CN1011595B - 使水基功能性液体具有极压性能的水溶性添加剂，功能性液体以及含有所述添加剂的浓水基组合物 - Google Patents

使水基功能性液体具有极压性能的水溶性添加剂，功能性液体以及含有所述添加剂的浓水基组合物

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CN1011595B
CN1011595B CN88102384A CN88102384A CN1011595B CN 1011595 B CN1011595 B CN 1011595B CN 88102384 A CN88102384 A CN 88102384A CN 88102384 A CN88102384 A CN 88102384A CN 1011595 B CN1011595 B CN 1011595B
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water
additives
salt
functional
functional composition
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CN88102384A (zh
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帕特里斯·盖内
河村徹志
热拉尔·沙温
沙宾·篷塞
查尔斯·卡斯特拉
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Societe National Elf Aquitaine
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Abstract

本发明涉及使用水溶性3-巯基丙酸二硫化物盐，作为水基功能性液体的极压添加剂。可将3-巯基丙酸氧化，然后再将制得的二硫化物与一种有机或无机碱接触来制备这些盐。功能性液体应用于工业操作，例如金属的机加工中。

Description

本发明涉及使水基功能性液体具有极压性能的添加剂并涉及功能性液体和含有所述添加剂的浓水基组合物。
许多种象金属机加工一类的工业操作，例如钻孔，磨削，车削，铣削，轧制，线材拉拨或型锻，都需要有所谓的功能性液体存在。
这些液体的作用是减小切削力、冷却工件从而得到良好的量钢特性、从切削区除掉切屑而使工件具有优良表面光洁度、以及延长刀具寿命。
水的比热，汽化潜热和热传导率都很高，是最好的冷却剂。同时还由于水最经济和对环境完全无害，所以应用水基功能性液体日益普遍。这些水基功能性液体可以是不同的添加剂在水中的真溶液，它们被称为合成液体，或者是微乳状液，它们被称为半合成液体。半合成液体，除含水外，还含有矿物油和表面活性剂。
对于高压力的机加工操作，水基功能性液体的使用尚未找到满意的解决办法。
在这些操作中，金属表面之间的摩擦力极大，因此必须使用极压添加剂。这些添加剂的作用是在金属表面形成一层保护层。此种保护层的膜可防止工件与加工刀具咬住，或在更糟的情况下，将工件与刀具熔接在一起。
在这些极压添加剂中，使用最普遍的是含硫添加剂，因为它们的效果最好。含硫化合物与热的金属表面接触时可使其分解，并形成一层保护性金属硫化物层，此种硫化物层是不断更新的。
在矿物油或乳状液的润滑剂中用做极压添加剂的含硫物质是二烷基多硫化物，含硫聚异丁烯，以及含硫脂肪酸酯。所有这些物质均为微溶或不溶于水。
为了克服此一缺点，曾试图使用可溶于水的极压添加剂。
英国石油有限公司的R.W.MOULD的文章（Journal    of    the    American    Society    of    Lubrication    Engineers    33（6）291-298（1977年））考察了许多水溶性卤化产物或含硫物质作为水基液体的极压添加剂的效能。卤化产物，一般是氯化产物的效能非常低。所研究的含硫物质，例如，硫代水杨酸、2-巯基丙酸、2，2′-二硫代二苯甲酸、2，2′-二硫代二丙酸的钠盐，左旋胱氨酸二钠盐，和二硫代二甘醇酸二钠盐都是非常不稳定，并且促使细菌的生长和硫化氢的释放。
为了使其稳定，在这些产品的配方中需加入大量杀菌剂，这些杀菌剂一般都是以乳状液形式使用，但是它们通常是不能在功能性液体中使用的。
美国专利42350046叙述了使用二乙醇二硫化物作为极压添加剂。但是，此种物质与半合成液体配方中常用的多种添加剂是不相容的。
本发明人现已发现一种水溶性的、有效的和稳定的极压添加剂。
根据本发明，用于水基功能性液体的极压添加剂，包括一种3-巯基丙酸二硫化物或3，3′-二硫代二丙酸（SCH2CH2CO2H2）的水溶性盐。所谓的水溶性盐，是指在室温条件下，在水中的溶解度至少为0.01%的任何无机或有机盐，而较好的是溶解度至少为0.1%的盐。
3-巯基丙酸二硫化物是一种公知的化合物， 将3-巯基丙酸用硫或一种惯用的氧化剂，例如过氧化氢来氧化即可容易地制成。
本发明所用的盐是采用本来就是公知的方法，即在水介质中，用有机或无机碱中和该二硫化物来制备的。因此，可以使用碱金属或碱土金属氧化物、氢氧化物或碳酸盐，氨水或含氮有机碱。在用含氮有机碱制备水溶性盐时，应该特别指出的是碳原子总数不超过8（最好是1至6）的单、二或三烷基胺，和环烷基胺，而该烷基胺的至少一个烷基带有一个或多个亲水基团，例如OH，COOH或聚（氧乙烯和/或氧丙烯）。
本发明的盐的水溶液是非常稳定的，可容易地贮存，甚至在pH是7的中性介质中亦不会释放出硫化氢。必要时，由无机碱所制备的盐还能够以晶体形态分离出来。
本发明的盐是以重量浓度在0.01至20%而较好的是在0.1至10%范围内的形式加入该水基液体中。
它们可以单独使用，但一般是与水基液体常用的其他添加剂混合使用。在这些添加剂中，可指出的是具有抗磨、防锈和消泡性能的添加剂。
水基功能性液体在本性上为合成的或半合成的两种。合成液体是各种不同添加剂在水中的真溶液。加入聚二醇可改进它们的润滑性能，例如聚乙二醇，聚丙二醇或它们的共聚物。
半合成液体是含有矿物油或合成油以及表面活性剂的微乳状液。这些油提高了该水基液体的润滑性能。
由于3-巯基丙酸二硫化物的盐在水介质中非常稳定，所以能够以添加剂的浓混合物的形式贮存，而在使用时再将其稀释。这些浓缩物含有1-50%（重量），而最好是15-35%的3-巯基丙酸二硫化物，并可任意选择加入其他常用添加剂，例如防锈、抗磨和消泡添加剂，表面活性剂，聚二醇，或者矿物油或合成油。
本发明的添加剂的效能评价是应用四球机进行所谓的10点试验（ASTM标准D2783）。
四球机试验包括10次相继进行的试验，将一个球固定在夹盘中，并且顶住放在一个槽斗中的另外三个球，旋转10秒钟，同时，在该槽斗中装满了要进行试验的极压液体。通过一系列的砝码，每做一次试验即增加一次该三个球顶住该旋转的球的压力（所用砝码重量按几何级数增大）。
