CN1087338C - 可生物降解的源于甘油三酯和油溶性铜的润滑剂组合物 - Google Patents

可生物降解的源于甘油三酯和油溶性铜的润滑剂组合物 Download PDF

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CN1087338C
CN1087338C CN97194615A CN97194615A CN1087338C CN 1087338 C CN1087338 C CN 1087338C CN 97194615 A CN97194615 A CN 97194615A CN 97194615 A CN97194615 A CN 97194615A CN 1087338 C CN1087338 C CN 1087338C
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oil
lubricant compositions
copper
acid
triglyceride level
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CN1218497A (zh
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W·W·加米尔
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Renewable Lubricants Inc
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Abstract

本发明揭示一种润滑剂组合物，其包括甘油三酯油润滑剂和油溶剂铜化合物。油溶性铜化合物为对于甘油三酯而言特别有效的抗氧化剂。润滑剂组合物可包括降低磨损的可溶性锌化合物和/或降低磨损并作为降低所需要油溶性铜数量的助抗氧化剂的可溶性锑化合物。较佳的锌和锑化合物为二硫代磷酸锌抗磨/抗氧化剂，二烷基二硫代氨基甲酸锑抗氧化剂助剂。

Description

可生物降解的源于甘油三酯和油溶性铜的润滑剂组合物
发明领域
本发明涉及一种可生物降解的源于植物油甘油三酯和油溶性铜的润滑剂组合物。润滑剂组合物可用于润滑引擎，传动装置，齿轮箱以及水力应用。特定的选择性加入的油溶性锑化合物能减少赋予抗氧化性所需的铜的数量。
背景
植物油甘油三酯已经应用于食品和烹调。许多此类的植物油含有在贮存期间会预防氧化的天然抗氧化剂，例如磷脂和固醇。甘油三酯被视为甘油与3分子羧酸的酯化产物。羧酸内不饱和数量影响甘油三酯氧化的容易程度。氧化反应包括通过在接近不饱和处原子处反应而连结二或多个甘油三酯的反应。这些反应可形成不溶解和褪色的较高分子量物质，例如淤渣。氧化也会造成酯键的裂解或甘油三酯的其它内部裂解。来自裂解的甘油三酯的碎片(分子量较低)更容易挥发。从甘油三酯所产生的羧酸基使润滑剂成为酸性。也会产生醛基。羧酸基会吸引氧化的金属且可将其溶解在油中，从一些表面移走金属。
由于甘油三酯有氧化问题，大部分商用润滑剂是源于不饱和数量较低的石油馏份，使润滑剂可抗氧化。石油馏份需要添加剂以减少磨损，减少氧化，降低凝点和改良粘度指数(以调整高或低温粘度)等。石油馏可抗生物降解，用于调整其特征的添加剂(通常含金属和反应性化合物)更降低所使用润滑剂的生物降解性。
碳碳键中含少量或不含不饱和度的合成酯润滑剂被用于特有品质机油中，这是因为具有所要的性质之故。然而，用于制造合成酯的酸和醇通常衍生自石油馏份而因此并非来自可再生的资源。因此该润滑剂比天然甘油三酯更贵，且更不具生物降解性。
美国专利第4,867,890号揭示用无灰分散剂和二烃基二硫代磷酸锌时可溶性铜化合物在矿物油润滑剂中预防氧化的应用。其中铜的有效量为5-500ppm。
发明概要
使用植物油甘油三酯于润滑油的应用已经受到限制，因为容易受到氧化降解。油溶性铜化合物经证实会赋予植物油甘油三酯抗氧化性，使甘油三酯适合用于多种包括需要较高温度应用的润滑剂组合物，如机油。源于高百分比油酸的甘油三酯的油倾向于被油溶性铜达到更佳的稳定。油溶性铜化合物和油溶性锑化合物的协同效果导致在低可溶性铜含量时达到有效的抗氧化防护。
本发明受美国政府支持(合约号为93-COOP-1-9542)受到美国农业部奖励及美国国防部赞助。
发明详述
本发明中受到铜稳定化的甘油三酯为一或多个下式的甘油三酯
Figure C9719461500061
其中R1，R2和R3为约含7至约23个碳原子的脂肪烃基，其中至少约20，30，40，50或60％的甘油三酯的R基为单不饱和，更佳者，其中约2至高达约90摩尔％的R1，R2和R3基(以甘油三酯的所有此类基的总数为基准)为油酸的脂肪部分。这些甘油三酯可取自多种植物或其种子，一般系称为植物油。
本文所用“烃基”一词代表含有直接连接于分子其余部份的碳原子的基。脂肪烃基包括以下所述：
(1)较佳为脂肪烃基；也就是烷基，例如庚基，壬基，十一烷基，十三烷基，十七烷基；含单一双键的烯基，例如庚烯基，壬烯基，十一碳烯基，十三碳烯基，十七碳烯基，二十一碳烯基；含2或3个双键的烯基，例如8，11-十七碳二烯基和8，11，14-十七碳二烯基。所有这些异构物也包括在内，但是以直链较佳。
(2)取代的脂肪烃基；也就是含非烃取代基者，在本发明中所述取代基不会改变该基的主要烃特性。本领域技术人员会明白合适的取代基；其实例为羟基，烷酯基，(特别是低级烷酯基)和烷氧基(特别是低级烷氧基)，“低级”一词代表含不超过7个碳原子者。
(3)杂原子基；也就是虽然含本发明之主要脂肪烃特性，但是在链或环中含不是脂肪碳原子组成的碳以外的原子。合适的杂原子对本领域技术人员而言系显而易见的，其包括，例如氧，氮和硫。
一般而言，脂肪酸部份(烃基R1，R2或R3加上羧基)为甘油三酯的R1，R2和R3基至少为30，40，50，或60％，较佳至少为70％和最佳至少为80％摩尔为单不饱和。一般向日葵油的油酸含量为25至40％。以基因工程改性向日葵的种子，所得到的向日葵油中的油酸含量占甘油三酯的酸的60％摩尔至约90％摩尔。美国专利第4,627,192号及4,743,402号揭示制备高油酸向日葵油，此部分内容并入本文作为本发明之参考资料。来自基因工程改性植物的油较佳适用于使用温度超过100℃，250℃或175℃者，例如内燃机引擎。例如，只包括油酸的甘油三酯的油酸含量约100％，因此单不饱和含量为100％。由70％油酸(单不饱和)，10％硬脂酸(饱和)，5％棕榈酸(饱和)，7％亚油酸(二-不饱和)和8％十六烷酸(单不饱和)之酸所组成的甘油三酸的单不饱和含量为78％。
