CN1045309C - 硫化水性切削液组合物 - Google Patents
硫化水性切削液组合物 Download PDFInfo
- Publication number
- CN1045309C CN1045309C CN94108478A CN94108478A CN1045309C CN 1045309 C CN1045309 C CN 1045309C CN 94108478 A CN94108478 A CN 94108478A CN 94108478 A CN94108478 A CN 94108478A CN 1045309 C CN1045309 C CN 1045309C
- Authority
- CN
- China
- Prior art keywords
- sulfuration
- water
- cutting fluid
- ester
- based cutting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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Abstract
本发明提供的水性切削液组合物，特别是水性金属加工液组合物，在金属和固体非金属工作件的机械成型和加工中显示出改进的摩擦力降低和改进的压力降低。这些组合物包含a)水，b)硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，以及它们的混合物所构成的一个组，c)硫化烃和d)二烷基二硫代氨基甲酸的脂族酯。
Description
本发明涉及用于金属和固体非金属工作件成型和加工的水性切削液组合物和使用切削液组合物的这类过程，本发明还涉及具有可使切削性能有所改善的含硫组份的水性切削液。
众所周知，油基(即非水性的)已知切削液在技术领域中被长期用于金属加工过程(即将金属进行机械成型和加工的过程)。这种液体在金属加工过程中显示出优异的能减少摩擦和分散热量的润滑和冷却性能，这种摩擦的减少和热的分散延长了工具的使用寿命，增加了生产能力并可获得高质量的金属成品。许多油基金属切削液中含有硫化的油，以便在金属加工过程中达到有效的摩擦力减少。这些硫化的油通常有高的硫含量并在金属加工操作过程中会产生气味问题，特别是在金属加工过程中产生足够热量时。尽管许多油基金属加工液有其有效性，但这类切削液显示出除气味问题外的许多问题，如丢弃问题，因蒸气引起的健康问题，安全问题，材料的可得性问题和价格问题，这些都导致了对水基金属加工液的需求和使用的日益增加。亦已发现水基金属加工液在丢弃、健康、安全和可得性方面问题比油基金属加工液要少。水基金属加工液具有低的火灾危害，通常较易丢弃，与油基金属加工液相比其价格要低许多倍，水基金属加工液尽管具有这些优点，但通常比油基金属加工液显示出较低的性能(即，较低的摩擦减少)。这种较低的性能往往导致生产能力和工具寿命的降低，在金属研磨操作中，这种较低的性能表现在有较大的轮磨损，较低的G-比，轮处理频率增高，较低的产量和部件精加工度较差。
金属加工操作通过切削和非切削过程对金属工作件进行成型和加工，切削过程包括例如，钻孔，研磨，铣削，攻螺丝，车削和拉削。非切削过程包括例如滚压，拉伸，挤压，拉伸和压薄，冲孔，模冲和旋压过程。
水基金属加工液的性能已经有所提高，且需继续提高。由于水基金属加工液有安全，环境和经济方面的优势，因此技术界一直试图改善这种加工液的性能。
因此，本发明的一个目的是为改进的金属和固体非金属工作件的机械成型和加工过程提供一种水性切削液组合物。本发明的另一个目的是提供一种能克服先有技术中的水性金属加工液的缺点的水性切削液组合物。本发明的再一个目的是提供一种能避免先有技术中的非水性的油基金属加工液的缺点的水性切削液组合物，
本发明的水性切削液组合物提供了这些和其它目的，对本技术领域的熟练者而言，可从下列描述和权利要求书中显而易见。现根据本发明提供一种水性切削液组合物，它包括水，由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，以及它们的混合物所组成的一组化合物中选出的一种硫化有机物，硫化烃和二烷基二硫代氨基甲酸的脂族酯。在本文的描述部分和所附的权利要求中所用的切削液组合物一词指用于切削成型及加工金属和固体非金属工作件或物体时与工作件接触的液体组合物。在本文的描述部分和所附的权利要求中所用的术语“工作件”是指待机械成型或进行加工的固体物件，非金属工作件将包括，但并不限于，玻璃，陶瓷和塑料工作件。金属工作件可包括，例如，钢，不锈钢，轧制钢，铁，铸铁，铝，铜，黄铜，钛和各种金属合金工作件或物体。
