CN88101188A - 润滑油组合物 - Google Patents

润滑油组合物 Download PDF

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Publication number
CN88101188A
CN88101188A CN88101188.6A CN88101188A CN88101188A CN 88101188 A CN88101188 A CN 88101188A CN 88101188 A CN88101188 A CN 88101188A CN 88101188 A CN88101188 A CN 88101188A
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China
Prior art keywords
lubricating oil
alpha
ethylene
random copolymers
olefin random
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CN88101188.6A
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CN1012902B (zh
Inventor
金重良辅
水井公也
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Mitsui Chemical Industry Co Ltd
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Mitsui Petrochemical Industries Ltd
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Publication of CN88101188A publication Critical patent/CN88101188A/zh
Publication of CN1012902B publication Critical patent/CN1012902B/zh
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Abstract

本发明公开的是一种包括如下主要组分的润滑油组合物，(A)合成烃类润滑油，(B)抗磨添加剂和(C)液态改性乙烯/α—烯烃无规共聚物。在该润滑油组合物中，抗磨添加剂被均匀稳定地掺入。该润滑油之所以重要就在于其能有效地克服合成烃类润滑油与抗磨添加剂的配伍性较差的缺点。

Description

本发明涉及一种含有合成烃类润滑油作基础油的润滑油组合物。本发明特别涉及一种与抗磨添加剂有良好配伍性的润滑油组合物。
众所周知，精制的石油类润滑油和合成烃类润滑油是具有代表性的润滑油类型。
前者精制的石油类润滑油，由于其在结构上含有不稳定的双键故易于氧化变质。此外，因为其分子量通常较低（少于500），所以蒸发损失较大并且耐磨性不足。
相反，后者合成烃类润滑油在结构上比前类润滑油更稳定，并且其分子量能在较宽范围内调整。尤其是在选择和聚合一种特定单体时，可制得具有低倾点和高粘度指数特性的润滑油。
然而，这种合成烃类润滑油与通常掺入到润滑油中的抗磨添加剂的配伍性较差，因此，这种润滑油的使用受到限制。
因此，本发明的主要目的是提供一种含有合成烃类润滑油作基础油并与抗磨添加剂有良好配伍性的润滑油组合物。