可供本发明使用的甘油三酯的实例为经过基因工程改性而含有高于一般油酸含量的植物油。换言之，高比例的R1，R2和R3基为十七烷基，且高比例连接于1，2，3-丙三基-CH2CHCH2-的R1COO-，R2COO-和R3COO-为油酸分子的残基。较佳的甘油三酯油为经过基因工程改性的高油酸(至少60％)甘油三酯油。本发明所采用典型的经过基因工程改性高油酸植物油为高油酸红花油，高油酸谷物油，高油酸菜子油，高油酸向日葵油，高油酸大豆油，高油酸棉花子油，高油酸花生油，高油酸里斯奎拉(lisquerella)油，高油酸美多丰(meadowform)油和高油酸棕榈油精。较佳的高油酸植物油为得自于Helianthus sp.的高油酸向日葵油。此产物可得自于SVO企业(Eastlake，Ohio)，为Sunyl高油酸向日葵油。Sunyl 80为高油酸甘油三酯，其中酸部分包括80％油酸。另一种较佳的高油酸植物油为高油酸菜子油，系得自于Brassica campestris或Brassica napus，也可得自于SVO企业的RS高油酸菜子油。RS 80代表酸部分包括80％油酸的菜子油。也是较佳者为高油酸谷物油以及高油酸向日葵油和高油酸谷物油的掺合物。
必须注意的是，作为植物油的橄榄油也包括在本发明不同具体实施方案中，或可被排除在外。橄榄油的油酸含量典型为65至85％。然而，此含量不是通过基因工程改性而达成，而是由天然形成的。作为此应用的植物油，蓖尔油也可以包括在内或者被排除在外。
另外必须注意的是经过基因工程改性的植物油具备高油酸含量而要牺牲二-和三-不饱和酸，例如亚油酸。一般的向日葵油含20至40％油酸部分以及50至70％亚油酸部分(二-不饱和)，造成90％含量的单-和二-不饱和酸部分(20+70)或(40+50)。经过基因工程改性的植物油含低的二-或三-不饱和部分。本发明经过基因工程改性油含油酸部分：亚油酸部分比例约2至约90。甘油三酯之60％油酸部分含量以及30％亚油酸部分含量，使油酸对亚油酸的比例为2。由80％油酸部分和10％亚油酸部分所构成的甘油三酯油得到的比例为8。由90％油酸部分和1％亚油酸部分所构成的甘油三酯油得到的比例为90。一般向日葵油的比例为0.5(30％油酸部分和60％亚油酸部分)。
上述甘油三酯与商用矿物油(烃)润滑原料比较之下具备许多令人想要的润滑性质。甘油三酯的烟雾点约为200℃，而闪点约为300℃(二者均由AOCS Ce 9a-48或ASTM D1310所测得)。在润滑油中，这会导致排放到环境的有机排放物低以及减少火灾危险。一般而言，烃油的闪点较低。甘油三酯油为极性特性，因此与非极性烃不同。这种现象可以解释甘油三酯被吸附在金属表面上成为非常薄的粘附薄膜的特有能力。薄膜的粘附特性确保润滑作用而薄的特性容许所设计的元件有较小的空间供润滑之用。一项为考察压力和温度作为影响润滑作用的基本因素对置于互为密切关系的滑面的操作而进行的研究，显示甘油三酯形成膜的性质在水力系上更具优势。除此之外，水无法像除去烃薄膜一般地除去金属面上所粘附的甘油三酯油薄膜。
甘油三酯分子结构一般对存在于水力系统中的机械和热应力比矿物油的直链结构稳定。除此之外，极性甘油三酯分子在一般性粘附到金属表面的能力改善这些甘油三酯的润滑性质。唯一可以阻止甘油三酯在所欲水力系统上应用的唯一性质是其容易被氧化的倾向。植物油在作为润滑原料方面对石油矿物油具备实质上的优点，这些优点包括：
(1)可再生—该基本原料为美国农业市场上可再生的来源。
(2)可生物降解—基本流体由于其在酯链结上可以裂解以及在接近碳-碳双链会氧化的能力而会完全的生物降解。
(3)无毒性—基本流体系可消化。此项优点配合生物降解性意味着流体在无法控制的外漏事件中对环境的危害比较不显著。
(4)安全—植物油具备非常高的闪点，平均而言高于290℃(570°F)，降低润滑油发生火灾的危险。
(5)减少引擎的排放量—由于甘油三酯性油的低挥发性和高沸点，较少的润滑油最终变成排放废气而作为颗粒物质。
(6)高粘度指数(HVI)—植物油具备所欲的温度粘度性质，其粘度指数(VI’s)大于200，在升高的引擎温度下有较佳的油粘度控制以及比较不需要昂贵的粘度指数改良添加剂。高粘度指数意味着油在加热之下比较不会变稀。因此，可以使用在室温下的粘度较低者。
(7)改善的燃料经济—燃料经济改善起因于甘油三酯油的磨损力降低。高粘度指数的甘油三酯油允许使用粘度较低的基本原料而能够符合活塞顶环和凹槽较高温度需求，如此会减少油损。
(8)现场润滑薄膜—热或氧化降解造成会粘附到表面的脂肪酸成分而改良抗磨性质。
(9)对污染物和腐蚀性的独特防护—高油酸植物油的化学脂肪酸结构提供独特的天然腐蚀防护能力，固有的清洁剂和溶解性性质。清洁剂和溶解性性质有助于使移动元件免于淤渣和沉积物。
所希望的是上述植物油和/或经过基因工程改性的植物油占至少约20，30，40，50或60％体积的调配润滑剂组合物，更希望的是例如当作为引擎润滑剂使用时，约40至约95或99％体积，较佳约50或60到约90或95％体积的润滑剂。
其它基本润滑流体例如石油馏份产物，异构化或氢裂解油，例如从烃分馏所合成者，聚α烯烃(PAOs)或合成酯油可包括多达30，40，50，60或70体积％，更希望为约1或3至约25％体积的调配润滑组合物。在有目的情况下加入这些可以赋予某些性质或者可以作为其它添加剂的载体而供润滑组合物使用。调配的润滑组合物也可含多达20体积％，更希望约5至约15体积％的润滑剂用添加剂商品。这些包括含金属的抗氧化剂，抗磨损添加剂，清洁剂，抑制剂，无灰分散剂，抗氧化剂锑助剂和凝点抑制剂，例如醋酸乙烯酯与椰子油醇的富马酸酯的共聚物。此润滑剂也可含多达35体积％的粘度指数改性剂，例如烯烃共聚物，聚甲基丙烯酸酯等。润滑组合物可以且通常含其它传统润滑添加剂，例如防锈剂如卵磷脂，山梨糖醇单油酸酯，十二烷基琥珀酸酐或乙氧基烷基酚。
铜抗氧化剂可掺入油中作为任何合适的油溶性铜化合物。所谓油溶性，吾人的意思为该化合物在一般掺合条件下可溶于油中或者溶于润滑剂组合物的添加剂包装中。铜化合物可为二烃基硫代-或二硫代-磷酸铜。类似的硫代和二硫代磷酸锌为熟知者，而硫代-或二硫代-磷酸铜化合物系制备于相应反应，其中1摩尔氧化铜或氧化亚铜可与1或2摩尔二硫代磷酸反应。或者，铜可以合成或天然羧酸的铜盐予以添加。其实例包括C3至C18饱和脂肪酸，例如硬脂酸或棕榈酸，但包括不饱和芳香酸，例如油酸或支链羧酸，例如分子量为200至500的萘酸。以合成的羧酸较佳，因为所得到铜羧酸盐的处理和溶解性质获得改善。较佳的实例包括2-乙基己酸铜，新癸酸铜，硬脂酸铜，丙酸铜，萘酸铜和油酸铜或其掺合物。
铜化合物也可以为式(RR′NCSS)nCu的油溶性二硫代氨基甲酸铜，其中n为1或2，R和R′为相同或不同的含1至18个碳原子，较佳含2至12个碳原子的烃基，包括烷基，烯基，芳烷基和环脂肪基。更优选含2至8个碳原子的烷基。也可以使用磺酸铜，醇盐和乙酰基丙酮盐。在一较佳的具体实施例中，油溶性铜化合物的有机部分没有碳，氢和氧以外的原子。
