CN1243863A - 润滑油配方 - Google Patents

润滑油配方 Download PDF

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Publication number
CN1243863A
CN1243863A CN99111884A CN99111884A CN1243863A CN 1243863 A CN1243863 A CN 1243863A CN 99111884 A CN99111884 A CN 99111884A CN 99111884 A CN99111884 A CN 99111884A CN 1243863 A CN1243863 A CN 1243863A
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Prior art keywords
lubricating oil
oil composition
weight
class
polymkeric substance
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CN99111884A
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CN1100856C (zh
Inventor
N·奥兹巴利克
S·斯里尼瓦桑
V·J·加托
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Ethyl Corp
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Ethyl Corp
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
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Abstract

具有优良的热和氧化稳定性、抗磨损、抗铜腐蚀并与密封材料良好相容性的润滑油组合物,它包含一种具有a)粘度指数大于110和苯胺点高于110℃和/或b)线型+单环链烷烃含量大于68wt%和至少一种选自烯烃(共)聚合物(类)、聚(甲基)丙烯酸烷基酯(类)及它们的混合物的聚合物。该润滑油组合物特别适于作为手工传动装置和轴润滑剂。

Description

润滑油配方
本发明涉及新的润滑油组合物,该组合物具有优良的热稳定性和氧化稳定性、低温粘流性、抗磨损、抗铜腐蚀以及与密封材料的良好相容性。该润滑油组合物特别适用于作为手工传动装置和轴润滑剂。
工业领域广泛认为,润滑油要获得一定等级的氧化稳定性和热稳定性只能采用全合成配方。本发明的目的在于采用矿物基质油以获得与全合成配方类似的效能,从而使人们认识到昂贵的合成基质油与低廉的矿物基质油之间存在着明显的成本差。
在一篇O′Connor等人发表的题为“轴效率-对合成润滑剂组分的响应”(SAE Paper No.821181)一文中,作者声称:“采用部分的和全合成基质配方的研究表明,与采用常规的石油基质齿轮油相比,其性能获得许多改善。采用全合成基质类配方获得最大效益。”然而该文没有指出采用本发明的矿物基质润滑油配方所获得的效益。
美国专利No.4,758,364涉及一种自动传动流体,包含矿物油或合成油,C2-C10单烯烃聚合物和甲基丙烯酸酯共聚物。该专利没有指出或推荐本发明特指的矿物油。
美国专利No.4,853,139涉及若干润滑油组合物,它们包含一种具有100℃下运动粘度为1.5至50cSt、倾点为-25℃或更低及粘度指数至少为60的基质油;一种具有数均分子量为1,000~8,000的乙烯-α-烯烃共聚物;以及选自下列的至少一种的添加剂:耐特压助剂、抗磨剂、油化剂和洗涤分散剂。该专利没有指出本发明特指的矿物油。
欧洲专利0281060 B1涉及若干用于牵引驱动装置的润滑油组合物,这些组合物包含一种特定的基质油;一种具有数均分子量为800~8,000的乙烯-α-烯烃共聚物;一种具有数均分子量为10,000~100,000的聚甲基丙烯酸酯,以及一种抗磨剂。该专利没有指出本发明特指的矿物油。
欧洲专利0790294 A2涉及若干润滑油组合物,它们包含一种基质油;5~30wt%至少一种具有重均分子量为小于10,000的聚合物;以及2~12wt%的具有重均分子量为大于15,000的一种聚合物。该文献也没有指出本发明特指的矿物油或没有认识到从本发明特指的组合物中所能获得的效益。
本发明涉及一种润滑油组合物,它包含:
(A)一种具有a)粘度指数大于110和苯胺点高于110℃和/或b)