更准确地说，本发明所提供的润滑油组合物包括如下主要组分，（A）100份重的合成烃类润滑油，（B）0.1至20份重的抗磨添加剂和（C）0.8至200份重的液态改性乙烯/α-烯烃无规共聚物，该改性无规共聚物是通过将不饱和的羧酸或其衍生物接枝键合到乙烯/α-烯烃无规共聚物上得到的，其中（ⅰ）在未改性的乙烯/α-烯烃无规共聚物中乙烯含量占30～75摩尔%，（ⅱ）不饱和羧酸或其衍生物的接枝比为每100份重的未改性乙烯/α-烯烃无规共聚物的0.2～50份重，和（ⅲ）在135℃的萘烷中测定的固有粘度〔η〕在0.01～0.3dl/g的范围内并且由凝胶渗透色谱法测定的分子量分布（ Mw/ Mn）不大于4。
本发明的润滑油组合物其特征在于除含有合成烃类润滑油〔组分（A）〕和抗磨添加剂〔组分（B）〕外还掺入了预定量的液态改性乙烯/α-烯烃无规共聚物〔组分（C）〕。
正如上面所指出的那样，作为组分（A）的合成烃类润滑油具有良好的润滑油特性，但其与抗磨添加剂的配伍性较差，因此其应用范围非常有限。
相反，根据本发明，通过掺入预定量的液态改性乙烯/α-烯烃无规共聚物，改善了合成烃类润滑油与抗磨添加剂的配伍性，并且每个组分都能均匀地混合。
此外，由于本发明中所用的液态改性乙烯/α-烯烃无规共聚物自身具有润滑作用，因此这种改性无规共聚物改善了润滑效果而没有降低可能是作为基础油的合成烃类润滑油的未改性乙烯/α-烯烃无规共聚物的特性。
下面详细叙述本发明。
合成烃类润滑油（A）
已知的润滑油在本发明中可用作基础油，例如可以使用聚α-烯烃油如聚癸烯-1，烷基芳香烃油如烷基苯，聚丁烯油，烷基环烷油如2，4-双环己基-2-甲基戊烷油，以及乙烯/α-烯烃无规共聚油如乙烯/丙烯无规共聚油。
可以使用的聚-α-烯烃油（例如低分子量的α-烯烃的低聚物）如：低分子量的有3～20个碳原子，特别是8（辛烯）至12（十二碳烯）个碳原子的α-烯烃的低聚物和这些α-烯烃的混合物。低粘度α-烯烃低聚物可通过齐格勒（Ziegler）催化作用、热聚合作用和自由基催化聚合作用，最好是通过BF3催化聚合作用来制备。已知一些使用BF3连同共催化剂的类似工艺，其在参考文献中已经公开，在美国专利4，045，508号说明书中公开了一种典型的聚合工艺技术。
在本发明中可以单独使用烷基苯类或与低粘度聚α-烯烃一起或与高粘度合成烃和低粘度酯混合使用。由苯和烯烃通过弗瑞德-克拉夫兹烷基化反应制备的烷基苯通常主要是烷基链有6～14个碳原子的二烷基苯。制备烷基苯所用的烷基化烯烃可以是直链或支链烯烃或其混合物。可根据美国专利3，909，432号说明书公开的工艺方法制备这些物质。
这些润滑油中，特别优先选用的是聚α-烯烃油，尤其是具有粘度为1～20厘斯的聚α-烯烃油和在下文中叙述的用作液态改性乙烯/α-烯烃无规共聚物（作为组分C）的基础油的未改性的乙烯/α-烯烃无规共聚物。
抗磨添加剂（B）
在边界和极压润滑的情况下，当把抗磨添加剂掺入到基础油中时，抗磨添加剂给予基础油载荷能力。抗磨添加剂大致分为油性添加剂和极压添加剂。
油性添加剂是一种在摩擦表面通过物理或化学吸附能够降低摩擦系数的一种化合物。能够提到的油性添加剂有高级脂肪酸例如油酸和硬脂酸，高级醇例如油醇、十八烷醇和十六烷醇，和高级胺例如油胺、十八烷胺和十六烷胺。极压添加剂是一种能够在局部高温和高压条件下通过与金属表面直接反应而避免磨损和粘住的化合物，此时，在摩擦表面形成一层极压涂层或形成一层添加剂热分解产物的涂层。
全部已知的极压添加剂均能在本发明中使用，能够使用的有：硫型极压添加剂例如二丁基二硫代氨基甲酸硫化物和二苄基硫;磷型极压添加剂例如磷酸二丁酯和磷酸二苯酯;卤型极压添加剂例如油酰氯和氯化石蜡;有机金属型极压添加剂例如二硫代磷酸锌、二硫代磷酸钼和环烷酸铅。通常，硫型极压添加剂有良好的抗胶住性，而磷型极压添加剂有良好的耐磨性。最好将硫型极压添加剂和磷型极压添加剂混合使用。