现已发现由本发明提供的能有效降低摩擦力的水性切削液组合物能减少金属和固体非金属工作件或物体在成型和加工(即切削)时(例如金属切削操作)时所产生的力，延长工具寿命，提高生产力，且能克服先有技术中的水性切削液组合物，特别是水性金属加工液组合物的许多缺点，所述本发明的水性切削液组合物包含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)硫化烃和d)二烷基二硫代氨基甲酸的脂族酯。此外，根据本发明提供的水性切削液组合物包含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1为含1-20个碳原子的脂族基，价态为n,R2和R3分别为含1-20个碳原子的烷基，n为1或2。根据本发明，还提供了水性切削液组合物，它们包含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂族酸及其酯和盐，和它们的混合物，所构成的一个组，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1,R2，和R3定义如上，n为1。根据本发明，还提供了水性切削液组合物，它们包含：a)水，b)硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化的不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1,R2和R3如上所述，n为2。根据本发明，还提供了水性切削液组合物，它们包含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：其中R1为含1-8个碳原子的脂族基，价态为n,R2和R3分别为含1-20个碳原子的烷基，n为1或2。水性切削液组合物包含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化的不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1为含1-20个碳原子的脂族基，价态为n,R2和R3分别为含1-8个碳原子的烷基，n为1或2。根据本发明的水性切削液组合物可含a)水，b)一种硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1为含1-20个碳原子的脂族基，价态为n,R2和R3分别为含1-8个碳原子的烷基，n为1。
R1,R2和R3较好地为烃基，在上式中当n为2时，二烷基二硫代氨基甲酸的脂族酯为双(二烷基二硫代氨基甲酸亚烷基酯)。双(二烷基二硫代氨基甲酸亚烷基酯)在其亚烷基中含1-8个碳原子，在其烷基中含1-20个，较好地为1-10个碳原子，这是较好的二烷基二硫代氨基甲酸的脂族酯。当二烷基二硫代氨基甲酸的脂族酯为单酯时，例如二烷基二硫代氨基甲酸烷基酯时，R1可为含1-20个，较好地为1-10个碳原子的一价脂族基(例如烷基)，R2和R3分别为含1-20个，较好地为1-10个碳原子的烷基。在本发明的另一个实践中，提供一种水性切削液组合物，特别是一种水性金属加工液体组合物，包含a)水，b)一种含6-22个碳原子的硫化不饱和脂族羧酸或其盐，c)一种硫化烃和d)具有下式的二烷基二烷代氨基甲酸的脂族酯：其中R1为含1一20个碳原子，较好地为1-10个碳原子的脂族基，价态为n,R2和R3分别为含1-20个碳原子，较好地为1-10个碳原子的烷基，n为1或2。本发明的实践也提供一种水性切削液组合物，较好地为一种水性金属加工液组合物，包含a)水，b)含1-22个碳原子的脂族羧酸的一种硫化不饱和酯，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1为含1-20个碳原子，较好地为1-10个碳原子的脂族基，价态为n,R2和R3分别为含1-20个碳原子，较好地为1-10个碳原子的烷基，n为1或2。本发明实践也可提供一种水性切削液组合物，较好地为水性金属加工液组合物，它包含a)水，b)一种硫化二聚不饱和脂肪酸或其盐或酯，c)一种硫化烃和d)具有下式的二烷基二硫代氨基甲酸的脂族酯：
其中R1为含1-20个碳原子，较好地为1-10个碳原子的脂族基，价态为n,R2和R3分别为含1-20个碳原子，较好地为1-10个碳原子的烷基，n为1或2。在本发明的组合物的实践中，可用含6-22个碳原子的硫化不饱和脂族羧酸或其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯和硫化二聚不饱和脂肪酸或其盐或酯的混合物作为硫化有机物质，根据本发明的水性切削液组合物可含石油烃油。在本发明的水性切削液组合物的实践中，所选定的a)硫化有机物质应选自含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，b)硫化烃和c)二烷基二硫代氨基甲酸的脂族酯应是水溶性的或水中可分散的。
可用于本发明的实践的含6-22个碳原子的硫化不饱和脂族羧酸可从含1-3个烯键型不饱和基团的脂族一元和二元羧酸按该技术领域中的熟知的方法加以制备，且也就包括了原先羧酸中不存在或存在一些烯不饱和基团的硫化脂族一元羧酸和二元羧酸制品。先有技术中的用于制备硫化不饱和脂族羧酸的方法包括通常在高温和随意地在一种惰性溶剂存在下将这些酸与硫，硫化氢，硫化钠，卤化硫，二氧化硫或类似的硫化剂进行反应的方法。可用于本发明的含6-22个碳原子的硫化不饱和脂族羧酸的实例包括，但不局限于，山梨酸，油酸，亚油酸，亚麻酸，桐酸，十八碳三烯-4-酮酸，蓖麻油酸，棕榈油酸，伞形花子油酸(petroselenic acid)，11-十八碳烯酸，芥酸和硬脂炔酸经硫化而得的硫化产物。含6-22个碳原子的硫化不饱和脂族羧酸的混合物可用作本发明的硫化有机物质，含6-22个碳原子的硫化不饱和脂族羧酸盐(例如，铵盐，胺盐，碱金属盐，碱土金属盐和铜盐)可用于本发明的实践，其实例包括，但不局限于，硫化油酸，亚油酸，山梨酸和蓖麻油酸的铵盐，钠盐，钾盐，钙盐，钡盐和铜盐。