   线型+单环链烷烃含量为68wt%或以上的矿物油;
(B)以润滑油组合物总重量计的约0.1~约40%(重量)的至少一
   种聚合物,该聚合物选自烯烃(共)聚合物(类)、聚(甲
   基)丙烯酸烷基酯(类)及它们的混合物;
(C)以润滑油组合物总重量计的2~25%(重量)的去垢剂/抑
   制剂组合物。
本发明涉及一种润滑油组合物,其中包含:
(A)一种具有a)粘度指数大于110和苯胺点高于110℃和/或
   b)线型+单环链烷烃含量为68wt%或以上的矿物油;
(B)以润滑油组合物总重量计的约0.1~约40%(重量)的至少
   一种聚合物,该聚合物选自烯烃(共)聚合物(类)、聚
   (甲基)丙烯酸烷基酯(类)及它们的混合物;
(C)以润滑油组合物总重量计的2~25%(重量)的去垢剂/抑
   制剂组合物。
在一个实施方案中,本发明的矿物油(A)是加氢处理、加氢裂化和/或异构脱蜡的矿物油,其粘度指数大于110,优选的为110~135,最优选的为110~120;苯胺点高于110℃,优选的为110~126。
在另一个实施例中,本发明的矿物油(A)是加氢处理、加氢裂化和/或异构脱蜡的矿物油,其具有的线型+单环(即非稠环的环烷烃)链烷烃含量为68wt%或以上,这个数值是按照C.J.Robison题为“低分辨质谱测定石油馏份中的芳香烃和饱和烃”(Analytical Chemistry,Vol.43,No.11,September 1971,pp.1425~1434)一文中叙述的分析技术测定的。该质谱方法对于测定石油馏份中高达25种饱和烃和芳烃化合物十分有用。
以润滑油组合物总重量计,矿物油(A)的含量为40~93%(重量),优选的为55~80%(重量)。
适于作为本发明的组分(B)的聚合物包括至少一种选自烯烃(共)聚合物(类)、聚(甲基)丙烯酸烷基酯(类)及它们的混合物之一的聚合物。最好,组分(B)包含聚合物的混合物,其中包含(b′)至少一种烯烃(共)聚合物(类)和(b″)至少一种聚(甲基)丙烯酸烷基酯(类),其中b′∶b″的比值为20∶1~1∶2。在一个优选的实施例中,全配制的油含有0.1~40wt%的烯烃(共)聚合物和0.1~20wt%的聚(甲基)丙烯酸烷基酯。更优选的配方是含有12%~20wt%的烯烃(共)聚合物和1%~6wt%的聚(甲基)丙烯酸烷基酯。
本发明中所用的烯烃(共)聚合物是由C2~C10烯烃经聚合而成的均聚物或共聚物,其数均分子量为1,000~10,000,优选为1,000~3,000,采用凝胶渗透色谱法(GPC)测定。C2~C10烯烃包括乙烯、丙烯、1-丁烯、异丁烯、2-丁烯、1-辛烯和1-癸烯。优选的(共)聚合物类包括聚丙烯、聚异丁烯、乙烯/丙烯共聚物和1-丁烯/异丁烯共聚物。聚异丁烯是最优选的烯烃聚合物。
适用于本发明的聚(甲基)丙烯酸烷基酯(类)是由C1~C30(甲基)丙烯酸酯经聚合而制得的。这些聚合物的制备还可包括采用含氮官能团、含羟基和/或烷氧基的丙烯酸单体,这些官能团为聚(甲基)丙烯酸烷基酯提供额外的性质,如改善分散性。聚(甲基)丙烯酸烷基酯类的数均分子量为10,000~250,000,优选的是20,000~200,000。聚(甲基)丙烯酸烷基酯(类)可采用常规的自由基或阴离子聚合法制备。
本发明所用的去垢/抑制剂(DI)组合物可含有一种或多种常用的添加剂,它们可选自下列一组添加剂:分散剂、流化剂、摩擦改良剂、缓蚀剂、防锈剂、抗氧剂、去垢剂、密封膨胀剂、耐特压添加剂、抗磨剂、倾点下降剂、除臭剂、消泡剂、破乳剂、染料和荧光着色剂。DI组合物的用量为润滑油组合物总重量的2~25%(重量)。
本发明所用的分散剂包含至少一种油溶性的无灰份分散剂,其分子中具有碱性氮和/或至少一个羟基。适用的分散剂包括链烯基琥珀酰亚胺、链烯基琥珀酸酯、链烯基琥珀酸酯-酰胺、曼尼期碱、烃基多胺或聚多胺。
琥珀基中含至少30个碳原子的烃取代基的链烯基琥珀酰亚胺在诸如美国专利Nos.3,172,892;3,202,678;3,216,936;3,219,666;3,254,025;3,272,746;和4,234,435中均有叙述。链烯基琥珀酰亚胺可用常规方法制得,例如将链烯基琥珀酸酐、酸、酸-酯、酰氯或其低级烷基酯与含至少一个伯胺基的多胺一起进行加热。通过将烯烃与马来酸酐的混合物加热至例如180~220℃的方法可很容易制得链烯基琥珀酸酐。优选的烯烃是由低级单烯烃,如乙烯、丙烯、1-丁烯、异丁烯等及它们的混合物聚合而得到的聚合物或共聚物。更优选的链烯基来源是聚异丁烯,其凝胶渗透色谱法(GPC)测得的数均分子量为10,000或更高,优选的范围是约500~约2,500,最优选的范围是约800~约1,200。
