成MWF含有显著量的水，通常至多50-60重量％，约10-40重量％的矿物油、约10-20重量％乳化剂、约10-20重量％胺和其它功能性添加剂诸如滑润剂、腐蚀抑制剂、增溶剂、pH中和剂、杀生物剂等。半合成MWF通常在最终用户的地点用水稀释至1-20重量％的浓度，更典型地5-7重量％的浓度。半合成流体具有平衡的润滑性和冷却性能，因此对于用作MWF是有吸引力的。在本公开中，微生物生长控制剂和/或杀生物剂可用作半合成流体或其它MWF中的pH中和剂。
在一个实施方案中，本发明公开的微生物生长控制剂和/或杀生物剂可描述为二醇醚胺。合适的二醇醚胺包括但不限于：2-丁氧基-乙胺、1-甲氧基-2-丙胺、1-丁氧基-2-丙胺、1-[1-甲基-2-(1-甲基-2-丙氧基乙氧基)乙氧基]-2-丙胺、1-(2-丁氧基-1-甲基乙氧基)-2-丙胺、1-(2-甲氧基-1-甲基乙氧基)-2-丙胺和1-(1-甲基-2-丙氧基乙氧基)-2-丙胺。令人惊奇地发现，这种二醇醚胺是对抗MWF中存在的细菌和其它微生物的良好杀生物剂。
在另一个实施方案中，本发明公开的杀生物组合物可以是至少包含二醇醚胺的组合物，其中所述伯醚胺化合物具有下式：
其中R1是C1-C6烷基基团，更优选C3-C4烷基基团，并且R2和R3独立地是CH3或CH2-CH3，并且m是0-6(或优选0-2)。
MWF中二醇醚胺的浓度范围可以是0.01重量％-30重量％，更优选5重量％-20重量％，这取决于给定制剂的预期用途。大多数二醇醚胺是液体，但在MWF中使用固体和液体胺两者。
微生物生长控制剂可进一步包含一种或多种额外的二醇醚胺，其可组合使用以达成特定微生物生长控制目标。
(任选的)乳化剂可以是阴离子、阳离子或非离子的。合适的阴离子表面活性剂或乳化剂的示例是碱金属皂、铵皂和胺皂；此类皂的脂肪酸部分优选地含有至少10个碳原子。这些皂还可“原位”形成；换句话讲，可在油相中加入脂肪酸，并且在水相中加入碱性物质。
合适的阴离子表面活性剂或乳化剂的其他示例是烷基-芳基磺酸的碱金属盐、二烷基磺基琥珀酸钠、硫酸化或磺化油，例如硫酸化蓖麻油；磺化牛脂，以及短链石油磺酸的碱金属盐。
合适的阳离子表面活性剂或乳化剂是长链伯胺、仲胺或叔胺的盐，诸如油酰胺乙酸盐、鲸蜡胺乙酸盐、二-十二烷基胺乳酸盐、氨基乙基-氨基乙基硬脂酰胺的乙酸盐、二月桂酰基三亚乙基四胺二乙酸盐、1-氨基乙基-2-十七碳烯基咪唑啉乙酸盐；和季铵盐，诸如溴化鲸蜡基吡啶鎓、氯化十六烷基乙基吗啉鎓和氯化二乙基二-十二烷基铵。
合适的非离子表面活性剂或乳化剂的示例是高级脂肪醇与环氧乙烷的缩合产物，诸如油醇与10个环氧乙烷单元的反应产物；烷基苯酚与环氧乙烷的缩合产物，诸如异辛基苯酚与12个环氧乙烷单元的反应产物；高级脂肪酸酰胺与5个或更多个环氧乙烷单元的缩合产物；长链脂肪酸的聚乙二醇酯，诸如四乙二醇单棕榈酸酯、六乙二醇单月桂酸酯、壬乙二醇单硬脂酸酯、壬乙二醇二油酸酯、十三乙二醇单花生酸酯、二十二乙二醇单山嵛酸酯；多元醇部分高级脂肪酸酯，诸如脱水山梨糖醇三硬脂酸酯；多元醇部分高级脂肪酸酯的环氧乙烷缩合产物及其内部酸酐(甘露醇-酸酐，称为缩甘露醇；山梨醇-酸酐，称为脱水山梨糖醇)，诸如甘油单棕榈酸酯与10个环氧乙烷分子反应，季戊四醇单油酸酯与12个环氧乙烷分子反应，脱水山梨糖醇单硬脂酸酯与10至15个环氧乙烷分子反应，缩甘露醇单棕榈酸酯与10至15个环氧乙烷分子反应；长链聚乙二醇，其中一个羟基基团与高级脂肪酸发生酯化，并且另一个羟基基团与低分子的醇发生醚化，诸如甲氧基聚乙二醇550单硬脂酸酯(550表示聚乙二醇醚的平均分子量)。可使用这些表面活性剂中的两者或更多者的组合；例如，阳离子可与非离子共混，或者阴离子与非离子共混。
由本发明公开的杀生物剂控制的微生物生长通常由污染物组成，所述污染物是细菌和真菌混合物。一些典型的真菌和细菌污染物包括但不限于嗜水气单胞菌(Aeromonashydrophila)(ATCC 13444)、白色念珠菌(Candida albicans)(ATCC 752)、脱硫脱硫弧菌(Desulfovibrio desulfuricans)(ATCC 7757)、大肠杆菌(Escherichia coli)(ATCC8739)、铁黄杆菌(Flavobacterium ferrugineum)(ATCC 13524)、尖孢镰刀菌(Fusariumoxysporum)(ATCC 7601)、肺炎克雷伯菌(Klebsiella pneumoniae)(ATCC 13883)、奇异变形杆菌(Proteus mirabilis)(ATCC 4675)、铜绿假单胞菌(Pseudomonas aeruginosa)(ATCC 8689)、食油假单胞菌(Pseudomonas oleovorans)(ATCC 8062)和酿酒酵母(Saccharomyces cerevisiae)(ATTC 2338)。以上列出的菌株可在世界各地变化，并且本发明被完全设想为可用于对抗任何常见MWF微生物污染物的广谱微生物生长控制剂和/或杀生物剂。