可用作本发明的实践中的硫化有机物质的含1-22个碳原子的脂族羧酸的硫化不饱和酯包括一元，二元或三元醇(例如，乙醇，乙二醇和甘醇)的全酯或偏酯。可赖以制取酯的一元，二元和三元醇包括直链和带支链的饱和和不饱和脂族醇，二醇和三醇及聚乙二醇均聚物和共聚物醇(即，一羟基醇)和二醇(即，二羟基醇)作为醇的部分，以饱和和不饱和羧酸作为酸的部分，其要求是，所得的酯被硫化后能含不饱和性，这些酯可以是天然存在的或由该技术领域中熟知的酯化法合成而得(例如，醇(如乙醇)和不饱和脂族羧酸(如油酸)之间的酸催化酯化反应)。然后该酯与硫化剂如硫，硫化氢，二氧化硫，卤化硫和硫化钠按该技术领域中熟知的和此中先前所述的方法进行反应而被硫化。含1-22个碳原子的脂族羧酸的硫化不饱和酯的例子包括，但不局限于，硫化油酸甲酯，硫化山梨酸己酯，硫化亚麻酸十二烷基酯，和硫化二亚油酸亚乙酯，二蓖麻油酸-1,6-亚己酯，甘油三棕榈油酸酯，聚氧乙烯二油酸酯，聚氧丙烯二山梨酸酯和甘油二亚油酸酯。用于本发明的水性切削液组合物中的含6-22个碳原子的不饱和脂族羧酸的硫化酯可以是一种硫化脂肪或一种硫化脂肪油，而已被硫化的脂肪或脂肪油可以来自动物或植物，这种用于本发明的实践中的硫化脂肪物质的例子包括，但不局限于，硫化牛脂，硫化鲸油，硫化棕榈油，硫化椰子油，硫化的莱籽油，硫化猪油和硫化蓖麻油。天然存在或合成制备的多羟基醇的硫化脂族酸酯可作为本发明实践中的硫化有机物质使用。这种多羟基醇的硫化脂族酸酯可包括亚烷基二醇，聚氧亚烷基二醇和亚烷基三醇的硫化脂肪酸酯，可被硫化而生成对本发明的实践有用的硫化有机物质的不饱和酯的其它例子包括，但不局限于，硬脂酸烯丙酯，亚油酸烯丙酯，丁酸油(基)酯，己酸油(基)酯，和二油酸亚丁酯。用于本发明的硫化脂肪或脂肪油，其硫含量的范围为2％-45％(重量)，较好地，硫的含量范围为10％-20％(重量)，硫化脂肪和硫化脂肪油可按该技术领域中熟知的方法加以制备，例如通常在高温下(例如50℃-350℃)，在惰性溶剂存在或不存在下，使合适的硫化剂如硫，硫化氢，卤化硫，硫化钠或二氧化硫与脂肪或脂肪油反应。硫化甘油或二醇(例如乙二醇)的完全或部分脂肪酸酯可用作本发明的硫化有机物质，从含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物构成的-个组中选出的硫化有机物质在本发明的水性切削液组合物中的可使用的量的范围为0.01％-30％(重量)，较好地为0.5％-20％(重量)。
可作为本发明的硫化有机物质使用的硫化聚合不饱和脂肪酸及其盐和酯通常为从含12-36个碳原子的含烯键的不饱和脂族酸聚合而得的聚合的不饱和脂族酸制得的硫化聚合不饱和脂肪酸。通常，聚合不饱和脂族酸含2-4个单体单元，2-4个羧酸基和剩余的烯不饱和部分。含烯键的不饱和脂肪酸的聚合在该技术领域中是已知的，且这种酸和聚合方法在U.S.Pat.3,256,304中已有披露，含烯键的不饱和脂族酸的这种聚合成二聚体，三聚体和四聚体酸的反应在技术领域中是已知的，且通常被认为生成脂环结构。这样，例如，在文献中曾报道从亚油酸获得的二聚体酸，具有下列可以顺式和反式形式存在的结构：
由含烯键的不饱和脂肪酸制得的二聚体，三聚体和四聚体酸可以商品购得，例如，亚油酸的二聚体可以商品EMPOL 1022购自Emery Industries(EMPOL为Emery Industries的注册商标)，该二聚体酸含2-5％未聚合的亚油酸和19-22％三聚体酸，聚合的含烯键的不饱和脂肪酸含有含烯键的不饱和脂族酸，二聚体酸，三聚体酸和四聚体酸的混合物，其比率视起始的含烯不饱和脂肪酸和聚合反应进行时的条件而变，用技术领域中熟知的前述关于含6-22个碳原子的不饱和脂族羧酸及其酯的方法来硫化聚合不饱和脂族酸。硫化聚合不饱和脂肪酸的盐可包括，但不局限于，铵盐，胺盐，碱金属盐，碱土金属盐和铜盐，铁盐，铝盐和类似的金属盐，可被硫化而生成本发明的硫化有机物质的聚合不饱和酸的酯包括，但不局限于，二聚亚油酸单甲酯，二聚亚油酸二甲酯，二聚亚油酸的单聚亚氧烷基(例如聚氧乙烯)乙二醇酯，二聚亚油酸的酸封端聚氧化烯(例如聚氧乙烯)乙二醇二酯，二聚亚油酸的醇封端聚氧化烯(例如聚氧乙烯)乙二醇酯醇，二聚亚油酸的酸封端聚氧化烯(例如聚氧丙烯)乙二醇多酯，和二聚亚油酸的醇封端聚氧化烯(例如聚氧丙烯氧乙烯)乙二醇多酯。硫化聚合不饱和脂肪酸包括，但不局限于，硫化聚合油酸，硫化聚合亚油酸，硫化聚合月桂烯酸，硫化聚合11-十八碳烯酸，硫化聚合桐酸和硫化聚合亚麻酸。
可用于本发明的硫化烃的例子包括，但不局限于，硫化烯烃，烯烃硫醚，脂族烃硫醚(例如R5-S-R6，其中R5为含1-20个碳原子的烷基，R6为含3-20个碳原子的烷基)和硫化聚烯烃，特别是硫化低分子量的聚烯烃，希望硫化烃具有5％-45％(重量)的硫含量，较好地为32％-42％(重量)。硫化烃可按化学技术中的熟知方法加以制备，在此法的一种方法中，可在100℃-350℃的温度下，在惰性溶剂介质存在或不存在下，且通常在惰性氛围中，将烯烃与硫化剂如硫，硫化氢反应，在本发明的水性切削液组合物中，所用的硫化烃的量为0.01％-50％(重量)。较好的是，在本发明的水性切削液组合物中，硫化烃的含量为1.0％-30％(重量)。