此处所用的术语“琥珀酰亚胺”指的是包含由一种或多种多胺反应物与烃取代的琥珀酸或其酸酐(或类似的琥珀酰化试剂)的完全反应产物;该术语还意指包含这样一类化合物,其中该反应产物除了伯胺基与酸酐部分反应而产生的一类酰亚胺键外还可含有酰胺、脒和/或盐键。
含2~20个碳原子和2~6个羟基的多羟基醇与链烯基琥珀酸生成的酯和二酯可用于制备含磷无灰份的分散剂。代表性例子在美国专利Nos.3,331,776;3,381,022和3,522,179中均有叙述。这些酯类的链烯基琥珀基部分与上述琥珀酰胺中的链烯基琥珀基部分结构相同。
适用于制备含磷无灰份分散剂的链烯基琥珀酯-酰胺例如在美国专利Nos.3,184,474;3,576,743;3,632,511;3,804,763;3,836,471;3,862,981;3,936,480;3,948,800;3,950,341;3,957,854;3,957,855;3,991,098;4,071,548;和4,173,540中均有叙述。
可被磷酸化的烃基多胺分散剂通常的制备方法是将平均含至少约40个碳子的脂族或脂环族卤化物(或其混合物)与一种或多种胺,最好是聚亚烷基多胺进行反应。这类烃基多胺分散剂的例子在美国专利Nos.3,275,554;3,394,576;3,438,757;3,454,555;3,565,804;3,671,511;和3,821,302中均有叙述。
通常,烃基取代的多胺是分子中含碱性氮的高分子量的烃-N-取代的多胺。典型的烃基的数均分子量为约750~10,000,由GPC测得,更通常的数均分子量为约1,000~5,000;它们由合适的聚烯烃衍生而来。优选的烃基取代的胺或多胺是从聚异丁烯基氯和含有2~约12个胺氮原子和2~约40个碳原子的多胺制备的。
优选的曼尼期碱分散剂是在环上具有典型长链烷基取代基的烷基酚与一种或多种含1~约7个碳原子的脂族醛类(尤其是甲醛及其衍生物)以及多胺(尤其是聚亚烷基多胺)反应的产物。曼尼期缩合产物的例子及其制备方法在美国专利Nos.2,459,112;2,962,442;2,984,550;3,036,003;3,166,516;3,236,770;3,368,972;3,413,347;3,442,808;3,448,047;3,454,497;3,459,661;3,493,520;3,539,633;3,558,743;3,586,629;3,591,598;3,600,372;3,634,515;3,649,229;3,697,574;3,703,536;3,704,308;3,725,277;3,725,480;3,726,882;3,736,357;3,751,365;3,756,953;3,793,202;3,798,165;3,798,247;3,803,039;3,872,019;3,904,595;3,957,746;3,980,569;3,985,802;4,006,089;4,011,380;4,025,451;4,058,468;4,083,699;4,090,854;4,354,950;和4,485,023,中均有叙述。
制备曼尼期多胺分散剂优选的烃源是由基本上饱和的石油馏份和烯烃聚合物,优选含有2~约6个碳原子的单烯烃聚合物衍生而来。烃源一般含有至少约40个、优选的至少约50个碳原子,以便使分散剂具有基本的油溶性。从容易反应和低成本考虑,应优选具有GPC数均分子量为约600~5,000的烯烃聚合物。但是,较高分子量的聚合物也可使用。特别合适的烃源是异丁烯聚合物。
本发明所用的优选的曼尼期碱分散剂是由约1摩尔的长链烃取代的酚与约1~2.5摩尔的甲醛和约0.5~2摩尔的聚亚烷基多胺进行缩合而制得的曼尼期碱无灰份分散剂。
适于作为本发明无灰份分散剂的聚多胺分散剂是一类含有碱性胺基和油溶性基团(例如具有至少约8个碳原子的烷基侧基)的聚合物。用以说明这类物质的例子有由诸如甲基丙烯酸癸酯、乙烯基癸基醚或较高分子量的烯烃等各种单体与丙烯酸氨烷基酯和氨烷基丙烯酰胺生成的共聚物。聚多胺分散剂的例子在美国专利Nos.3,329,658;3,449,250;3,493,520;3,519,565;3,666,730;3,687,849;和3,702,300中均有叙述。
上述各种类型的无灰份分散剂可按照美国专利Nos.3,184,411;3,342,735;3,403,102;3,502,607;3,511,780;3,513,093;3,513,093;4,615,826;4,648,980;4,857,214;和5,198,133中所述方法进行磷酸化。
本发明的分散剂也可进行硼化。对上述各种无灰份分散剂进行硼化(硼酸化)的方法在美国专利Nos.3,087,936;3,254,025;3,281,428;3,282,955;3,284,409;2,284,410;3,338,832;3,344,069;3,533,945;3,658,836;3,703,536;3,718,663;4,455,243和4,652,387中均有叙述。