当与二烷基二硫代磷酸锌一起使用时，油中的铜数量对得到延长寿命的润滑剂所需要的抗氧化剂和抗磨损剂综合性质是很重要的。
较希望的是，润滑剂组合物含有约50至约3000ppm铜，更希望约50或100至约2000ppm，较佳从约100或150至约800ppm或1200ppm，(特别是含锑时)，最佳者约为100或150到约500，600，700或800ppm(以润滑剂组合物重量为基准)。
润滑剂组合物中的油溶性锑化合物可作为助剂抗氧化剂，可将润滑剂中典型所使用油溶性铜数量从约1000ppm至2000ppm减少至约500ppm，而同时保有相同的抗氧化防护。有效的锑化合物为二烷基二硫代氨甲酸锑，例如Vanlube73(R.T.Vanderbilt)，具备下式
Figure C9719461500101
其中R和R′为稍后叙述的烃基，含1至18个碳原子，更佳者含2至12个碳原子。更希望者，烃基为烷基或烯基。二烷基二硫代磷酸锑例如Vanlube622或648(也来自R.t.Vanderbilt)也有效。这些为类似于含下式的二烃基二硫代磷酸锌
Figure C9719461500111
其中R和R′为相同或不同的含1至18个碳，较佳含2至12个碳原子的烃基，例如在锌化合物中所述者。所希望者，烃基为烷基，烯基，芳基，芳烷基，烷芳基或环脂肪基。所希望者，润滑剂中锑浓度约为100至约4000ppm，更希望者为约100至约2000ppm，较佳约100或200至约800或1000ppm的锑(以润滑剂组合物为基准)。润滑剂组合物中较佳的锑化合物的商业制造建议约0.1至约1wt％(600ppm锑)，供抗磨损和/或极压用途为0.1至约5wt％。已经发现可溶性锑化合物的功能为抗磨损剂。如此会降低对造成触媒转化剂中磷中毒的二硫代磷酸锌的需求。
希望使用二烃基二硫代磷酸锌抗磨添加剂(磨损抑制剂)于组合物中，可依照公知技术加以制造，例如首先形成二硫代磷酸，通常系使醇或酚与P2S5反应，然后以合适的锌化合物中和二硫代磷酸。
可以使用醇的混合物，包括伯醇和仲醇的混合物。仲醇一般会赋予改良的抗磨损性质，而伯醇会改善热稳定性质。以上两种的混合物特别有用。一般而言，任何碱性或中性锌化合物均可供使用，但是氧化物，氢氧化物和碳酸盐一般最广为使用。商用添加剂经常含过量的锌，这是因为中和反应中使用过量的碱性锌化合物。
可供本发明使用的二烃基二硫代磷酸锌为二硫代磷酸的二烃基酯的油溶性盐，可由下式代表：
Figure C9719461500112
其中R和R′可为相同或不同的含1至18个碳原子，较佳含2至12个碳原子的烃基，包括如烷基，烯基，芳基，芳烷基，烷芳基和环脂肪。特佳的R和R′基为含2至8个碳原子的烷基。如此，烃基可为乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，戊基，正己基，正庚基，正辛基，癸基，十二烷基，十八烷基，2-乙基己基，苯基，丁苯基，环己基，甲基环戊基，丙烯基，丁烯基等。为了得到油溶性，二硫代磷酸中的碳原子总数(也就是R和R′)一般约为5或更大。所使用二硫代磷酸锌系希望使润滑剂组合物中的锌约为100至约3000ppm，更希望的是锌约500至约2500ppm。使用油溶性锑可减少对油溶性锌的需求。
在公知技术当中，除了二烷基二硫代磷酸锌以外，有时仍需要其它抗氧化剂以改善油的氧化稳定性。这些补充的抗氧化剂在油中的典型数量约为0.5至约2.5wt％。这些补充的抗氧化剂可用于此组合物中，包括酚，位阻酚，双酚和硫化酚，儿茶酚，烷基化儿茶酚和硫化烷基儿茶酚，二苯基胺和烷基二萘基胺，苯基-1-萘胺和其烷基衍生物，烷基硼酸酯和芳基硼酸酯，烷基亚磷酸酯和烷基磷酸酯，芳基硼酸酯和芳基磷酸酯，O，O，S-三烷基二硫代磷酸酯，O，O，S-三芳基二硫代磷酸酯和O，O，S-三取代二硫代磷酸酯(选择性同时含烷基和芳基)，二硫代酸之金属盐，亚磷酸盐，硫化物，肼类，三唑类。
然而，含有少量的铜一般就不需要这些补充的抗氧化剂。但包括补充抗氧化剂在内者落入本发明的范围内，特别是对于那些在此类补充抗氧化剂存在的条件下操作更为有利的油。
油溶性铜的使用可以部分地或者全部地不需要对补充抗氧化剂的需求。经常，在不含额外补充抗氧化剂或者以小于一般浓度用量，例如小于0.5wt％，更常见者为约小于0.3wt％的补充抗氧化剂时，可使得润滑剂组合物具备所要抗氧化剂性质。
润滑剂组合物的分散性可藉由传统润滑油无灰分散剂化合物予以加强，所述化合物为例如长链烃取代的羧酸衍生物，其中烃基含50至400个碳原子。这些一般为含氮的无灰分散剂，连接着相当高分子量脂肪烃油溶解基，或者为琥珀酸/酐的酯，连接着高分子量脂肪烃，系衍生自一元和多元醇，苯酚和萘酚。
含氮分散剂添加剂为那些在本领域中公知的起重机机油的淤渣分散剂。这些分散剂包括矿物油可溶盐，酰胺，酰亚胺，噁唑啉和各种胺的单和二羧酸(及酸酐)的酯，具备胺氮或杂环氮以及至少一种能够形成盐，酰胺，酰亚胺，噁唑啉或酯的酰胺基或羟基的含氮材料。其它可供本发明使用的含氮分散剂包括那些含氮多胺直接连接到长链脂肪烃上的那些，例如美国专利第3,275,554号及3,565,804号所述(一并为本发明之参考资料)，其中卤化烃的卤基被各种亚烷多胺所取代。有关无灰分散剂的其它详细资料在美国专利第4,867,890号中有记载，一并为本发明之参考资料。
本发明很希望使用较佳不含磷和锌的分散抑制添加剂，其包括至少一种金属过碱组合物和/或至少一种羧酸分散剂组合物，二芳基胺，硫化组合物和金属钝化剂(passivator)。分散抑制添加剂的目的系提供机械元件的清洁，抗磨损和极压防护，抗氧化功能和防腐作用。
有机酸的金属过碱盐为本领域技术人员所熟知，一般包括金属盐，其中金属含量超过化学计量。所述此类盐的转化率超过100％(换言之，将酸转化成为其“正常”，“中性”盐所需要的金属超过100％理论数量)。据述此类盐通常含有金属比例超过1(也就是盐中金属当量对有机酸当量之比大于提供正常或中性盐之1∶1化学计量所需要)。它们通常被称为过碱，高碱或超碱盐，常见者为有机硫酸，有机磷酸，羧酸，酚的盐或二或多个混合物。本领域技术人员应理解，也可以使用此类过碱盐的混合物。
先有技术及本发明中的术语“金属比例”一词系指过碱盐中金属的总化学当量对盐中金属化学当量的比例，其会预期造成即将被过碱化的有机酸之间反应，而仿照公知化学反应性与二反应物的化学计量进行金属化合物的碱性反应。在正常或中性盐中，金属比例为1，而在过碱盐中，金属比例大于1。
使用的过碱盐的金属比例通常至少约为3∶1。典型地，其金属比例至少约12∶1。常见的金属比例约超过40∶1。使用的典型盐为金属比例约12∶1至约20∶1。