按照润滑油所使用的目的，上述抗磨添加剂可以适当地单独使用或将两种或多种添加剂混合起来使用。
液态改性无规共聚物（C）
在本发明中，除上述组分（A）和（B）外还使用了液态改性乙烯/α-烯烃无规共聚物。
液态改性无规共聚物是通过接枝改性由乙烯和有3～20个碳原子的α-烯烃形成的液态乙烯/α-烯烃无规共聚物（以下通称为“未改性共聚物”）所得的一种共聚物。
所说的α-烯烃，能够使用的有3～20个碳原子的α-烯烃，例如：丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯和1-二十碳烯。
在用来制备改性无规共聚物以便达到本发明的效果（即改善配伍性的效果）的未改性的共聚物中，优选的乙烯含量（a）应是30～75摩尔%，最好是40～70摩尔%，而α-烯烃含量（b）应是25～70摩尔%，最好是30～60摩尔%（乙烯和α-烯烃的总量为100摩尔%）。
对于未改性液态共聚物，可以使用的未改性共聚物其在135℃的萘烷中测得的固有粘度为0.01～0.3dl/g，最好为0.03～0.25dl/g，用凝胶渗透色谱法测得的数均分子量（Mn）为300～12000，最好为500～8000，特别是500～4000，并且其分子量分布（ Mw/ Mn）为1.1～4，最好为1.2～3）。
优先使用具有Z值为10～300，尤其是15～250，并且δ值为0～3，尤其是0～2的未改性液态共聚物。
附带说明的是，在乙烯/α-烯烃无规共聚物中乙烯含量/丙烯含量比率用红外吸收光谱法测定，而固有粘度、分子量分布、数均分子量、Z值和δ值用下列方法测定。
（1）固有粘度（η）（dl/g）
固有粘度在135℃的萘烷中测定。
（2）分子量分布
分子量分布定义为重均分子量（ Mw）与数均分子量（ Mn）之比，用凝胶渗透色谱法（GPC）测定。
（3）数均分子量用GPC法测定。
（4）Z值
Z值是用下面详述的GPC法测定的分子量最大值与分子量最小值之比值。
（5）δ值
δ值按下列公式计算：
Figure 88101188_IMG2
通过使用不同混合比例的丙酮/己烷混合溶剂精馏共聚物，测定乙烯的含量（Ei）和按共聚物的总重计在第一馏中分萃取的共聚物的重量比（Wi）。δ值是表明共聚物组合物分布的一个度量。
关于分子量分布、数均分子量和Z值的较具体的测定方法在下面叙述。
共聚物的数均分子量和重均分子量按下列方法测定，该方法在《聚合物科学杂志》第A-Ⅱ部，8卷，89～103页（1970）上有详细叙述。
用GPC法（凝胶渗透色谱法）测定具有已知分子量（选自有500～840×104不同分子量的16个单分散聚苯乙烯试样）标准物的洗脱计数，作出表明分子量和洗脱计数之间关系的标准曲线。用GPC法作出共聚物试样的GPC谱图。由校准曲线可以读出各个计数点（i）的分子量（Mi），由GPC谱图可以读出各个计数点（i）的洗脱容积（Ni）。共聚物试样（均为聚苯乙烯）的数均分子量（ Mn）和重均分子量（ Mw）用下列公式计算：
Mn＝∑MiNi/∑Ni和
Mw＝∑M2 iNi/∑MiNi
分别地用GPC法测定角鲨烷（一种分子量为422的异构烷烃标准物）的分子量，计算方法同聚苯乙烯。
这样，本发明共聚物的 Mn、Q值和Z值用下列公式计算：
共聚物的 Mn= (按聚苯乙烯法算出的共聚物Mn)/(按聚苯乙烯法算出的角鲨烷的分子量) ×角鲨烷的分子
                                                                                            量（422）