二烷基二硫代氨基甲酸HS-C(=S)-N-(R2)(R3)的各种酯，其中R2和R3定义如前，可用于本发明。双(二烷基二硫代氨基甲酸)亚烷基酯是较好的酯，其例包括，但不局限于，双(二丁基二硫代氨基甲酸)亚甲酯，双(二丙基二硫代氨基甲酸)亚乙酯，双(二丁基二硫代氨基甲酸)亚乙酯，(四亚甲基二硫代氨基甲酸)(二丁基二硫代氨基甲酸)亚乙酯，双(二乙基二硫代氨基甲酸)亚丙酯，双(二丙基二硫代氨基甲酸)亚己酯，双(癸基二硫代氨基甲酸)-1,4-亚丁酯，双(二异丙基二硫代氨基甲酸)-1,8-亚辛酯和双(四亚甲基二硫代氨基甲酸)亚甲酯，可能使用亚烷基中有1-20个碳原子的双(二烷基二硫代氨基甲酸)亚烷基酯。通式为R1-S-C(=S)-N (R2)(R3)的二烷基二硫代氨基甲酸烷基酯，其中R1,R2和R3定义如前，可用于本发明。这种烷基酯的例子包括，但不局限于，二丁基二硫代氨基甲酸甲酯，二丙基二硫代氨基甲酸乙酯，二丁基二硫代氨基甲酸癸酯，二癸基二硫代氨基甲酸己酯，二异丙基二硫代氨基甲酸十八烷基酯，甲基丙基二硫代氨基甲酸辛酯和丙基癸基二硫代氨基甲酸异丁酯。宽范围浓度的二烷基二硫代氨基甲酸酯可被使用于本发明的水性切削液组合物中。按此，使用的二烷基二硫代氨基甲酸酯的浓度范围，为以本发明的水性切削液的总量为基，可为0.01％-30％(重量)，较好地为0.5％-20％(重量)。
业已发现，在水性切削液组合物(即，水性金属加工液流体)中由a)从由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，以及它们的混合物所构成的一个组中选出的一种硫化有机物质，b)硫化烃和c)二烷基二硫代氨基甲酸的脂族酯所成的结合体与单含硫化有机物质，硫化烃或二硫代氨基甲酸脂族酯或其成对的结合体(即3种物质中的任何2种的结合)的水性切削(即金属加工)液组合物相比，能提供更优异的性能，摩擦力的减少有改进，机加工(即金属切削)操作过程中的力则更低了。下述各组份a)从含6-22个碳原子的硫化不饱和脂族羧酸，硫化聚合不饱和脂肪酸及其盐和酯，以及它们的混合物所构成的一个组中选出的硫化有机物质，b)硫化烃和c)二烷基二硫代氨基甲酸的脂族酯所成的各种结合体可用于本发明的水性切削液组合物中。一种这样的结合体可为硫化猪油，烯烃硫醚和双(二丁基二硫代氨基甲酸)亚甲基酯。其它结合体包括，但不局限于，a)硫化鲸油，硫化烯烃和双(二丁基二硫代氨基甲酸)亚乙酯b)硫化棕榈油，烯烃硫醚和双(二丁基二硫代氨基甲酸)亚甲酯，c)硫化椰子油，二异丁基二硫化物和双(二丙基二硫代氨基甲酸)亚乙酯，d)硫化菜籽油，二辛基多硫化物和双(癸基二硫代氨基甲酸)-1,4-亚丁酯，e)硫化猪油，烯烃硫醚和(二丁基二硫代氨基甲酸)丙酯，f)硫化棕榈油，二-十八烷基硫醚和(二丙基二硫代氨基甲酸)癸酯，g)硫化牛脂，十八烷基硫醚和(四亚甲基二硫代氨基甲酸)(二丁基二硫代氨基甲酸)亚乙酯，h)硫化猪油，烯烃硫醚和双(二异丙基二硫代氨基甲酸1,8-亚辛酯，i)硫化猪油，二异丁基二硫化物和(四亚甲基二硫代氨基甲酸)亚甲酯，j)硫化棕榈油，丙基癸基硫醚和双(二乙基二硫代氨基甲酸)-1,12-亚十二烷基酯，k)硫化鲸油，硫化聚烯烃和双(二丁基二硫代氨基甲酸)-1,1-亚乙酯，l)硫化油酸，硫化烯烃和双(二丁基二硫代氨基甲酸)亚甲酯，m)硫化亚油酸，烯烃硫醚和双(二丁基二硫代氨基甲酸)亚乙酯，n)硫化山梨酸，十八烷基硫醚和二丁基二硫代氨基甲酸丙酯，o)硫化十八碳三烯-4-酮酸，二辛基多硫化物和双(四亚甲基二硫代氨基甲酸)亚甲酯，p)硫化芥酸，二异丁基二硫化物和双(癸基二硫代氨基甲酸)-1,4-亚丁酯，q)硫化油酸乙酯，硫化烯烃和双(二丁基二硫代氨基甲酸)亚甲酯，r)硫化山梨酸丙酯，烯烃硫醚和双(二丁基二硫代氨基甲酸)亚乙酯，s)硫化亚油酸辛酯，二异丁基二硫化物和二丁基二硫代氨基甲酸丙酯，t)硫化桐酸癸酯，十八烷基硫醚和(二丙基二硫代氨基甲酸)癸酯，u)硫化酮酸癸酯，十八烷基硫醚和(二丙基二硫代氨基甲酸)癸基酯，v)硫化二油酸亚乙酯，硫化烯烃和双(二丁基二硫代氨基甲酸)亚甲酯，w)硫化二亚油酸亚己酯，烯烃硫醚和双(二丁基二硫代氨基甲酸)亚乙酯，x)硫化聚氧乙烯二油酸酯，硫化烯烃，二异丙基二硫代氨基甲酸辛酯和y)硫化聚氧丙烯二亚油酸酯，十八烷基硫醚和双(二异丙基二硫代氨基甲酸)-1,4-亚丁酯。
本发明的水性切削液组合物可按本技术领域中熟知的常规法来制备，这样，在按本发明制备水性切削液组合物时可按各种次序加入硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，以及它们的混合物所构成的一个组，硫化烃和二烷基二硫代氨基甲酸脂族酯。当使用水可分散的硫化有机物质，硫化烃或二烷基二硫代氨基甲酸脂族酯，有可能需使用表面活性剂或乳化剂以分散任何或所有的这些组分，这样，当使用表面活性剂，乳化剂或其它分散剂时，可在加入任何或所有的硫化有机物质，硫化烃或二烷基二硫代氨基甲酸脂族酸之前，将上述添加剂加至水介质中。或者，在水介质中加入任何或所有这些组份之前，将表面活性剂，乳化剂或其它分散剂与硫化有机物质，硫化烃或二烷基二硫代氨基甲酸脂族酯混合起来，这也是可能的，本技术领域中的熟练者将很易明白，在制备本发明的组合物时，各种操作步骤都可采用，所以希望本发明的水性切削液组合物将不受其制备方式所限制。