对上述一类无灰份分散剂进行磷酸化和硼化的优选方法在美国专利Nos.4,857,214和5,198,133中均有叙述。
按“活性组份基质”(即排除其中与之相关的杂质,稀释剂和溶剂的重量)计算的无灰份分散剂的含量通常为约0.5~约7.5重量百分数(wt%),典型的为约0.5~5.0wt%,优选的为约0.5~约3.0wt%,最优选的为约2.0~约3.0wt%,以上重量百分数均以成品润滑油为基准计。
在本发明中也可使用流化剂。合适的流化剂包括油溶性二酯类。优选的二酯包括C8~C13烷醇(或其混合物)的己二酸酯、壬二酸酯、癸二酸酯和C4~C13烷醇(或其混合物)的邻苯二甲酸酯。两种或两种以上不同种类的二酯混合物(例如己二酸二烷酯与壬二酸二烷酯等)也可使用。这类材料的例子包括己二酸、壬二酸和癸二酸的正辛基、2-乙基己基、异癸基和十三烷基二酯和邻苯二甲酸的正丁基、异丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和十三烷基二酯。
一般能赋于等效性能的其它酯类还有多元醇的酯类,例如由EmeryGroup of Henkel Corporation生产的Emery 2918,2939和2995酯类以及Hatcol 2926,2970和2999。
为了某种应用目的,在成品润滑油配方中加入一种或多种摩擦改良剂或许是理想的。合适的摩擦改良剂包括下列一类化合物,它们是:脂族胺或乙氧基化脂族胺、脂族脂肪酸酰胺、脂族羧酸、脂族羧酸酯、脂族羧酸酯-酰胺、脂族膦酸酯、脂族磷酸酯、脂族硫代膦酸酯脂族硫代磷酸酯或它们的混合物。典型的脂族基团含有至少约8个碳原子,以赋于化合物合适的油溶性。由一种或一种以上的脂族琥珀酸或其酸酐与氨反应所生成的脂族取代的琥珀酰亚胺也是适用的。
一组优选的摩擦改良剂包括N-脂族烃取代的二乙醇胺,其中N-脂族烃取代基至少是一个无乙炔不饱和键且具有约14~约20个碳原子的直链脂族烃基。
优选的摩擦改良剂混合物包括由至少一种N-脂族烃取代的二乙醇胺和至少一种N-脂族烃取代的三亚甲基二胺构成的混合物,其中N-脂族烃取代基至少是一个无乙炔不饱和键且具有约14~约20个碳原子的直链脂族烃基。涉及这种摩擦改良剂体系的细节在美国专利Nos.5,372,735和5,441,656中均有叙述。
另一优选的摩擦改良剂混合物是由下列(i)和(ii)构成的混合物,其中,(i)至少一种二羟烷基脂族叔胺,其中羟烷基是相同的或不同的,每一羟烷基含2~约4个碳原子,且其中脂族基是含约10~约25个碳原子的环烃基,(ii)至少一种羟烷基脂族咪唑啉,其中羟烷基含2~约4个碳原子,且其中脂族基是含约10~约25个碳原子的环烃基。有关该摩擦改良剂体系的更多细节应参见美国专利No.5,344,579。
可用于本发明的另一类摩擦改良剂包括化学式如下的化合物:
Figure A9911188400121
Figure A9911188400122
式中Z是R1R2CH-基,其中的R1和R2各自独立地是含1~34个碳原子的直链或支化链烃基,且R1和R2基中的碳原子总数为11~35。基团Z可以是例如1-甲基15烷基,1-丙基13碳烯基,1-戊基13碳烯基,1-13碳烯基15碳烯基或1-14烷基二十碳烯基。优选的是,R1和R2基团中的碳原子数为16~28,更常见的为18~24。特别优选的是,R1和R2中的碳原子总数为约20~22。一种优选的摩擦改良剂是该分子式所示的琥珀酰亚胺,其优选的琥珀酰亚胺是3-C18~24链烯基-2,5-吡咯烷二酮,即在链烯基中含有平均原子数为18~24的化合物。
这些化合物均有市售,或者也可应用或采用已知技术制得(例如参见EP 0020037和美国专利Nos.5,021,176;5,190,680及RE-34,459,此处引为参考)。
摩擦改良剂的使用是任选的。但是,在使用摩擦改良剂的应用领域,本发明的组合物将含有多达约1.25wt%、优选的为约0.05~约1wt%的一种或一种以上的摩擦改良剂。
本发明的润滑油组合物还典型地含有某些抑制剂。这些抑制剂的组份具有不同功能,包括抑制锈蚀、抑制腐蚀和抑制起泡。抑制剂可以以预制的添加剂组合物的形式引入,这种组合物可额外地含有一种或一种以上本发明组合物中所用的其它组份。或者说,抑制剂组份可以单独地或以不同的次组合方式引入。虽然抑制剂含量可在合理范围内变动,但本发明的成品流体中抑制剂的典型总含量约为0~约15wt%,它以“活性组份基重”为重量基数,即排除惰性物质如通常与之有关的溶剂或稀释剂后的重量为基数计算的。