Figure 88101188_IMG3
读出共聚物GPC谱图的最小和最大洗脱计数并从校准曲线读出按聚苯乙烯法计算出的共聚物相应的最小和最大分子量。从下列公式计算出Z曲线：
Z值＝ (按聚苯乙烯法算出的共聚物的最大分子量)/(按聚苯乙烯法算出的共聚物的最小分子量)
在制备乙烯无规共聚物作为基础聚合物中，要与乙烯共聚合的有3～20个碳原子的α-烯烃的具体实例包括：丙烯、1-丁烯、11-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯和1-二十碳烯，优选的有3～10个碳原子的α-烯烃例如：丙烯、1-丁烯、1-己烯、1-辛烯和1-癸烯，特别是丙烯和1-丁烯。它们或单独应用或结合使用。
乙烯和α-烯烃的共聚合作用可以使用该领域熟知的齐格勒催化剂进行，最好使用日本专利申请公开说明书117595/82和123205/82及欧洲专利申请60609（A1）中所公开的方法。例如，在日本专利申请公开说明书123205/82中公开了一种使用由可溶钒化合物和有机铝化合物制成的催化剂，在氢气的存在下，在液相中乙烯与至少有3个碳原子的α-烯烃共聚合的方法。用该方法可以连续地进行共聚合。将聚合体系中钒化合物的浓度调到每升液相中至少有0.3毫摩尔，并将所要加入聚合体系中的钒化合物在聚合介质中稀释，以便使其浓度不大于5倍的聚合体系中钒化合物的浓度。
本发明中用作基本组分的乙烯无规共聚物在常温下最好为液体。
本发明所用的液态改性无规共聚物是通过接枝改性上述未改性共聚物与不饱和羧酸或其衍生物来获得的。
作为接枝共聚单体组分用的不饱和羧酸或其衍生物为有3-20个碳原子，最好是3～10个碳原子的不饱和羧酸或其衍生物，例如，可用的不饱和羧酸有：丙烯酸、异丁烯酸、马来酸、富马酸、衣康酸、柠康酸、四氢化邻苯二甲酸和双环〔2.2.1〕庚-2-烯-5，6-二羧酸;不饱和羧酸酐有：马来酐、衣康酐、柠康酐、四氢化邻苯二甲酐和双环〔2.2.1〕-庚-2-烯-5，6-二羧酸酐;不饱和羧酸的酯类例如：丙烯酸甲酯、甲基丙烯酸甲酯、马来酸二甲酯、马来酸一甲酯、富马酸二乙酯、衣康酸二甲酯、柠康酸二乙酯、四氢化邻苯二甲酸二甲酯和双环〔2.2.1〕-庚-2-烯-5，6-二羧酸二甲酯。
这些化合物中，优先选用马来酐。
在本发明中，为了改善配伍性，最好接枝比应是每100份重的未改性乙烯α-烯烃共聚物用0.2～50份重，尤其是0.5～40份重的不饱和羧酸或其衍生物。
在本发明中，为了改善组分（B）（即抗磨添加剂）的配伍性，液态改性乙烯型无规共聚物的固有粘度（η）在135℃的萘烷中测定最佳应是0.01～0.3dl/g，特别是0.03～0.25dl/g，并且用GPC法测定的分子量分布（ Mw/ Mn）不大于4，最好为1.2～3。
本发明中上述液态改性乙烯型共聚物的数均分子量通常为310～8000，最好为500～4000。
另外，液态改性无规共聚物可用我们前面推荐的在日本专利申请公开说明书123205/82和欧洲专利公开说明书183493中公开的方法由未改性共聚物来制备。
本发明中的液态改性无规共聚物可在自由基引发剂存在下，用改性剂和乙烯的无规共聚物反应（接技共聚合）来制备。该反应通常在惰性气体气氛中，在有溶剂或没有溶剂的情况下进行。该反应能够在有或没有溶剂的情况下，并在搅拌下通过连续或间歇地把改性剂化合物和自由基引发剂加到加热的液体乙烯的无规共聚物中来进行。加入到该接技共聚合反应中的改性剂和自由基引发剂的比例和反应温度以及时间随改性剂的类型等等而变化。通常，这些反应条件可以根据改性剂化合物的类型从下面所列的表中选择。