虽然可以使用其它碱性反应金属化合物，用来制造这些过碱盐的碱性反应金属化合物通常为碱金属或碱土金属化合物(也就是IA，IIA和IIB族金属，不包括钫和镭，典型将铷，锶和铍除外)。钙，钡，镁，钠和锂化合物，例如其低烷醇的氢氧化物和烷氧化物通常被采用于制造这些过碱盐，但是其它如公知技术领域所示被采用者一并为参考资料。含二或多个这些金属离子的混合物的过碱盐可供本发明使用。
过碱盐可为油溶性有机硫酸，例如磺酸，氨基磺酸，硫代硫酸，sulfmic，硫酸部分酯，亚硫酸和硫代硫酸。一般而言，过碱盐为羧酸或脂肪磺酸的盐。有机酸的各种金属过碱盐之进一步资料在美国专利第5,427,700号中有记载，一并为本发明之参考资料。
希望金属钝化剂如甲苯基-三唑或二巯基噻二唑的油溶性衍生物存在于润滑剂组合物中。
可作为制备含二巯基噻二唑核的油溶性衍生物的起始材料的二巯基噻二唑具备以下化学式和名称：
2，5-二巯基-1，3，4-噻二唑
Figure C9719461500141
2，5-二巯基-1，2，4-噻二唑
Figure C9719461500142
3，4-二巯基-1，2，5-噻二唑
Figure C9719461500143
4，5-二巯基-1，2，3-噻二唑
Figure C9719461500144
在这些当中，最容易取得，也是适合本发明目的的较佳者为2，5-二巯基-1，3，4-噻二唑。有时称此化合物为DMTD。然而，应理解的是任何其它二巯基噻二唑可以取代全部或部分的DMTD。
DMTD可方便地在碱性媒介中将1摩尔肼，或肼盐，与2摩尔二硫化碳进行反应，接着进行酸化而制备。
DMTD的衍生物在先有技术中已有记载，任何此类化合物可包括在内。制备一些DMTD衍生物在E.K.Fields“Industrial and EngineeringChemistry”，49，1361-4页(1957年9月)有记载。为了制备油溶性的DMTD衍生物，可以使用已经制备成的TDMD，或者原地制备并接着加入与DMTD反应的原料。对各种金属钝化剂和其制备的进一步资料在美国专利第5,427,700中有记载，一并为本发明之参考资料。
本发明也选择性使用包含粘度指数改性剂的粘度改性组合物，在较高温度之下提供充分的粘度。改性组合物包括含羧基共聚物的含氮酯，该共聚物具备降低的比粘度，约0.05至约2，该酯系实质上不含可滴定的酸性，其特征为其聚合结构中有着下列三种极性侧基至少之一：(A)酯基中至少含8个脂肪碳原子的相对高分子量羧酯基，(B)酯基中含有不超过7个脂肪碳原子的相对低分子量羧酯基，和(C)衍生自含有一个伯或仲胺基的多胺化合物羰基多胺基，其中(A)∶(B)∶(C)的摩尔比例为(60-90)∶(10-30)∶(2-15)。
较佳的粘度改性添加剂的主要成分在于酯为混合酯，换言之，是一种同时存在高分子量酯基和低分子量酯基者，特别是具有上述比例者。同时以粘度改性特征以及其对于在润滑组合物中作为添加剂的增稠效果的观点而言，此类同时存在两种酯基对混合酯的粘度性质十分重要。
参考酯基的大小，酯基系由下式所代表
                       -C(O)(OR)
而酯基碳原子总数为羰基碳原子以及酯基(也就是(OR))碳原子的总数。粘度改性添加剂的进一步资料在美国专利第5,427,700中有记载。一并为本发明之参考资料。
润滑剂组合物包括合成酯基础油。合成酯基础油包括下式的单羧酸
                        R16-COOH
或二羧酸或多羧酸，例如下式的二羧酸
Figure C9719461500151
与下式醇的反应产物
                        R18(OH)m
其中R16为含约5至12个碳原子的烃基，R17为氢或含约4至约50个碳原子的烃基，R18为含1至约18个碳原子的烃基，m为0至约6的整数，n为1至约6的整数。
当R17为氢时，有用的单羧酸为戊酸，己酸，辛酸，壬酸，癸酸，十一烷酸和十二烷酸的异构酸。有用的二羧酸为琥珀酸，顺丁烯二酸，壬二酸，辛二酸，癸二酸，富马酸和己二酸。当R17为含4至约50个碳原子的烃基时，有用的二羧酸为烷基琥珀酸和烯基琥珀酸。可使用的醇包括甲醇，乙醇，丁醇，异构戊醇，异构己醇，癸醇，2-乙基己醇，乙二醇，二甘醇，丙二醇，新戊二醇，季戊四醇，二季戊四醇等。这些酯的特定实例包括己二酸二丁酯，癸二酸二(2-乙基己酯)，富马酸二-正-己酯，癸二酸二辛酯，壬二酸二异辛酯，壬二酸二异癸酯，酞酸二辛酯，酞酸二癸酯，癸二酸二(二十烷)酯，亚麻酸二聚物的2-乙基己基二酯，1摩尔癸二酸与2摩尔四甘醇以及2摩尔2-乙基己醇酸反应所形成的复合酯，1摩尔己二酸与2摩尔衍生自1-丁烯二聚物的氧方法(oxo process)的9个碳原子醇的反应所形成的酯。
实施例
宾州大学的化学工程系磨损学组开发的加速学氧化稳定微反应器系用来试验油的挥发度和氧化稳定性。该试验使用孔深为0.95±0.35毫米的金属块来试验油样品，与恒温热重力分析十分类似，唯一不同的是不溶解淤渣(沉积物)必须分开测定。该装置在J.M.Perez等人在“Diesel DepositForming Tendencies-Microanalysis Methods”SAE paper No.910750(1991)中有记载。一般而言，在225℃测试30分钟相当于在车辆引擎中运转约3000-6000英里，在225℃测试60分钟相当于在车辆引擎中运转约12000英里(6000-20000英里)，依引擎设计以及应用中负载因子而定。任何样品中的液体可藉由胶渗透层析加以评估以得到流体分子量分布对试验试验条件的变化函数资料。低分子量产物因蒸发而损失，较高分子量产物最终形成沉积物。
表1显示对10种植物油进行的加速氧化稳定试验。很明显，克兰(crambe)油具备一些天然抗氧化剂。30分钟试验所形成一般大量沉积物显示此油未经改性之前无法使用于引擎油基本原料。
表2显示铜添加剂对加速天然油氧化稳定性试验的效应。试验时间从表1所示的30分钟延长到1至3小时，显示油溶性铜化合物赋予显著的抗氧化性。铜数量系以ppm表示，显示油溶性铜化合物相关铜的数量。所有1小时的试验结果均可接受，显示稳定化润滑剂组合物具备对车辆引擎用途具备可接受的抗氧化性(约12000英里当量)。含铜的高油酸含量植物油(向日葵，菜子油，大豆，高油酸谷物和谷物)的抗氧化性优于蓖尔油(含高百分比的蓖麻酸，一种单不饱和羟基酸)。此显示可溶性铜化合物和脂肪或烯烃羧酸(特别是油酸)的甘油三酯之间有着某种程度的协同作用。注意表1中蓖尔油中，未添加抗氧化剂的蓖尔油具备优于所有克兰油以外的高油酸油的抗氧化性。表2说明含2000ppm可溶性铜化合物的植物油在车辆引擎应用上有充分的氧化稳定性。