抑泡剂构成适于作为本发明组合物抑制剂组份的一类抑制剂。这些包括硅氧烷、聚丙烯酸酯类、表面活性剂等等。
铜腐蚀抑制剂构成另一类适于作为本发明组合物的添加剂。这类化合物包括噻唑类、三唑类和噻二唑类。这类化合物的例子包括苯并噻唑、甲苯基三唑、辛基三唑、癸基三唑、十二烷基三唑、2-巯基苯并噻唑,2,5-二巯基-1,3,4-噻二唑,2-巯基-5-烃硫代-1,3,4-噻二唑、2-巯基-5-烃二硫代-1,3,4-噻二唑,2,5-双(烃硫代)-1,3,4-噻二唑和2,5-双(烃二硫代)-1,3,4-噻二唑。优选的化合物是1,3,4-噻二唑类(许多这些化合物均有市售),以及三唑类如甲苯基三唑与1,3,5-噻二唑,如2,5-双(烷基二硫代)-1,3,4-噻二唑的组合物。市售的这类物质有Cobratec TT-100和HiTEC314 additive和HiTEC 4313 additive(Ethyl Petroleum Additives,Inc.)。1,3,4-噻二唑类通常由肼与二硫化碳按已知方法合成。例如参见美国专利Nos.2,765,289;2,749,311;2,760,933;2,850,453;2,910,439;3,663,561;3,862,798;和3,840,549。
锈蚀或腐蚀抑制剂构成本发明所用的另一类抑制添加剂。这类材料包括单羧酸和多羧酸。合适的单羧酸的例子有辛酸、癸酸和十二烷酸。合适的多羧酸包括由妥尔油脂肪酸、油酸、亚油酸等制成的二聚体和三聚体酸。这类产品当前均可从市面购得,例如Humko ChemicalDivision of Witco Chemical Corporation以HYSTRENE商品注册名销售的和Henkel Corporation以EMPOL商品注册名销售的二聚体和三聚体酸。另一类在本发明实施中有用的一类有效的锈蚀抑制剂包括链烯基琥珀酸和链烯基琥珀酸酐腐蚀抑制剂,例如四聚丙烯基琥珀酸、四聚丙烯基琥珀酸酐、十四碳烯基琥珀酸、十四碳烯基琥珀酸酐、十六碳烯基琥珀酸、十六碳烯基琥珀酸酐等。还有一类有用的抑锈剂是在链烯基中有8~24个碳原子的链烯基琥珀酸与聚乙二醇一类的醇生成的半酯。其它合适的锈蚀或腐蚀抑制剂包括醚胺类;酸式磷酸酯类;胺类;聚乙氧基化类化合物,例如乙氧基胺类、乙氧基酚类和乙氧基醇类;咪唑啉类;氨基琥珀酸类或其衍生物类等。这类物质均有市售。也可使用这类锈蚀或腐蚀抑制剂的混合物。
在本发明的润滑油配方中也可含有抗氧剂。合适的抗氧剂包括酚类抗氧剂、芳胺类抗氧剂、硫代酚类抗氧剂、有机亚磷酸酯类,等等。酚类抗氧剂的例子包括2,6-二叔丁基苯酚、叔丁基化酚类的液体混合物,2,6-二叔丁基-4-甲基苯酚,4,4′-亚甲基双(2,6-二叔丁基苯酚),2,2′-亚甲基双(4-甲基-6-叔丁基苯酚),混合桥亚甲基多烷基酚类和4,4′-硫代双(2-甲基-6-叔丁基苯酚)。N,N′-二-仲丁基-对苯二胺、4-异丙基氨基二苯基胺、苯基萘胺以及环烷基化的二苯基胺作为芳香胺抗氧剂的例子。最优选的是具有空间位阻的叔丁基化酚类、环烷基化的二苯胺类及它们的混合物。
所用的抑制剂各成份的含量某种程度上取决于各该成份的组成及这些成分在成品组合物中的效用。但是一般而言,成品流体将典型地含有如下所列的抑制剂各成分(活性组份基质)的浓度(重量百分数):
抑制剂 典型范围 优选范围
抑泡剂 0至0.1 0.01至0.08
铜腐蚀抑制剂 0至1.5 0.01至1
抑锈剂 0至0.5 0.01至0.3
抗氧剂 0至1 0.1至0.6
在本发明实施中可以使用各种含硫抗磨剂和/或耐特压助剂。这些助剂的例子有二烃基多硫化物类、硫化烯烃类、天然和合成的硫化脂肪酸酯类、三硫酮类、硫化噻吩衍生物类、硫化萜烯类、C2~C8单烯烃的硫化齐聚物类,以及硫化Diels-Alder加合物,如美国再公布专利Re27,331所公开的那些。具体例子包括硫化聚异丁烯、硫化异丁烯、硫化二聚异丁烯、硫化三聚异丁烯、二环己基多硫化物、二苯基多硫化物、二苄基多硫化物、二壬基多硫化物以及二叔丁基多硫化物的混合物,如二叔丁基三硫化物、二叔丁基四硫化物和二叔丁基五硫化物的混合物,等等。也可使用这类含硫的抗磨和/或耐特压助剂的混合物,例如硫化异丁烯和二叔丁基三硫化物的混合物、硫化异丁烯和二壬基三硫化物的混合物、硫化妥尔油和二苄基多硫化物的混合物。
为本发明需要起见,在化学结构中同时含有磷和硫的组份被认为是含磷的抗磨和/或耐特压助剂而不称为含硫的抗磨和/或耐特压助剂。
也可使用各种各样的含磷油溶性抗磨和/或耐特压助剂,例如油溶性有机磷酸酯类、有机亚磷酸酯类、有机膦酸酯类、有机亚膦酸酯等以及它们的含硫同系物。本发明中也可使用这样一类含磷抗磨和/或耐特压助剂即那些既含磷又含氮的化合物。可用于本发明的含磷油溶性抗磨和/或耐特压助剂包括美国专利Nos.5,464,549;5,500,140和5,573,696中所叙述的那类化合物,这些专利的公开说明此处引为参考。