在每次试验中，测量在三个固定球上所形成的疤痕直径，并且以对数座标绘制曲线A，此曲线表示疤痕直径与所加负载的函数关系。
咬住（发生咬住以前的最后负载）是保持曲线A与称为HERTZ线的理想线不发生偏离的最高负载。它相当于在各球之间的接触部位上有少量熔接点存在的情况。该种疤痕或磨损痕的直径在此时突然增大。
熔接（或熔接负载）是保持使四个球不发生互相熔接从而使上面的球不能再顶住该三个球继续旋转的最高负载。
MHL（最大HERTZ负载）是一个无量纲系数，是根据上面的球顶住下面的三个固定球所形成的疤痕的测量来确定的。此系数值越大（它本身无实际物理意义），根据极压的观点，则认为进行试验的油就越好。
下列实例1至7说明本发明，但是不能限制本发明。
按照下列典型实例制备所用的盐，并按下列典型实例配制的水溶液形式使用：
典型制备方法：在一个装有搅拌器的反应器中，将1050克（5摩尔）3-巯基丙酸二硫化物溶解于1590毫升水中，然后缓缓地加入610克（10摩尔）纯单乙醇胺。所制得的含有约50%3，3′-二硫代二丙酸二（单乙醇胺）盐的溶液，即可以原浓度使用，或稀释后使用。
实例1    3-巯基丙酸二硫化物的二乙醇胺盐（DEA    DAM    3P）
将此盐以不同浓度加入含有5%ELF    XT    6720的合成液体（水溶液）中，或加入含有5%ELF    XT    6760的半合成液体（微滴乳状液）中。
ELF    XT    6720和6760是市售添加剂浓缩物，它们使水具有良好的润滑性能（润滑性，抗腐蚀性能等等）。
XT    6720是一种含有聚二醇的水溶性浓缩液。
XT    6720是一种主要是含有表面活性剂和矿物油的可微乳化的浓缩物。
添加剂    来自DEADAM3P    四球机试验结果
浓缩物    的硫，%    （所谓的10点试验）
咬住    熔接    MHL
XT6720（5%）    0    80daN    126daN    34
″    0.15    80    160    37.6
″    0.5    80    400    74.0
″    1    80    400    78.1
XT6760（5%）    0    80daN    126daN    32
″    0.15    80    160    38.6
″    0.5    80    400    74.7
″    1    100    500    77.6
在惯用的市售配制剂中加入DEADAM3P能显著改进前者的极压性能。（MHL由32或34增加至77-78）。
实例2：使用单乙醇胺盐（MEADAM3P），其余与前述相同
添加剂    来自MDEDAM3P    四球机试验结果
浓度    的硫，%    咬住    熔接    MHL
XT6720（5%）    0    80daN    126daN    34
″    0.15    80    160    38
″    0.5    80    400    73.2
″    1    100    500    79.0
XT6760（5%）    0    80daN    126daN    32
″    0.15    80    160    38.7
″    0.5    80    400    74.5
″    1    100    500    78.6
实例3：使用铵盐（NH    DAM3P），其余同前
添加剂    来自NHDAM3P    四球机试验结果
浓缩物    的硫，%    咬住    熔接    MHL
XT6720（5%）    0    80daN    126daN    34
″    0.15    80    160    37.7
″    0.5    80    400    70.9
″    1    80    400    75.5
XT6760（5%）    0    80daN    126daN    32
″    0.15    80    160    37.9
″    0.5    80    400    71
″    1    80    400    75.4
实例4：使用钠盐（Na    DAM3P），其余同前
添加剂    来自NaDAM3P    四球机试验结果
浓缩物    的硫，%    咬住    熔接    MHL
XT6720（5%）    0    80daN    126daN    34
″    0.15    80    140    37.3
″    0.5    80    400    72.7
″    1    80    400    75.5
XT6760（5%）    0    80daN    126daN    32
″    0.15    80    160    38.1
″    0.5    80    400    73.5
″    1    80    400    76.0
实例5：使用钙盐（Ca    DAM    3P），其余同前
添加剂    来自CaDAM3P    四球机试验
浓缩物    的硫，%    咬住    熔接    MHL
XT6720（5%）    0    80daN    126daN    34
″    0.15    80    160    37.7
″    0.5    80    400    71.9
XT6760（5%）    0    80daN    126daN    32
″    0.15    80    160    38.4
″    0.5    80    400    72.2
实例6：使用3-巯基丙酸二硫化物的二乙醇胺盐（DEA    DAM3P）。向在该水相中加入平均分子量为400的聚乙二醇（称为PEG    400），以改进其润滑性能。
添加剂    来自DEADAM3P    四球机试验
的硫，%    咬住    熔接    MHL
PEG    400（12%）    0    200daN    20daN    28
″    0.5    250    50    45
实例7：使用上述盐（DEA    DAM3P），加入平均分子量为425的聚丙二醇（称为PPG    425）以改进其润滑性能。
添加剂    来自DEADAM3P    四球机试验
的硫，%    咬住    熔接    MHL
PEG425（12%）    0    126daN    13daN    14
″    0.1    126    32    29
″    0.5    200    40    38