实施例
测试本发明公开的微生物生长控制剂和其他微生物生长控制剂的功效的实验可如下进行。
表1-稀释的金属加工流体成分
成分 重量百分比 功能 来源
二酸 0.14重量％ 腐蚀剂 益海嘉里
2-乙基己酸 0.28重量％ 增溶剂 陶氏化学公司
UCONTM润滑剂MWL-4 0.47重量％ 润滑剂 陶氏化学公司
环烷油 2.0重量％ 油性剂 衡水玺昊公司
烷基磺酸钠 0.225重量％ 乳化剂 润泽化学有限公司
KAO EMULGEN 107 0.65重量％ 乳化剂 花王
胺 0.91重量％ pH中和剂 陶氏化学公司
DI水 95.325重量％ 水相 陶氏化学公司
表2-测试的醚胺
测试1-微生物生长抑制测试
为了测试新公开的微生物生长控制剂，将表1中所示的稀释的金属加工流体与表2中列出的各种醚胺混合。首先，用250mL玻璃烧杯制备100g碱性稀释金属加工流体，除胺成分外，按表1配方配制，搅拌得到澄清溶液。重复第一步骤以得到8种碱性稀释的金属加工流体溶液。第二，添加来自表2的每种胺或胺组合作为比较例1-2和实施例1-6。第三，将50g比较例1-2和实施例1-6加入8个直径为10cm的培养皿中，并加入0.5ml混合的微生物接种物。7天后测量培养皿中的微生物生长，并重复投配混合微生物接种物并分5次测量。对于第一次和第二次投配，使用0.5ml混合接种物；在第三和第四次投配时，使用1ml混合接种物；并且在第五次投配中，使用3ml混合接种物。MWF微生物接种物是通过将0.1mL每种细菌过夜肉汤培养物和1.0mL每种酵母肉汤培养物加入10mL霉菌悬浮液中并共混而制备的。该实验中使用的微生物菌株列于下表3中(8种细菌、2种霉菌和2种真菌)。将这些菌株分别在营养肉汤中培养，然后将它们共混在一起。然后将混合的菌株注射到每个测试的MWF和胺样品中并充分混合。
表3-测试的微生物
在该实验的第0天，用0.5ml混合微生物接种物投配50克用胺样品(例如实施例1-5和比较例1-2)处理的MWF中的每一个。这种接种物引入每毫升样品约106-107菌落形成单位(CFU/ml)的微生物。
然后将混合的接种样品在30℃下温育以测定测试的胺对微生物的杀生物效果。7天后，观察培养皿中存活的微生物数，并且如果菌落生长小于10，则认为是通过。在测量存活微生物的数量后，完成混合微生物接种物的另一轮投配。进行5次观察和随后投配的步骤以激发所测试的实施例的微生物生长抑制能力。对于第一次和第二次投配，使用0.5ml混合接种物；在第三次和第四次投配时，使用1ml混合接种物；并且在第五次投配时，使用3ml混合的接种物。结果报告在下表4中。
表4-相容性测试结果
如上所示，二醇醚胺(实施例1-6)已证明比传统胺(比较例1-2)更好的微生物生长抑制性能。

Claims (9)

1.一种适用于金属加工流体的微生物生长控制剂，所述微生物生长控制剂包含至少一种具有以下结构的二醇醚胺：
其中R1为C1-C6烷基基团，并且R2为CH3或CH2-CH3，并且R3为CH3或CH2-CH3，并且m为0-6。
2.根据权利要求1所述的微生物生长控制剂，其中R1为C3-C4烷基基团或m为0-2。
3.根据权利要求1所述的微生物生长控制剂，其中所述至少一种二醇醚胺是作为以下物质的二醇醚胺：2-丁氧基-乙胺、1-甲氧基-2-丙胺、1-丁氧基-2-丙胺、1-[1-甲基-2-(1-甲基-2-丙氧基乙氧基)乙氧基]-2-丙胺、1-(2-丁氧基-1-甲基乙氧基)-2-丙胺、1-(2-甲氧基-1-甲基乙氧基)-2-丙胺或1-(1-甲基-2-丙氧基乙氧基)-2-丙胺。
4.根据权利要求1所述的微生物生长控制剂，其中将所述试剂与金属加工流体混合。
5.根据权利要求1所述的微生物生长控制剂，还包含第二二醇醚胺。
6.一种通过使用微生物控制剂来控制金属加工流体中的微生物生长的方法，其中所述微生物控制剂包含具有以下结构的一种二醇醚胺：
其中R1为C1-C6烷基基团，并且R2为CH3或CH2-CH3，并且R3为CH3或CH2-CH3，并且m为0-6。
7.根据权利要求6所述的方法，其中使用至少一种其它二醇醚胺。
8.根据权利要求6所述的方法，其中所述方法用于控制金属工作流体中的微生物生长。
9.根据权利要求6所述的方法，其中所述方法用于控制金属加工流体中的细菌、霉菌或酵母。
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