有一类含磷含氮的抗磨和/或耐特压助剂可用于本发明的实施方案中,这类含磷含氮的组合物在英国专利1,009,913;G.B.1,009,914;美国专利3,197,405和/或3,197,496中均有叙述。一般而言,这些组合物的制备方法是,将硫代磷酸的羟代三酯与无机磷酸、氧化磷或卤化磷反应制成酸性中间体,然后再用胺或羟基取代的胺对这种酸性中间体的主体部分进行中和。在本发明组合物中可用的另一类含磷含氮抗磨和/或耐特压助剂包括羟基取代的磷杂丁环的胺盐或羟基取代的硫代磷杂丁环的胺盐和磷酸及硫代磷酸部分酯的胺盐。
某些助剂组份是以活性成分溶于惰性稀释剂或溶剂如稀释油中的溶液形式供应的。除非作为对照另加说明外,每一助剂组份含量和浓度均以活性助剂表示,即可能与这些组份相关的溶剂或稀释剂用量均排除在外。
由于其优良的热稳定性和氧化稳定性、抗磨损性、低温粘流性、抗铜腐蚀及与密封材料的相容性,本发明的润滑油组合物特别适于作为手工传动装置的润滑油和轴润滑油。
在本发明的一个实施方案中,该润滑油组合物是一种手工传动装置用的润滑油。一种优选的手工传动装置用的润滑油配方含有DI组合物,它包含无灰份分散剂,至少一种抗氧剂和至少一种抑制剂。优选的DI组合物为成品油提供0.2~5wt%无灰份分散剂(类)、提供0~1.0wt%、优选的为约0.2~1.0wt%抗氧剂(类)、提供0.01~2wt%选自铜腐蚀抑制剂、锈蚀抑制剂及它们的混合物之一的抑制剂(类)。优选的手工传动装置用的润滑油配方含有0~5wt%硫和30~5000ppm磷,两者均以润滑油配方总重量计。
在本发明的另一实施方案中,该润滑油组合物是一种轴润滑油。一种优选的轴润滑油配方含有DI组合物,它包含含硫的耐特压助剂、至少一种含磷的抗磨剂、至少一种无灰份分散剂和至少一种抑制剂。更优选的DI组合物为成品油提供3~15wt%的含硫耐特压助剂(类)、2~10wt%的含磷抗磨剂(类)、0.2~5wt%的无灰份分散剂和0.01~2wt%的选自铜腐蚀抑制剂(类)、抑锈剂(类)及它们的混合物之一的抑制剂。优选的轴润滑配方包含0.5~5wt%的硫和200~5000ppm的磷,两者均以润滑油配方的总重量计。
聚α-烯烃(PAOs)在润滑油组合物总重量中的含量可达40%。但是,因本发明之矿物油基的润滑油具有优良的热稳定性和氧化稳定性,优选的配方是,该润滑油组合物含有低于10wt%、更优选的低于5wt%的聚α-烯烃。在最优选的实施方案中,该润滑油组合物中没有聚α-烯烃。
本发明优选配制的润滑油中所用的各组份比例应满足该组合物在100℃下的运动粘度至少为13.5cSt,优选的为至少15.9cSt的要求。在本发明的一个优选实施例中,全配制的油在20小时锥形轴承剪切测试中其最大粘度降为15%或低于15%。锥形轴承测试法是公开发表于题为“传动润滑油粘度剪切稳定性”一文中的标准测试方法,在CECL-45-T-93中有所叙述,而且也发表于DIN 51350,第6部分中。当本发明配制的润滑油用于作为轴或手工传动装置润滑油时,其优选的配方是使其具有-40℃下的Brookfield粘度小于150,000cP,优选的小于130,000cP。
实施例
本发明的润滑油组合物具有优良的热稳定性和氧化稳定性。表1说明采用本发明权利要求范围内的一种基质油和VII混合物所获得的意料之外的超水平的热稳定性和氧化稳定性。表1列出了三种配制的润滑油在300小时的L-60-1测试中的结果。L-60-1测试测定了润滑油在苛刻氧化条件下的劣化结果。表中的全部润滑油均含有11wt%的DI助剂组合物(包括稀释油),9.5wt%的数均分子量为2100的聚异丁烯,5.5wt%的数均分子量为38,000的聚甲基丙烯酸酯,24wt%的4厘沲(cSt)的PAO,10wt%的100cSt的PAO和40wt%的矿物基油。测试了三种不同的矿物油,它们的物理性质列于表1的脚注中。表1    300小时L-60-1测试结果
矿物油 运动粘度(100℃) 油泥 粘度增加(%) 戊烷不可溶物(%)   甲苯不可溶物(%)
 A(本发明Inv) 14.60 9.75 83.91 0.17 0.01
 B(对比) 15.03 9.44 103.26 0.22 0.08
C(对比) 14.92 9.36 117.29 0.20 0.14
矿物油A:粘度指数(VI)115;苯胺点113℃;线型+单环脂肪烃含
     量73.9。矿物油B:粘度指数(VI)101;苯胺点108℃;线型+单环脂肪烃含
     量64.7矿物油C:粘度指数(VI)100;苯胺点107℃;线型+单环脂肪烃含
     量62.3。