在接技共聚合反应中所用的自由基引发剂是一般的有机过氧化物，最好是具有分解温度（该点的半值是1分钟）为60～270℃，最佳为150～270℃的有机过氧化物。有机过氧化物和有机过酸酯的具体实例为：过氧化苯甲酰、过氧化二氯苯甲酰、过氧化二枯基、过氧化二叔丁基、2，5-二甲基-2，5-二（过氧苯甲酸酯）己炔-3、1，4-双（叔丁基过氧异丙基）苯、过氧化月桂酰、叔丁基过乙酸酯、2，5-二甲基-2，5-二（过氧叔丁基）己炔-3、2，5-二甲基-2，5-二（过氧叔丁基）己烷、过苯甲酸叔丁酯、过乙酸苯叔丁酯、过异丁酸叔丁酯、过仲辛酸叔丁酯、过新戊酸叔丁酯、过新戊酸枯基酯和过二乙基乙酸叔丁酯。
能够作溶剂使用的例子有芳烃例如：苯、甲苯、二甲苯、一氯苯和二氯苯;和脂族烃或脂环烷或其卤化产物，例如：戊烷、己烷、环己环、庚烷和辛烷。芳烃溶剂是优选的。没有溶剂也是优选的。
将改性乙烯的无规共聚物从反应混合物中分离及其提纯均可以用本领域熟知的方法进行，例如蒸馏或溶剂分馏。
润滑油组合物的制备
本发明的润滑油组合物可很容易制备，将组分（B）0.1～20份重，最好1～15份重的抗磨添加剂和（C）0.8～200份重，最好1～150份重的液态改性乙烯/α-烯烃无规共聚物掺入到（A）100份重的合成烃类润滑油中即成。掺入过程可以在常温（25℃）下或在加热下进行。然而，最好采用先将组分（B）和（C）在加热（50～250℃）下混合，然后再将作基础油用的润滑油（A）加入到该混合物中的方法。
为了获得良好的配伍性，最好在混合抗磨添加剂（B）和液态改性乙烯/α-烯烃无规共聚物（C）时将（C）/（B）的混合比控制在0.05～200，尤其是1～150。
在本发明的润滑油组合物中，除去前述三种组分（A）至（C）外，还可以掺入精炼的石油润滑油或合成润滑油，例如：聚醚油、酯油或硅油，其用量按作为组分（A）的合成烃类润滑油计可以达到100%（重）。
此外，也可以加入一些已知的添加剂，例如粘度指数改进剂如聚甲基丙烯酸酯、聚异丁烯、苯乙烯/异丁烯/苯乙烯嵌段共聚物和苯乙烯/丁二烯/苯乙烯嵌段共聚物;降凝剂例如氯化石蜡/萘缩合物和聚烷基异丁烯酸酯;防锈剂例如十二烷胺和十二烷基硬脂酸铵;清净分散剂例如烷基芳香烃磺酸的金属盐和琥珀酰亚胺;消泡剂如二甲基聚硅氧烷;着色剂如油溶染料和抗氧剂如酚化合物和胺化合物。这些添加剂的加入量根据添加剂的种类而不同，但通常加入添加剂的量按合成烃类润滑油的重量计为0.1～10%。
本发明的润滑油组合物具有良好的液体稳定性，即使加入各种各样的抗磨添加剂也并不会产生沉淀物，而且配伍性也非常好。从涉及内燃机润滑油特性的JIS    K-2215规定不许生成水或沉淀物来看，这种特性非常重要，非常有用。
此外，由于各种各样的抗磨添加剂都能任意与润滑油掺和并有良好的配伍性，因此尽可能地按照使用目的给予润滑油以很高的载荷能力。
从下面给出的实施例可以明显地看到，本发明的润滑油组合物能够在-50℃～250℃的很宽温度范围内使用，并且氧化安定性和剪切安定性都非常高，而且这些性能能够持续很长时间，其结果则是换油期可延长。
下面将参照下列实施例对本发明进行详细描述，但这不意味着限制本发明的范围。
首先，用下面参考例来说明液态改性乙烯/α-烯烃无规共聚物的制备。
参考例    1
用具有下列性质的乙烯/丙烯共聚物作为要接枝改性的共聚物。
乙烯含量：    50摩尔%
数均分子量（ Mn）： 810
Mw/ Mn： 1.40
固有粘度〔η〕：    0.04dl/g
Z值：    80
δ值：    0.1
运动粘度（100℃）：    22.8厘斯
向配置有一个氮气吹入管、一个水冷冷凝器、一个温度计、两个滴液漏斗和一个搅拌器的2升玻璃反应器中装入800克的上述乙烯/丙烯共聚物，用氮气置换内部气体2小时以逐出溶解的氧。