可能要在本发明的水性切削液组合物中加入常规量的，本技术领域中熟知的，各种添加剂，例如本技术领域中熟知的腐蚀抑制剂，杀生物剂，杀真菌剂，杀菌剂，表面活性剂，抗氧剂，防沫剂和金属颗粒沉淀剂。
本技术领域中的共同的习惯是，将水性切削液组合物(例如水性金属加工液组合物)以浓缩形式进行配制和运输。这种浓缩形式然后由最终使用者(即，液的使用者)用水稀释至使用浓度并将稀释的液用于机加工操作。浓缩形式的液体通常含少量的水，通常小于10％，然而在制成的并进行运输液体组合物中也可含较大量的水，然后再用水将其稀释至最终使用浓度。配制并运输浓缩形式的水性切削液的优点在于，它避免了将大量的水从液的制造商运至液的使用者，因为使用者能经济地将水加至液中以获得所需的使用浓度。这样，配制并运输浓缩形式的水性切削液组合物比配制及运输最终使用浓度的切削液具有经济上的优势。在本文描述和所附的权利要求部分的文本中，希望并将会明白，本发明的水性切削液组合物包括着浓缩形式，最终使用的释释形式，和居间的所有浓度。
本发明的水性切削液组合物可被使用于通过切削或非切削方法用于机械成型并加工对金属(例如钢)工作件进行机械成型和加工，也可用于固体非金属工作件的机械成型和加工，例如对玻璃和陶瓷工作件的机械切削操作如锯，车削，钻孔和磨，以及对塑料工作件的机械切削成型操作如锯和钻孔。
现举以下非限定性的实施例对本发明作进一步描述，除非另有说明，组份的量都是重量百分数。
实施例1
三乙醇胺 18.00
乳化剂(1) 10.00
新癸酸 0.40
水 71.60
实施例2
2,5-二巯基-1,3,4-噻二唑二钠(2) 6.10
水 93.90
实施例3
硫化猪油(14-16％硫) 6.80
三乙醇胺 18.00
乳化剂(1) 10.00
新癸酸 0.40
水 64.80
实施例4烯烃硫醚(36-39％硫) 2.60三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 69.00
实施例5双(二丁基二硫代氨基甲酸)亚甲酯 3.30三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 68.30
实施例62,5-二巯基-1,3,4-噻二唑二钠(2) 3.05硫化猪油(14-16％硫) 3.40三乙醇胺 9.00乳化剂(1) 5.00新癸酸 0.20水 79.35
实施例72,5-二巯基-1,3,4-噻二唑二钠(2) 3.05烯烃硫醚(36-39％硫) 1.30三乙醇胺 9.00乳化剂(1) 5.00新癸酸 0.20水 81.45
实施例82,5-二巯基-1,3,4-噻二唑二钠(2) 3.05双(二丁基二硫代氨基甲酸)亚甲酯 1.65三乙醇胺 9.00乳化剂(1) 5.00新癸酸 0.20水 81.10
实施例9硫化猪油(14-16％硫) 3.40烯烃硫醚(36-39％硫) 1.30三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 66.9
实施例10硫化猪油(14-16％硫) 3.40双(二丁基二硫代氨基甲酸)亚甲酯 1.65三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 66.55
实施例11烯烃硫醚(36-39％硫) 1.30双(二丁基二硫代氨基甲酸亚甲酯 1.65三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 68.65
实施例122,5-二巯基-1,3,4-噻二唑二钠(2) 2.03硫化猪油(14-16％硫) 2.26烯烃硫醚(36-39％硫) 0.87三乙醇胺 12.00乳化剂(1) 6.67新癸酸 0.27水 74.90
实施例132,5-二巯基-1,3,4-噻二唑二钠(2) 2.03硫化猪油(14-16％硫) 2.26双(二丁基二硫代氨基甲酸)亚甲酯 1.10三乙醇胺 12.00乳化剂(1) 6.67新癸酸 0.27水 75.67
实施例142,5-二巯基-1,3,4-噻二唑二钠(2) 2.03烯烃硫醚(36-39％硫) 0.87双(二丁基二硫代氨基甲酸)亚甲酯 1.10三乙醇胺 12.00乳化剂(1) 6.67新癸酸 0.27水 77.06
实施例15硫化猪油(14-16％硫) 2.26烯烃硫醚 0.87双(二丁基二硫代氨基甲酸)亚甲酯 1.10三乙醇胺 18.00乳化剂(1) 10.00新癸酸 0.40水 67.37
实施例162,5-二巯基-1,3,4-噻二唑二钠(2) 1.53硫化猪油(14-16％硫) 1.70烯烃硫醚(36-39％硫) 0.65双(二丁基二硫代氨基甲酸)亚甲酯 0.83三乙醇胺 13.50乳化剂(1) 7.50新癸酸 0.30水 73.99
实施例17双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化猪油(14-16％硫) 2.26烯烃硫醚(36-39％硫) 0.87三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 67.37
实施例18双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化猪油(14-16％硫) 2.26硫化烯烃(33％硫) 1.01三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 67.23