Claims (7)

1、一种用于金属机加工的含有一种极压添加剂的合成的或半合成的水基功能性组合物，其特征在于，所述极压添加剂是一种3-巯基丙酸二硫化物的水溶性盐，其重量浓度为0.01至20%，而较好的是0.1至10%。
2、按照权利要求1的水基功能性组合物，其特征在于，该水溶性盐是一种碱金属或碱土金属盐。
3、按照权利要求1的水基功能性组合物，其特征在于，该种盐是由氨水或一种含氮有机碱形成的。
4、按照权利要求3的水基功能性组合物，其特征在于，该种含氮有机碱是选自碳原子总数不超过8的单、二或三烷基胺或环烷基胺，而该烷基胺的至少一个烷基带有一个或多个亲水基团。
5、按照权利要求4的水基功能性组合物，其中该种含氮有机碱是单、二或三乙醇胺。
6、按照权利要求1的水基功能性组合物，其特征在于，此种组合物还含有一种聚二醇，例如聚乙二醇，聚丙二醇或它们的共聚物。
7、水基功能性组合物在进行金属机加工中的应用，其特征在于所述的组合物含有一种3-巯基丙酸二硫化物的水溶性盐。
CN88102384A 1987-04-24 1988-04-23 使水基功能性液体具有极压性能的水溶性添加剂，功能性液体以及含有所述添加剂的浓水基组合物 Expired CN1011595B (zh)

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