然后，将反应器的内部温度升至160℃，分别向两个滴液漏斗中装入40克的马来酐（已在60℃下液化）和8克的二叔丁基过氧化物并在4小时之内逐滴加入到反应器中。
在逐滴加完后，反应继续进行4小时，将反应器的内部温度升高到180℃，并在0.5mmHg的减压下除去未反应的马来酐和二叔丁基过氧化物的分解产物。
得到具有下列性质的液态改性乙烯/丙烯共聚产物：
外观：    黄色透明液体
固有粘度〔η〕：    0.04dl/g
数均分子量（ Mn）： 815
Mw/ Mn＝1.40
运动粘度（100℃）：    33.8厘斯
接枝比：每100份重的乙烯/丙烯共聚物为4.5份重。
参考例    2
除使用具有下列性质的乙烯/丙烯共聚物外，用参考例1所述的相同方法制备接枝改性液态乙烯/丙烯共聚物。
乙烯含量：    50摩尔%
数均分子量（ Mn）： 1450
Mw/ Mn＝1.7
固有粘度〔η〕：    0.05dl/g
Z值：    100
运动粘度（100℃）：    110厘斯
δ值：    0.1
所获得的液态改性乙烯/丙烯共聚物的性质如下：
外观：黄色透明液体
固有粘度〔η〕：    0.08dl/g
数均分子量（ Mn）： 1455
Mw/ Mn＝1.7
运动粘度（100℃）：    135厘斯
接枝比：    4.4份重
参考例    3
除用80克的马来酐和16克的二叔丁基过氧化物在8小时内逐滴加入外，用参考例1的相同方法制备液态改性乙烯/丙烯共聚物。
外观：    黄色透明液体
固有粘度〔η〕：    0.09dl/g
数均分子量（ Mn）： 820
Mw/ Mn＝1.5
运动粘度（100℃）：    170厘斯
接枝比：    9.6份重
参考例    4
使用具有下列性质的乙烯/丙烯共聚物作为要接枝改性的共聚物：
乙烯含量：    49摩尔%
数均分子量（ Mn）： 1500
Mw/ Mn＝1.65
固有粘度〔η〕：    0.05dl/g
Z值：    110
运动粘度（100℃）：    145厘斯
δ值：    0.1
向1升的玻璃反应器中装入595克这种乙烯/丙烯共聚物，并将其温度升至140℃。
然后，加入105克甲基丙烯酸正丁酯和9.0克二叔丁基过氧化物，并将热反应进行4小时。
在10mmHg的减压同时保持温度在140℃下进行排气处理以除去挥发性组分，然后，冷却反应产物，得到液态改性乙烯/丙烯共聚物。
所得共聚物的性质如下：
外观：无色透明液体
固有粘度〔η〕：    0.06dl/g
数均分子量（ Mn）： 1500
Mw/ Mn＝1.63
运动粘度（100℃）：    200厘斯
接枝比：    16份重（甲基丙烯酸正丁酯）
参考例    5
向126份重数均分子量为1260的异丁烯聚合物中加入10份重的马来酐，在180℃搅拌下使反应进行5小时。
在减压下用蒸馏法除去未反应的马来酐，得到酸性改性异丁烯共聚物。
这种改性共聚物的数均分子量为1360，并且马来酐的接枝比是每100份重的异丁烯聚合物为7.8份重。
实施例1～7和对照例1～7
在室温（25℃）下混合参考例1-4中获得的液态改性乙烯/丙烯共聚物、原料乙烯/丙烯共聚物和抗磨添加剂，见表1，在100℃下加热该混合物得到均匀的组合物。
将这样得到的每种润滑组合物在室温下静置7天，然后用肉眼按下列等级评价透明度：
○：透明
△：半透明
×：不透明或非连续的
为了便于比较，将参考例1至3中所用的原料乙烯/丙烯共聚物和抗磨添加剂的液态混合物进行上述实验。
得到的结果列于表1。
Figure 88101188_IMG4