实施例19双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化猪油(14-16％硫) 2.26二叔壬基多硫化物(40％硫) 0.83三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 67.41
实施例20双(二丁基二硫代氨基甲酸)亚甲酯 1.10Sul-Perm 110(3) 3.50烯烃硫醚(36-39％硫) 0.87三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 66.13
实施例21双(二丁基二硫代氨基甲酸)亚甲酯 1.10Sul-Perm 110(3) 3.50硫化烯烃(33％硫) 1.01三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 65.99
实施例22双(二丁基二硫代氨基甲酸)亚甲酯 1.10Sul-Perm 110(3) 3.50二叔壬基多硫化物(40％硫) 0.83三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 66.17
实施例23双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化菜籽油(10％硫) 3.30烯烃硫醚(36-39％硫) 0.87三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 66.33
实施例24双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化菜籽油(10％硫) 3.30硫化烯烃(33％硫) 1.01三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 66.19
实施例25双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化菜籽油(10％硫) 3.30二叔壬基多硫化物(40％硫) 0.83三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 66.37
实施例26双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化油酸(13％硫) 2.56烯烃硫醚(36-39％硫) 0.87三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 67.07
实施例27双(二丁基二硫代氨基甲酸)亚甲酯 1.10硫化聚乙二醇400二油酸酯(7.9％硫) 4.23烯烃硫醚(36-39％硫) 0.87三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 65.40
实施例28双(二丁基二硫代氨基甲酸)亚甲基酯 1.10硫化油酸(13％硫) 2.56硫化烯烃(33％硫) 0.83三乙醇胺 18.00乳化剂(1) 10.002,2-二甲基辛酸 0.40水 67.11(1)用9.5mol氧乙烷使壬基酚乙氧基化(2)2,5-二巯基-1,3,4-噻二唑二钠的30％水溶液(3)含10％硫，购自Keil Chemical Division of the Ferro corp.的动物和植物脂肪的酯的硫化复杂混合物。Sul-Perm是Keil Chemical Division of the Ferro Corp.的注册商标实施例1-14和16为对比配方，实施例15和17-28为本发明的配方，实施例1-28中的硫含量保持恒定，调节三乙醇胺，乳化剂和新癸酸的量以生成稳定的乳化液。
实施例1-28的配方，在下述金属切削试验步骤中进行了评估，所得结果示于下表中。
实验方法
将楔形高速工具压在1/4英寸厚的旋转的(每分钟95表面呎)SAE 1026钢管的末端，工具的进给压力以能在管壁上切出V-槽为准，削片从切削区排出，成为两件(楔形工具的每一面各成为一份)，工作件的旋转和工具的进给所造成于工具上的压力由连接于Gould记录器的刀架测力计测定，削片在工具上的任何熔接累积反映于削片排出的中断(目测)和工作件旋转阻力的增加。切割试验是系使用3000g循环试验液在工具一削屑界面于全过程中被淹没的情况下加以完成的。工具和工作件在该时间内保持恒定的动态接触，而且在刀刃的每一棱边都达到完全接触之后才开始试验。试验持续3分钟。
用上述实施例所示的配方作成的试验液进行上述试验操作，所得结果列于下表中。实施例号 实施例配方号 压力(磅)
29 1 475
30 2 488
31 3 415
32 4 428
33 5 448
34 6 428
35 7 435
36 8 448
37 9 428
38 10 456
39 11 455
40 12 468
41 13 445
42 14 444
43 15 391
44 16 414
45 17 391
46 18 400
47 19 397
48 20 386
49 21 379
50 22 392
51 23 389
52 24 405