表3说明了可溶性铜化合物提供的稳定性优于传统稳定剂组合物(package)(用于矿物油作为商业用的氧化、抗磨，分散剂等添加剂)，标记引擎油组合物(Eng Pack)以及SG使用等级添加剂组合物(SGPack)。此也包括含氯添加剂之专利品(氯添加剂)，Ketjen lube聚合物(AKZO化学公司)以及K-2300另类商用润滑油添加剂。Eng.Pack，SGPack，含氯添加剂和Ketjen lube添加剂在30分钟作为抗氧化剂具备边际性能，而在60分钟处无法被接受。油溶性铜在30和60分钟提供优良的结果，不管是单独使用或者与其它添加剂一起使用。5体积％的K-2300似乎没有抗氧稳定性。在矿物油中作为抗氧化剂/抗磨损添加剂的二硫代磷酸锌(ZDP)提供含高油酸向日葵油(有或无氯添加剂和/或Ketjen lube)某些抗氧化防护作用。然而，ZDP与铜一起使用时会稍微降低氧化稳定性。如同在此表的最后4个油实例所见者，含氯添加剂专利品当与SG Pack及含铜或不含铜一起使用时会降低氧化稳定性，即使如同在实例4-8所见在不含这些成分时仍可以提供某种程度氧化稳定性。这说明了调配润滑组合物的复杂性。
表4说明经传统抗氧化剂稳定的不含铜植物油和以矿物油为基的机油(10W30和10W40)的加速稳定性试验。其中包含使用过的10W-30植物油润滑剂，在V6 1986 Oldsmobile汽车实际使用249英里。该组合物系用于说明调配后的油可以在汽车引擎操作，在使用之后会有残留的氧化稳定性。在稍后润滑油配方中使用油溶性铜提供超出此处证实的额外氧化稳定性。提供以矿物油为基础的机油资料以作为已商品化及可接受的氧化稳定性对照值。使用非铜抗氧化剂的前两个实例说明空气环境比氮气环境更会造成更多不想要的沉积物。第三个实例显示非铜抗氧化剂在60分钟内造成过量沉积物。多重量(multi-weight)矿物油(10W30和10W40)说明10W30会过度蒸发，而10W40会形成沉积物。相对于这些商用矿物油组合物，后表中经油溶性铜稳定过的植物油具备想要的低沉积物以及低蒸发。
表5说明经含油溶性铜抗氧化剂稳定的油组合物的氧化稳定性。前五个实例说明2000ppm铜的稳定效果在加速氧化试验当中仅仅在3小时后(例如在约180至210分钟)就开始降低。经观察，油溶性铜会增加向日葵油的磨损(抗磨性质降低)，而下五个实例说明合1体积％二硫代磷酸锌(ZDP)的更具抗磨性的油组合物。含铜的克兰，向日葵和谷物油的实例显示较高油酸含量的植物油(克兰和向日葵)比一般谷物油更能达到稳定抗氧化效果。四个含2000，1500，1000和200ppm铜的向日葵样品说明了1000至2000ppm铜在60分钟试验具备所要优良氧化稳定性质。
表5中，含铜和锑的组合物具备一般相当于单独使用铜样品的氧化稳定性。这些含铜和锑的组合物仅含500-600ppm铜和500-600ppm锑就可以发挥相当于含2000ppm铜的氧化稳定性。如此，锑使得在较低铜浓度时发挥作用。因此可以减少金属总ppm量。锑系以二烷基二硫代氨基甲酸锑添加的。使用锑助剂抗氧化剂可避免分散2000ppm油溶性铜的问题及减少油溶性铜对油的不良磨损增加情况。
表6说明许多传统抗氧化剂即在175℃使用(也就是比先前试验低50℃)也不会损害氧化稳定性。表6中的试验系在175℃进行，因大部分抗氧化剂在225℃非常容易挥发，一般知道比可溶铜的效果差。这些抗氧化剂会适合应用于某些低温水力流体方面。
宾州大学化学工程系磨损学组也进行如图1所示的四球磨损试验。其中，球(E)直径为1.27公分，52-100钢球轴承，侧臂(C)支撑球座(D)使其固定，(B)是球座(D)的润滑水平，底部三个球系固定的，热偶(A)测定温度，加热垫(F)控制温度，最上端的球由轴(G)所施以作用力而旋转。此试验方法包括一标准试验方法以及后续试验方法。后续试验方法系补充改良磨损试验以决定在使用特殊润滑剂之下所需要的负载。后续试验中对润滑剂的球特征的磨损如表2所示。典型含添加剂的矿物油磨损如标记为A的上端曲线所示。添加极压添加剂到矿物油会造成类似标记为B的曲线。优良的抗磨添加剂会造成类似C曲线，其中在此实例中进行30分钟之后便没有或者稍微增加磨损。底线D为Hertz弹性变形线，代表球因为在试验操之前的接触压力所造成弹性变形的接触区。表7中的Δ磨损值代表在每一段三个顺序试验之前和之后的磨损痕迹之差异。
表7说明含不同添加剂的植物油和矿物油之磨损性质的差异。比较润滑剂1和2，很明显的发现植物油在作业及稳定状态I和II期间固有地具备较佳的抗磨损性质。比较润滑剂1，2和3时说明油溶性铜会降低植物油的固有抗磨性。来自含1体积％的二硫代磷酸锌(ZDP)的向日葵油润滑剂5说明仅需要少量的二硫代磷酸锌(ZDP)便能达到相当于或优于SAE 10W30矿物油(润滑剂11)的抗磨性。润滑剂6和7说明1体积％ZDP提供优良抗磨性(与SAE 10W30润滑剂11一样优良)。润滑剂8和9说明LB-400极度磨损添加剂不像ZDP一样有效地提供抗磨性，而LB-400的数量会改变其效率。LB-400为磷酯，系一种可自Rhone-Poulonc的抗磨损添加剂的含抗氧化油性铜的植物油在操作或磨损方面的表现均类似或者优于矿物油产物。
如加速氧化试验所显示，二硫代磷锌(ZDP)降低经油溶性铜稳定的植物油的抗氧化性。如同上述油溶性铜增加磨损而ZDP减少磨损(提供抗磨防护)。组合可溶性铜和ZDP提供有效率的低磨损和低氧化的组合物。如同先前所提到的锑化合物也可作为铜和锌化合物的助剂抗氧化剂。油溶性锑可替代部分或全部的油溶性锌，例如(ZDP)。
在许多交通的应用上，例如活塞环和衬里，传动装置，齿轮箱，水力泵，除了优良的减少磨损力和磨损性质之外，润滑剂必须要有极压(极温)性质以防止磨损(scuffing)，轴承磨损而卡死(galling)和会酿成灾害的磨损缺陷。先前所述在磨损力磨损的研究可藉由增加负载直到发生磨损而予以补充磨损评估试验。商用矿物油基础引擎油典型的磨损负载为80kgf或以下。植物油组合物可被调配成为磨损负载超过100kgf。油溶性铜确实会降低磨损负载。来自植物油的脂肪酸不会提高磨损负载，而是会减少磨损力。
表8说明植物油固有抗磨损性与矿物基础原料(石油镏份)相同或更佳。磨损负载为四球磨损试验机(图1所示)需要造成磨损的负载(公斤)(界定为Δ磨损超过20毫米者)。此试验系增加四球磨损试验机的负载直到发生磨损。试验机评估高压迫使润滑剂薄膜变得愈来愈稀时，润滑剂组合物保护金属元件的能力。此性质对活塞环和衬里，传动装置，齿轮箱和水力泵是十分重要的。在抗磨损试验机中，以磨损力对负载作图时，一般可以看到3个直线区。在第一区域中，磨损力随负载直线增加。润滑剂和添加剂控制磨损。在可测得的负载，润滑剂和添加剂无法控制磨损而磨损似更快的速度发展成为大到足以承受负载的磨损痕迹。然后，磨损以介于前二个速度之间的中等速度持续进行，直到发生元件缺陷为止。