采用本发明范围内的矿物油(矿物油A)所配制的润滑油与采用本发明范围外的矿物油(矿物油B和C)所配制的润滑油相比,前者具有更好的热稳定性和氧化稳定性,因为从其明显低的粘度增加值即获得证明。
另一个测试用以显示本发明的润滑油组合物的热/氧化稳定性。将三种配制的润滑油在164℃下用10.0升/小时干燥空气喷吹,经历表2中所列的不同时间。这些配制的润滑油的区别仅在于采用不同的矿物基质油。该配制的润滑油与表1中所列的相同。表2中列出了对于每种矿物基质油其粘度增加的百份数作为时间的函数值。
表2    氧化稳定性测试-粘度增加百份数
时间(小时) 矿物油A(本发明) 矿物油B(对比) 矿物油C(对比)
0 -- -- --
96 21.8 25.6 27.1
144 29.0 36.2 39.6
240 67.5 93.7 114.1
287 114.1 200.9 283.0
表2表明,本发明的矿物油配方(A)与由含有本发明权利要求范围外的矿物油(B和C)所配制的润滑油配方相比,前者具有意外地改善了的热稳定性和氧化稳定性,因为含矿物油A的润滑油配方具有低得多的粘度增加值即获证明。
含表1脚注所述矿物油A但不含PAO的全配制的润滑油进行了300小时的L-60-1测试。这种全配制的油含18wt%具有数均分子量2100的聚异丁烯、4.5wt%具有数均分子量38,000的聚甲基丙烯酸酯和5wt%DI组合物。该DI组合物为成品润滑油提供了约4wt%的含磷和硼的琥珀酰亚胺分散剂、约0.5wt%受阻酚和胺抗氧剂的混合物和约0.04wt%的噻二唑腐蚀抑制剂。润滑油测试结束时粘度仅增加11%,油泥和C/V等级分别为9.13和9.75。这种油特别适合于作为手工传动装置用油。
要求润滑油,例如重负荷手工传动装置用油在整个使用期内能有效地保护黄色金属,尤其是铜免遭腐蚀,因其通常用作传导冷却器的盘管。上述润滑油抑腐活性的寿命在ASTM D 130铜腐蚀测试中作了说明。这种测试是对新鲜油和经过121℃恒定空气流老化240小时后的油分别进行的。对这两种油的测试均获得1b评价等级,表明经过荷刻的热、氧化作用后该种油仍保持抑腐活性。
在本发明的详述中多处引用了若干美国专利和公开的外国专利申请。所有这些被引用的文献都清楚地全部纳入本发明的公开说明之中,此处特予说明。
本发明在实施中可以有相当多的变化。显然,本发明不受前述特定举例的限制。相反,本发明的精神实质和包括的范围均在权利要求书中,包括其法律根据的等效物。
本专利权人无意将任何公开的实施方案提供给公众,因此从这种意义上说,任何公开的改良内容或变更内容从文字上讲可能不落入本权利要求的范围之内,但根据等效原则,这些内容的改良和变更均认为是本发明的一部分。

Claims (42)

1.一种润滑油组合物,其中包含:
(A)一种具有粘度指数大于110和苯胺点大于110℃的矿物油;
(B)以润滑油组合物总重量计,其含量为约0.1~约40%(重量)
   的至少一种选自烯烃(共)聚合物(类)、聚(甲基)丙烯
   酸烷基酯(类)及它们的混合物之一的聚合物;
(C)以润滑油组合物总重量计,其含量为2~25%(重量)的除
   垢剂/抑制剂组合物。
2.权利要求1的润滑油组合物,其中包含:
(A)具有粘度指数大于110和苯胺点大于110℃的一种矿物油;
(B)以润滑油组合物总重量计,其含量为约0.1~40%(重量)的
   聚合物类混合物,所述聚合物包含(b′)至少一种烯烃(共)
   聚合物和(b″)至少一种聚(甲基)丙烯酸烷基酯;
(C)以润滑油组合物总重量计,其含量为2~25%(重量)的除
   垢剂/抑制剂组合物。
3.权利要求1的润滑油组合物,其中(B)包含至少一种数均分子量为约1,000~约10,000的烯烃(共)聚合物。
4.权利要求2的润滑油组合物,其中烯烃(共)聚合物(b′)的数均分子量为约1,000~约10,000。
5.权利要求3的润滑油组合物,其中烯烃(共)聚合物含有至少一种聚异丁烯。
6.权利要求4的润滑油组合物,其中烯烃(共)聚合物(b′)含有至少一种聚异丁烯。
7.权利要求6的润滑油组合物,其中聚异丁烯的数均分子量为约1,000~约3,000。
8.权利要求4的润滑油组合物,其中(b′)和(b″)的比例b′∶b″等于20∶1~1∶2。
9.权利要求4的润滑油组合物,其中烯烃(共)聚合物(b′)的含量为以润滑油组合物总重量计的12~20%(重量)。
10.权利要求1的润滑油组合物,其中(B)包含至少一种数均分子量为10,000~250,000的聚(甲基)丙烯酸烷基酯。
11.权利要求2的润滑油组合物,其中聚(甲基)丙烯酸烷基酯(b″)的数均分子量为10,000~250,000。
12.权利要求11的润滑油组合物,其中聚(甲基)丙烯酸烷基酯(b″)的含量为以润滑油组合物总重量计的0.1~20%(重量)。