53 25 398
54 26 366
55 27 366
56 28 375
Claims (27)
1．一种水性切削液组合物，以该组合物的重量计，包含a)小于10％-大于75％水，b)0.01-30％硫化有机物质，该物质选自由含6-22个碳原子的硫化不饱和脂族羧酸及其盐，含1-22个碳原子的脂族羧酸的硫化不饱和酯，硫化聚合不饱和脂肪酸及其盐和酯，和它们的混合物所构成的一个组，c)0.01-50％硫化烃，如硫化烯烃，烯烃硫醚，脂族烃硫醚和硫化聚烯烃，和d)0.01-30％二烷基二硫代氨基甲酸的脂族酯，其中脂族基含1-20个碳原子。
2．如权利要求1所述的水性切削液组合物，其特征在于，所述的二烷基二硫代氨基甲酸酯具有下列通式：
其中R1为含1-20个碳原子的脂族基，自由价态为n,R2和R3分别为含1-20个碳原子的烷基，n为整数1或2。
3．如权利要求2所述的水性切削液组合物，其特征在于，R1为含1-20个碳原子的亚烷基，n为2。
4．如权利要求2所述的水性切削液组合物，其特征在于，R1为含1-20个碳原子的烷基，n为1。
5．如权利要求2所述的水性切削液组合物，其特征在于，R1为含1-10个碳原子的烷基，R2和R3分别为含1-10个碳原子的烷基，n为1。
6．如权利要求2所述的水性切削液组合物，其特征在于，R1为含1-10个碳原子的亚烷基，R2和R3分别为含1-10个碳原子的烷基，n为2。
7．如权利要求2所述的水性切削液组合物，其特征在于，硫化有机物质为含6-22个碳原子的不饱和脂族羧酸的硫化酯。
8．如权利要求5所述的水性切削液组合物，其特征在于，硫化有机物质为硫化三酸甘油酯。
9．如权利要求5所述的水性切削液组合物，其特征在于，硫化有机物质为硫化三酸甘油酯，硫化烃为烯烃硫醚。
10．如权利要求5所述的水性切削液组合物，其特征在于，所述的组合物为一种水性金属加工液组合物。
11．如权利要求6所述的水性切削液组合物，其特征在于，硫化有机物质为硫化三酸甘油酯。
12．如权利要求6所述的水性切削液组合物，其特征在于，硫化烃为烯烃硫醚。
13．如权利要求6所述的水性切削液组合物，其特征在于，硫化有机物质为含1-22个碳原子的脂族羧酸的硫化不饱和酯。
14．如权利要求6所述的水性切削液组合物，其特征在于，硫化有机物质为硫化三酸甘油酯，硫化烃为烯烃硫醚。
15．如权利要求13所述的水性切削液组合物，其特征在于，硫化烃为硫化烯烃。
16．如权利要求14所述的水性切削液组合物，其特征在于，亚烷基为亚甲基。
17．如权利要求15所述的水性切削液组合物，其特征在于，亚烷基为亚甲基。
18．如权利要求14所述的水性切削液组合物，其特征在于，所述的水性切削液为水性金属加工液组合物。
19．如权利要求14所述的水性切削液组合物，其特征在于，二烷基二硫代氨基甲酸的脂族酯为双(二丁基二硫代氨基甲酸)亚甲酯。
20．如权利要求6所述的水性切削液组合物，其特征在于，所述的水性切削液为水性金属加工液组合物。
21．如权利要求2所述的水性切削液组合物，其特征在于，所述的水性切削液为浓缩物。
22．如权利要求2所述的水性切削液组合物，其特征在于，硫化有机物质为含6-22个碳原子的硫化不饱和脂族羧酸或其盐。
23．如权利要求2所述的水性切削液组合物，其特征在于，硫化有机物质为硫化聚合不饱和脂肪酸或其酯或盐。
24．如权利要求6所述的水性切削液组合物，其特征在于，硫化有机物质为含6-22个碳原子的硫化不饱和脂族羧酸或其盐，硫化烃为硫化烯烃，二烷基二硫代氨基甲酸酯为双(二丁基二硫代氨基甲酸)亚甲酯。
25．如权利要求6所述的水性切削液组合物，其特征在于，硫化有机物质为硫化聚合不饱和脂肪酸或其酯或盐，硫化烃为硫化烯烃，二烷基二硫代氨基甲酸酯为双(二丁基二硫代氨基甲酸)亚甲酯。
26．如权利要求24所述的水性切削液组合物，其特征在于，硫化有机物质为硫化油酸或其盐。
27．如权利要求25所述的水性切削液组合物，其特征在于，硫化有机物质为硫化聚合亚油酸或其酯或盐。
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| US156323 | 1993-11-23 | ||
| US08/156,323 US5391310A (en) | 1993-11-23 | 1993-11-23 | Sulfurized aqueous machining fluid composition |
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| AU694429B2 (en) * | 1993-08-04 | 1998-07-23 | Lubrizol Corporation, The | Lubricating compositions, greases, and aqueous fluids containing the combination of a dithiocarbamate compound and an organic polysulfide |
-
1993
- 1993-11-23 US US08/156,323 patent/US5391310A/en not_active Expired - Lifetime
-
1994