表9说明二种不同植物油引擎润滑剂和一种矿物油(石油镏份)商品10W-30的粘度和金属含量。
表1
天然油加速氧化稳定性试验(40μl氧化试验)
温度为225℃，对低碳钢进行微氧化，40μl样品，开放系统30分钟
  样  品   沉积物(重量％)   液体(重量％)     蒸发(重量％)
向日葵油     63     24     13
高油酸向日葵油     52     33     15
蓖尔豆油     45     48     7
高油酸菜子油     55     31     14
沙拉大豆油     68     23     9
大豆油     67     24     9
高油酸谷物油     58     30     12
谷物油     59     31     10
克兰油     10     83     7
油精油     63     30     7
表2
铜添加剂对加速天然油氧化稳定试验的效应
温度为225℃，对低碳钢进行微氧化，40μl样品，开放系统
试验期间          1小时          2小时          3小时
样  品   沉积物重量％   蒸发重量％   沉积物重量％    蒸发重量％   沉积物重量％   蒸发重量％
向日葵油+2000ppm铜     1     3     2.5     6     3.5     9
蓖尔豆油+2000ppm铜     7     1     70     8     80     15
高油酸菜子油+2000ppm铜     1.5     1     4     4     36     8
精制漂白大豆油+2000ppm铜     N/A*     N/A     37     4     N/A     N/A
沙拉大豆油+2000ppm铜     N/A     N/A     60     10     N/A     N/A
高油酸谷物油+2000ppm铜     1     2     17     6     37     10
传统谷物油+2000ppm铜     10     4     60     10     N/A     N/A
*N/A意味着无法取得试验结果
表3
含不同添加剂对向日葵油配剂之加速氧化稳定试验
温度为225℃，低碳钢，样品40μl，开放系统
    样    品              30分钟             60分钟
  沉积物    液体    蒸发   沉积物    液体    蒸发
高油酸向日葵油     52     33     15     N/A     N/A     N/A
  +11体积％Eng.Pack     6     87     7     10     78.5     11.5
  +11体积％SG Pack     5.5     88     6.5     N/A     N/A     N/A
高油酸向日葵油+1.5体积％的60％氯添加剂     8     83     9     47     35     18
  +5体积％Ketjen Lube     6     88     6     22     71     7
  +5体积％K-2300     20     70     10     N/A     N/A     N/A
  +11体积％Eng.Pack     7     89     9     20     69     11
  +11体积％SG Eng.Pack     7.5     83.5     9     21     70     9
向日葵油     63     24     13     N/A     N/A     N/A
    +1体积％的二硫代磷酸锌(ZDP)氧化抑制剂     13     77     10     N/A     N/A     N/A
    +2000ppm铜     0.5     99.5     0     1     1     4
  +2000ppm铜+1％ZDP     1.5     97.5     1     2.5     2.5     7.5
表3(续)
含不同添加剂对向日葵油配剂之加速氧化稳定试验
温度为225℃，低碳钢，样品40μ1，开放系统
  样  品               60分钟             120分钟
沉积物   液体   蒸发   沉积物   液体   蒸发
高油酸向日葵油     63*     24*     13*     N/A     N/A     N/A
    +2000ppm铜     1     95     4     2.5     90.5     6
    +1体积％ZDP     15     75     10     N/A     N/A     N/A
    +2000ppm铜+1体积％ZDP     2.5     90     7.5     11     82     7
高油酸向日葵油+1.5体积％氯添加剂     47     35     18     N/A     N/A     N/A
    +2000ppm铜     1.5     97     1.5     4.5     89.5     6
    +1体积％ZDP     11     76     13     N/A     N/A     N/A
    +2000ppm铜+1体积％ZDP     6     86     8     33     52     14
高油酸向日葵油+1.5体积％的60％氯添加剂+5体积％Ketjenlube     22     71     7     N/A     N/A     N/A
    +2000ppm铜     N/A     N/A     N/A     5.5     86     8.5
    +1％ZDP     6     86     8     37     48     15
    +2000ppm铜+1体积％ZDP     3     89     8     34     51     15
高油酸向日葵油+11体积％SG Pack     10     78.5     7     N/A     N/A     N/A
    含1.5体积％氯添加剂     20     70     10     N/A     N/A     N/A
    +2000ppm铜     3.5     91     5.5     10     75     15