Figure 88101188_IMG5
注：
表1中的所有量用重量份数表示。
实施例    8
在室温下向60份重的参考例2中制备的液态改性共聚物中掺入并溶解2份重的二硫代磷酸钼〔SAKURA-LUBE
Figure 88101188_IMG6
＃300，由Asahi Denka提供，Mo含量＝9.0%（重），P含量＝3.2%（重），S含量＝10.5%（重）〕获得棕色透明液体混合物。
将所得到的液态混合物加入到100份重在参考例2所用的原料未改性共聚物中，并充分搅拌该混合物，得到绿色透明稳定的液态混合物。
对照例    7
除根本不使用液态改性共聚物外，用同样的方法重复实施例8的步骤，但是未改性的乙烯/丙烯共聚物仍与二硫代磷酸钼混合。这两种组分不但相互不相容，而且还相互分离。
实施例9～11和对照例8～10
使用一种市场上买得到的极压添加剂〔Package A，由德士古提供的TC-7978，S含量＝2.7%（重），Ca含量＝4.1%（重），Zn＝1.0%（重），P含量＝1.0%（重）〕作抗磨添加剂。
将13份重的Package    A、预定量的液态改性乙烯/丙烯共聚物和50份重的酯油（己二酸二异癸酯）混合，在100℃加热30分钟，制备成液体混合物。
然后，将100份重具有下列性质的液态乙烯/丙烯无规共聚物加入到上面所得到的液态混合物中，在室温下搅拌该混合物得到润滑油组合物。
乙烯含量：    50摩尔%
数均分子量（ Mn）： 1030
Mw/ Mn： 1.5
固有粘度〔η〕：    0.05dl/g
运动粘度（100℃）：    40厘斯
Z值：    90
δ值：    0.1
对上面得到的每一种组合物，用与实施例1叙述的相同方法评价其配伍性，得到的结果列于表2中。
从表2中的结果可以明显地看出，如果掺入的液态改性乙烯/丙烯共聚物的量少，则该混合物不透明并且在混合物静置时产生沉淀，因此，该混合物不适合作润滑油。
附带说明，在制备润滑油组合物时，重要的是应在先加热的条件下将极压添加剂（Package    A）与液态改性乙烯/丙烯无规共聚物混合，然后再加入未改性的乙烯/丙烯共聚物。如果两种共聚物同时加入或不进行加热，则很难得到透明的组合物。
实施例12
将3份重的市场上买到的极压添加剂（Package    B，Anglamol    98A，由Nippon    LUBRIZOL    INDUSTRIES提供）、6份重在参考例2中制备的液态改性乙烯/丙烯无规共聚物和13份重的酯油（己二酸二异癸酯）在100℃下加热混合30分钟制备一种液态混合物。
将84份重参考例2中所用的原料未改性乙烯/丙烯共聚物和16份重的聚癸烯-1低聚物（在100℃时测得运动粘度为12.5厘斯）与上述液态混合物混合，在室温（25℃）下搅拌该混合物得到一种透明、稳定的润滑油组合物。
对照例    11
按实施例12的方法制备一种润滑油组合物，只是不掺入液态改性乙烯/丙烯无规共聚物。
该润滑油组合物不透明，并且当该组合物静置时会产生沉淀物。
实施例    13
用实施例9所述方法制备润滑油组合物，只是用市场上买得到的极压添加剂package C〔LZ3928，由Nippon Brisol提供，S含量＝3.3%（重），Ca含量＝4.4%（重），Zn含量＝0.94%（重），P含量＝0.85%（重），N含量＝0.25%（重）〕作为抗磨添加剂。
得到的润滑油组合物是透明的并有良好的配伍性。
对照例    12
用实施例13所述的方法制备润滑油组合物，只是不用液态改性乙烯/丙烯共聚物。
该组合物不透明，并且在静置期间产生沉淀物。
实施例    14
用市场上买到的有机钼极压添加剂（二硫代磷酸钼）〔SAKURA-LUBE