- 1994-05-19 NZ NZ260556A patent/NZ260556A/xx not_active IP Right Cessation
- 1994-05-27 ZA ZA943732A patent/ZA943732B/xx unknown
- 1994-06-08 AU AU64628/94A patent/AU671211B2/en not_active Expired
- 1994-07-08 CA CA002127680A patent/CA2127680C/en not_active Expired - Lifetime
- 1994-07-14 JP JP16220694A patent/JP3813188B2/ja not_active Expired - Fee Related
- 1994-07-19 DK DK94111265.8T patent/DK0656415T3/da active
- 1994-07-19 DE DE69406092T patent/DE69406092T2/de not_active Expired - Lifetime
- 1994-07-19 EP EP94111265A patent/EP0656415B1/en not_active Expired - Lifetime
- 1994-07-19 ES ES94111265T patent/ES2107093T3/es not_active Expired - Lifetime
- 1994-07-19 AT AT94111265T patent/ATE159043T1/de active
- 1994-07-21 CN CN94108478A patent/CN1045309C/zh not_active Expired - Lifetime
- 1994-09-03 KR KR1019940022185A patent/KR970011369B1/ko not_active Expired - Lifetime
- 1994-10-20 BR BR9404172A patent/BR9404172A/pt not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4485044A (en) * | 1982-02-24 | 1984-11-27 | Ferro Corporation | Sulfurized esters of polycarboxylic acids |
| CN87105448A (zh) * | 1986-08-08 | 1988-04-13 | 切夫尔昂研究公司 | 总碱值高、粘度低的ii族金属的高碱性硫化烷基酚盐 |
| CN1015117B (zh) * | 1987-10-26 | 1991-12-18 | 纳幕尔杜邦公司 | 制造改进的粘结聚酯填絮纤维垫的方法 |
| CN1013592B (zh) * | 1990-05-26 | 1991-08-21 | 冶金工业部钢铁研究总院 | 无氰连续镀铜生产方法 |
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| WO1993011137A1 (en) * | 1991-12-06 | 1993-06-10 | The Lubrizol Corporation | Organophosphoryl borates and lubricants and aqueous fluids containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0656415T3 (da) | 1998-01-12 |
| BR9404172A (pt) | 1995-07-18 |
| EP0656415A1 (en) | 1995-06-07 |
| ZA943732B (en) | 1995-02-06 |
| AU671211B2 (en) | 1996-08-15 |
| US5391310A (en) | 1995-02-21 |
| CA2127680C (en) | 1998-02-17 |
| ES2107093T3 (es) | 1997-11-16 |
| JPH07157793A (ja) | 1995-06-20 |
| JP3813188B2 (ja) | 2006-08-23 |
| NZ260556A (en) | 1995-09-26 |
| CA2127680A1 (en) | 1995-05-24 |
| KR950014277A (ko) | 1995-06-15 |
| DE69406092T2 (de) | 1998-02-26 |
| DE69406092D1 (de) | 1997-11-13 |
| CN1120067A (zh) | 1996-04-10 |
| AU6462894A (en) | 1995-06-01 |
| ATE159043T1 (de) | 1997-10-15 |
| EP0656415B1 (en) | 1997-10-08 |
| KR970011369B1 (ko) | 1997-07-10 |
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