  +1.5体积％氯添加剂+2000ppm铜     6.5     82.5     11     29     51     20
*以30分钟取代60分钟
表4
经传统抗氧化剂稳定的无铜植物油和矿物油机油的加速氧化试验
温度为225℃，低碳钢，干燥气流约20立方公分/分钟
40μl样品
样品     试验条件   重量％沉积物     液体     蒸发
10W-30植物油无铜抗氧化剂(AO)     氮气中30分钟     0.2     71.3     25.2
10W-30植物油无铜抗氧化剂     空气中30分钟     6.4     66.5     31.5
10W-30植物油无铜抗氧化剂     空气中60分钟     16.9     51.9     35.2
使用过的10W-30植物油与无铜抗氧化剂     空气中30分钟     8.2     79.0     17.6
矿物油10W-30无铜抗氧化剂(AO)     空气中30分钟     -0.2     47.5     52.5
矿物油10W-30无铜抗氧化剂(AO)     空气中60分钟     1.5     26.6     71.9
矿物油10W-30无铜抗氧化剂(AO)     空气中120分钟     8.7     6.0     85.3
矿物油10W-40无铜抗氧化剂(AO)     空气中30分钟     0.5     86     13.5
矿物油10W-40无铜抗氧化剂(AO)     空气中60分钟     5.9     74.4     19.7
矿物油10W-40无铜抗氧化剂(AO)     空气中120分钟     17.0     50.9     32.1
表5
经铜稳定的植物油的加速氧化试验
温度为225℃，
样品   试验条件   重量％沉积物     液体     蒸发
向日葵油+2000ppm铜     空气中60分钟     0.7(0.7)    102.8(95.7)     3.9(3.6)
向日葵油+2000ppm铜     空气中120分钟     2.6(2.5)     97.1(91.9)     6(5.7)
向日葵油+2000ppm铜     空气中180分钟     3.4(3.1)     98(89.1)     8.6(7.8)
向日葵油+2000ppm铜     空气中210分钟     52.3(49.2)     43.4(40.8)     10.7(10.1)
向日葵油+2000ppm铜     空气中360分钟     55.5(56.3)     19.2(19.5)     23.9(24.2)
向日葵油+2000ppm铜+1体积％ZDP     空气中30分钟     1.5(1.4)     104(97.7)     1(0.9)
向日葵油+2000ppm铜+1体积％ZDP     空气中60分钟     2.6(2.5)     92.5(89.7)     8(7.8)
向日葵油+2000ppm铜+1体积％ZDP     空气中120分钟     11.2(12.4)     72(80.0)     6.8(7.6)
向日葵油+2000ppm铜+1体积％ZDP     空气中180分钟     27.9(26.6)     61.5(58.6)     15.6(14.9)
向日葵油+2000ppm铜+1体积％ZDP     空气中210分钟     56.3(56.9)     25.2(25.5)     17.5(17.7)
表5(续)
经铜稳定之植物油的加速氧化试验
温度为225℃
样品     试验条件   wt％沉积物     液体     蒸发
克兰+铜     空气中60分钟     5.1     70     24.9
向日葵+铜     空气中60分钟     5.5     67     27.5
谷物+铜     空气中60分钟     14     53     33
向日葵油+2000ppm铜     空气中60分钟     1     99     0
向日葵油+1500ppm铜     空气中60分钟     1.4     98     0.6
向日葵油+1000ppm铜     空气中60分钟     2     94.2     3.8
向日葵油+200ppm铜     空气中30分钟     14     77     9
50％谷物+50％向日葵+550ppm铜+600ppm锑     空气中60分钟     2.6     72     25.4
高油酸向日葵油+550ppm铜+600ppm锑     空气中60分钟     1.4     72     26.6
高油酸向日葵油+铜     空气中60分钟     3.2     70     26.8
*括号内的数目被校正到100％
表6
经传统抗氧化剂稳定的无铜植物油的加速氧化试验
温度为175℃
低碳钢，60分钟，干燥空气20立方公分/分钟，40μl样品
    样  品  重量％沉积物    液体    蒸发
含1％重量双酚的植物油     2     96     2
含1％重量单酚的植物油     2     95     3
含1％重量硫代氨基甲酸酯的植物油     2     97     1
含1％重量萘胺的植物油     2     100     -2
含1％重量苯胺的植物油     2     97     1
含0.5％重量胺型态抗氧化剂的高油酸向日葵油     2     98     -0.5
含1.0％重量胺型态抗氧化剂的高油酸向日葵油     1.5     99     -1
含0.5％重量胺型态抗氧化剂的高油酸向日葵油     0.5     102     -3
表7
油磨损性质比较
四球磨损试验数据：钢对钢，40公斤负载(75℃)，空气中，600rpm
# 润滑剂 操作(30分钟)[毫米] 稳定状态I(+30分钟)[毫米] 稳定状态II(+30分钟)[毫米]
1 向日葵油     0.46(0.16)      0.51(+0.05)      0.55(+0.04)
2 矿物油基础7828     0.54(0.24)      0.64(+0.10)      0.72(+0.08)
3 向日葵油+2000ppm铜     0.56(0.26)磨损     0.57(+0.01)      0.58(+0.01)
4 向日葵油+2000ppm铜     0.67(0.37)磨损      0.81(+0.14)      0.90(+0.09)