13.权利要求11的润滑油组合物,其中聚(甲基)丙烯酸烷基酯(b″)的含量为以润滑油组合物总重量计的1~6%(重量)。
14.权利要求1的润滑油组合物,它含有低于10%(重量)的聚α-烯烃。
15.权利要求1的润滑油组合物,它不含聚α-烯烃类。
16.权利要求1的润滑油组合物,其100℃下的运动粘度大于13.5cSt。
17.一种润滑油组合物,其中包含:
(A)具有线型+单环链烷烃含量为68%或以上的一种矿物油;
(B)以润滑油组合物总重量计,其含量为约0.1~约40%(重量)
   的至少一种选自烯烃(共)聚合物(类)、聚(甲基)丙烯
   酸烷基酯(类)和它们的混合物之一的聚合物;
(C)以润滑油组合物总重量计,其含量为2~25%(重量)的除
   垢剂/抑制剂组合物。
18.权利要求17的润滑油组合物,其中包含:
(A)具有线型+单环链烷烃含量为68%或以上的一种矿物油;
(B)以润滑油组合物总重量计,其含量为约0.1~约40%(重量)
   的聚合物混合物,它含有(b′)至少一种烯烃(共)聚合物
   和(b″)至少一种聚(甲基)丙烯酸烷基酯;
(C)以润滑油组合物总重量计,其含量为2~25%(重量)的除
   垢剂/抑制剂组合物。
19.权利要求17的润滑油组合物,其中(B)含有至少一种数均分子量为约1,000~10,000的烯烃(共)聚合物。
20.权利要求18的润滑油组合物,其中烯烃(共)聚合物(b′)的数均分子量为约1,000~约10,000
21.权利要求19的润滑油组合物,其中烯烃(共)聚合物含有至少一种聚异丁烯。
22.权利要求20的润滑油组合物,其中烯烃(共)聚合物(b′)含有至少一种聚异丁烯。
23.权利要求22的润滑油组合物,其中聚异丁烯的数均分子量为约1,000~3,000。
24.权利要求20的润滑油组合物,其中(b′)和(b″)的比例b′∶b″等于20∶1~1∶2。
25.权利要求20的润滑油组合物,其中烯烃(共)聚合物(b′)的含量为以润滑油组合物总重量计的12~20%(重量)。
26.权利要求17的润滑油组合物,其中(B)含有至少一种数均分子量为10,000~250,000的聚(甲基)丙烯酸烷基酯。
27.权利要求18的润滑油组合物,其中聚(甲基)丙烯酸烷基酯(b″)的数均分子量为10,000~250,000。
28.权利要求27的润滑油组合物,其中聚(甲基)丙烯酯酸烷基酯(b″)的含量为以润滑油组合物总重量计的0.1~20%(重量)。
29.权利要求27的润滑油组合物,其中聚(甲基)丙烯酸烷基酯(b″)的含量为以润滑油组合物总重量计的1~6%(重量)。
30.权利要求17的润滑组合物,它含有低于10%(重量)的聚α-烯烃。
31.权利要求17的润滑油组合物,它不含聚α-烯烃。
32.权利要求17的润滑油组合物,其100℃下的运动粘度大于13.5cSt。
33.一种改善润滑油组合物热稳定性和氧化稳定性的方法,所述组合物包含一种矿物油,一种烯烃(共)聚合物、一种聚(甲基)丙烯酸烷基酯和一种去垢剂/抑制剂组合物,所说改善包括采用了一种粘度指数大于110,苯胺点高于110℃的矿物油作为矿物油。
34.一种改善润滑油组合物热稳定性和氧化稳定性的方法,所述组合物包含一种矿物油,一种烯烃(共)聚合物、一种聚(甲基)丙烯酸烷基酯和一种去垢剂/抑制剂组合物,所说改善包括采用了一种其线型+单环链烷烃含量为68%或以上的矿物油作为矿物油。
35.权利要求1的润滑油组合物,其中去垢剂/抑制剂组合物为成品润滑油提供0.2~5wt%的分散剂(类)、0~1.0wt%的抗氧剂(类)和0.01~2wt%的抑制剂(类)。
36.权利要求35的润滑油组合物,其中抗氧剂(类)的含量为0.2~1.0wt%。
37.权利要求35的润滑油组合物,其中抗氧剂包含至少一种选自酚类抗氧剂、芳胺类抗氧剂、硫代酚类抗氧剂、有机亚磷酸酯类及它们的混合物的抗氧剂。
38.权利要求35的润滑油组合物,其中分散剂包含至少一种选自链烯基琥珀酰亚胺类、链烯基琥珀酸酯类、链烯基琥珀酸酯-酰胺类、曼尼期碱类、烃基多胺类和聚多胺类的分散剂。
39.权利要求38的润滑油组合物,它包含至少一种磷酸化、硼化或既磷酸化又硼化的分散剂。
40.一种使手工传动装置润滑的方法,该方法包括将权利要求35的润滑油组合物引入到手工传动装置中。
41.权利要求1的润滑油组合物,其中去垢剂/抑制剂组合物为成品油提供3~15wt%含硫耐特压助剂(类)、2~10wt%含磷抗磨剂(类)、0.2~5wt%分散剂(类)和0.01~2wt%抑制剂(类)。
42.一种使车辆轴润滑的方法,该方法包含将权利要求41的润滑油组合物添加并引入车辆轴中。
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