Figure 88101188_IMG8
＃300，由Asahi Denka提供，Mo含量＝9.0%（重），P含量＝3.2%（重），S含量＝10.5%（重）〕作为抗磨添加剂。
将5份重的上述极压添加剂和10份重在参考例2中制备的液态改性乙烯/丙烯共聚物在60℃下加热、混合15分钟，制备成液态混合物。
用100份重的具有下列性质的未改性乙烯/丙烯共聚物与上述液体混合物在室温下混合搅拌，得到一种蓝绿色均匀透明的润滑油组合物。
未改性乙烯/丙烯共聚物的性质：
乙烯含量：    50摩尔%
数均分子量（ Mn）： 810
Mw/ Mn： 1.40
固有粘度〔η〕：    0.04dl/g
运动粘度（100℃）：    20厘斯
该润滑油组合物具有良好的配伍性。
对照例    13
用与实施例14相同的方法制备润滑油组合物，只是不掺入液态接枝改性乙烯/丙烯共聚物。
该组合物是不透明的，并且当静置时该组合物会产生沉淀物。
实施例    15
试验在实施例10中制备的润滑油的润滑性能。所得结果列于表3。
Figure 88101188_IMG9
对照例    14
用与实施例15相同的方法试验一种市场上买到的含有精制石油润滑油作基础油的矿物油型发动机润滑油（用于赛车）。
所得结果列于表3。
为了比较，将对照例8中制备的润滑油组合物和除掺入参考例5的改性异丁烯聚合物代替参考例2中液态改性乙烯/丙烯共聚物外而用与实施例10相同的方法制备的润滑油组合物做类似的试验，但由于存在着沉淀物，试验无法进行。
附带说明，当试样经受超声波照射（10KH2，40℃，30分钟）时，可以观察到用100℃时运动粘度的减小系数表示的剪切安定性。
实施例    16
除用100份重的聚α-烯烃低聚物（PAO-6，Synfluid    CST6，由雪弗龙化学公司提供，运动粘度＝6厘斯/100℃，粘度指数＝135）用作合成烃类油代替100份重实施例1中用的原料未改性乙烯/丙烯共聚物外，用相同的方法重复实施例1的步骤。评价其配伍性为“O”级（透明）。
实施例    17
除用100份重的聚α-烯烃低聚物（PAO-100，SHF-1001，由Mobil化学公司提供，运动粘度＝100厘斯/100℃）作为合成烃类油代替100份重实施例1中用的原料未改性乙烯/丙烯共聚物外，用相同的方法重复实施例1的步骤。评价其配伍性为“O”级（透明）。

Claims (4)

1、一种具有良好配伍性的润滑油组合物，其包括以下主要组分：
(A)100份重的合成烃类润滑油，(B)0.1～20份重的抗磨添加剂和(C)0.8～200份重的液态改性乙烯/α-烯烃无规共聚物，该共聚物是通过在乙烯/α-烯烃无规共聚物上接枝上不饱和的羧酸或其衍生物形成的，其中(i)在未改性乙烯/α-烯烃无规共聚物中乙烯含量为30～75摩尔%，(ii)不饱和羧酸或其衍生物的接枝比为每100份重的未改性乙烯/α-烯烃无规共聚物是0.2～50份重和(iii)在135℃的萘烷中测得的固有粘度[η]为0.01～0.3dl/g，并且由凝胶渗透色谱法测定的分子量分布( Mw/ Mn)不大于4。
2、根据权利要求1的润滑油组合物，其中抗磨添加剂（B）和液态改性乙烯/α-烯烃无规共聚物（C）的掺混重量比（B）/（C）为0.05～200。
3、根据权利要求1的润滑油组合物，其中合成烃类润滑油（A）是聚α-烯烃油或乙烯/α-烯烃无规共聚物油。
4、根据权利要求3的润滑油组合物，其中液态改性乙烯/α-烯烃无规共聚物（C）是所说的乙烯/α-烯烃无规共聚物油的接枝改性产物。
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