5 向日葵油+1体积％ZDP     0.36(0.06)      0.39(+0.03)      0.41(+0.02)
6 向日葵油+200ppm铜+1％ZDP     0.34(0.04)      0.35(+0.01)      0.365(+0.015)
7 向日葵油+2000ppm铜+1％ZDP     0.34(0.04)      0.35(+0.01)      0.36(+0.01)
8 向日葵油+2000ppm铜+0.5％LB-400     0.54(0.24)磨损      N/A      N/A
9 向日葵油+2000ppm铜+2.0％LB-400     0.41(0.11)      0.48(+0.07)      0.54(+0.06)
10 植物性机油10W 30     0.34(+0.04)      0.35(+0.01)      0.36(+0.01)
11 SAE 10W 30     0.37(0.07)      0.40(+0.03)      0.43(+0.03)
12 向日葵或谷物和向日葵+500-600ppm铜+500ppm锑     0.328(0.028)      0.339(0.011)      0.467(0.128)
Δ磨损显示于括号中。
操作中之Δ磨损为最终磨损痕迹和代表球在40公斤负载下的弹性一致性之赫兹直径(Hertz diameter)之间的差异。
稳定状态磨损的磨损是在30分钟稳定状态试验中的磨损痕迹的差异。52-100钢球在40公斤负载时的赫兹直径为0.30毫米。
表8
一些以天然油为基础的润滑剂的极压性质
润滑剂     磨损负载(公斤)
矿物油基础原料7828     40
向日葵油     50
谷物油     50
向日葵油+2000ppm铜     40
向日葵油+氯添加剂+5％K-2300     ＜60
谷物10W30(E-85燃料)     ＞110
向日葵10W30     110
向日葵10W30+2000ppm铜     ＞100
商品SAE 10W30     ＜80
向日葵或谷物和向日葵油掺合物+500-600ppm铜+500ppm锑，1700ppm来自二硫代磷酸锌的锌 160
表9
调配油的典型性质
    油 粘度@100℃ cSt@40℃ 粘度指数 TBN*                     金属含量ppm
  镁   钙   锌   磷   铜   锑
植物油+铜 10.9 58.0 180 9.5 550 1700 1700 1550 2000 0
植物油+铜+锑   9.8   49.0  170   8.0   440   1350   1350   1250   500   600
植物油+铜+锑(含少量二硫代磷酸锌)   9.8   49.0  170   8.0   440   1350   675   625   500   600
商用(矿物)10W-30   11.5   80  140   7.0   550   1400   1400   1300     0     0
*TNB为媒介的中和效率，控制TNB以确保媒介不变酸，酸媒介会腐蚀金属元件N/A表示没有数值
虽然依照专利法规提出最佳模式和较佳具体实施例，本发明的范围并不受其限制，而是由所附权利要求范围加以界定。

Claims (21)

1.一种润滑剂组合物，其包括：
(a)约20至约100％体积的一种或多种下式植物油甘油三酯其中R1，R2和R3各自独立为含7至23个碳原子的脂肪烃基，该一种或多种甘油三酯的烃基的约20至约100％摩尔为单不饱和，和
(b)占该润滑剂组合物重量约50至约3000ppm的铜，该铜为油溶性形式。
2.根据权利要求1的润滑剂组合物，其还包括约500至约2500ppm的锌，该锌为油溶性形式。
3.根据权利要求2的润滑剂组合物，其中该一种或多种甘油三酯的R1，R2和R3组合中约60至约100％摩尔为油酸烯链部分。
4.根据权利要求2的润滑剂组合物，其中该植物油甘油三酯包括经过基因工程改性植物的油，所述植物包含向日葵，红花，谷物，大豆，菜子，克兰(crambe)，里斯奎拉(lesquerella)，花生，棉花子，卡诺拉(canola)，美多丰(meadowfoam)或其混合物。
5.根据权利要求1的润滑剂组合物，其中该铜系以羧酸铜形式加入。
6.根据权利要求5的润滑剂组合物，其中该羧酸铜的羧酸部分不含碳，氧和氢以外的原子。
7.根据权利要求1的润滑剂组合物，其中该铜的数量占该润滑剂组合物重量约100ppm至约800ppm。
8.根据权利要求7的润滑剂组合物，其中该锑以二烷基二硫代氨基甲酸锑形式添加。
9.根据权利要求7的润滑剂组合物，其还包括占该润滑剂组合物约500ppm至约2500ppm的锌，该锌为油溶性形式。
10.根据权利要求8的润滑剂组合物，其还包括占该润滑剂组合物约500ppm至2500ppm的锌，该锌为油溶性形式且以二硫代磷酸锌形式被添加。
11.根据权利要求8的润滑剂组合物，其还包括甲苯三唑(tolutriazole)化合物。
12.根据权利要求7的润滑剂组合物，其中该一种或多种甘油三酯的R1，R2和R3组合中约60至约100％摩尔为油酸烯链部分。
13.根据权利要求12的润滑剂组合物，其中该植物油甘油三酯包括经过基因工程改性植物的油，所述植物包含向日葵，红花，谷物，大豆，菜子，卡诺拉(canola)，克兰(crambe)，花生，棉花子，里斯奎拉(lesquerella)，美多丰(meadowfoam)或其混合物。
14.根据权利要求10的润滑剂组合物，其中该一种或多种甘油三酯的R1，R2和R3组合中约60至约100％摩尔为油酸烯链部分。
15.根据权利要求14的润滑剂组合物，其中该植物油甘油三酯包括经过基因工程改性植物的油，所述植物包含向日葵，红花，谷物，大豆，花生，棉花子，菜子，里斯奎拉(lesquerella)，美多丰(meadowfoam)或其混合物。
16.根据权利要求5的润滑剂组合物，其中该植物油甘油三酯占该润滑剂组合物约40至约99体积％。
17.根据权利要求7的润滑剂组合物，其中该植物油甘油三酯占该润滑剂组合物约40至约99体积％。
18.根据权利要求12的润滑剂组合物，其中该植物油甘油三酯占该润滑剂组合物约40至约99体积％。
19.根据权利要求1的润滑油组合物，其还包括约100至约4000ppm的锑。
20.根据权利要求1的润滑油组合物，其中该一种或多种甘油三酯的R1，R2和R3组合中至少60％摩尔为不包括COOH的油酸部分。
21.根据权利要求19的润滑油组合物，其还包括约100至约4000ppm为油溶性形式的锑。
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