CN1045467C - 二冲程发动机润滑油 - Google Patents

二冲程发动机润滑油 Download PDF

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CN1045467C
CN1045467C CN94109568A CN94109568A CN1045467C CN 1045467 C CN1045467 C CN 1045467C CN 94109568 A CN94109568 A CN 94109568A CN 94109568 A CN94109568 A CN 94109568A CN 1045467 C CN1045467 C CN 1045467C
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lubricating oil
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polybutene
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J·麦马洪
J·D·福瑟林汉姆
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Abstract

本发明涉及含有在聚合物主链中具有很低或几乎没有正丁烯的聚丁烯基础油的二冲程发动机润滑油。在聚丁烯中没有正丁烯大大地减少了使用发动机润滑油时产生的废气中的排烟量。特别优先选用诸如几乎不含氯并具有高的端基不饱和度的ULTRAVISR聚丁烯。

Description

二冲程发动机润滑油
本发明涉及含有在聚合物主链中具有很低或几乎没有正丁烯的聚丁烯基础油的二冲程发动机润滑油。
二冲程发动机润滑油通常是起润滑作用的组合物，它们用于与燃料掺和并起润滑二冲程发动机运动部件的作用。这类发动机可以包括功率大于50马力并高达100马力的外装发动机和不但可用于摩托车而且，例如，也可用于链锯、机动雪撬及摩托雪撬的空气冷却的发动机。这些发动机的一个特点是高速旋转，结果它们比迄今所用的发动机更热。
起初，对于这类发动机的润滑油的基本要求是润滑油能在受影响的部位形成一种稳定和连续的润滑油膜，从而使发动机不仅在低温下容易启动，而且在相对较高的操作温度下能避免在发动机部件上由于形成沉积物而产生污垢，从而降低发动机的性能或导致损害受影响的部件。
近来，人们的注意力集中在对环境有利的润滑油上，即产生于燃料和润滑油的燃烧的废烟是干净的，具有最小的气味，不释放出可见的烟雾，而且降低了油/燃料比。
用聚丁烯作为二冲程润滑油的组分已经许多年了，与矿物油相比，其优点在于排出可见的废烟少，因而在发动机排气系统形成的碳沉积也少。例如GB-A-1287579(英国石油有限公司，1968年申请)叙述了采用聚异丁烯聚合物作为润滑油。然而，典型的是这份说明书既没有给出聚(异)丁烯聚合的生产方法，事实上也没有给出作为生产这些聚异丁烯的原料的C4馏分的来源。众所周知，迄今所用的聚(异)丁烯总是从包括正丁烯和异丁烯的丁烯混合物，即从主要是丁二烯提余液的馏分或从流化催化裂化(FCC)工艺的粗C4馏分的含有20～40％正丁烯的原料来生产的。在GB-A-1287579申请前后就是这种情况，从GB-A-1340804(Labofina SA,1972年申请)申请这种情况是很明显的，该申请叙述了从含有4个碳原子的烃的馏分来生产聚合物，而由此制得的聚合物据说含有不同比例的聚丁烯和聚异丁烯，一般为5～70％聚异丁烯和95～30％聚正丁烯。
现在已经发现在其聚合物主链中含有更低含量或几乎没有正丁烯的聚丁烯不仅在减少从二冲程发动机排放出的废气中的可见烟雾方面，而且在形成低的碳沉积物方面都具有优越性能。
因此，本发明是含有分子量(Mn)为300～2000的聚丁烯聚合物或聚合物的混合物的二冲程发动机润滑油，其特征是在聚合物主链中正丁烯的比例：当聚丁烯的分子量(Mn)值等于或小于700时为小于0.2，而当聚丁烯的分子量(Mn)大于或等于700时为小于0.12，该比例由聚合物中-CH2CH2-正丁烯单元在740cm-1的红外吸收与C-H在4315～4345cm-1，通常为4335cm-1之间的泛频吸收的红外吸收的比值来定义。
聚合物主链中正丁烯比例(下文称“NB”)的定义一直由红外吸收技术来确定，因为要定量确定是困难的想法。为避免这些问题，决定开发一种土办法，通过比较市售的聚丁烯和现在所用的低正丁烯含量的聚异丁烯(PIB)的相应的红外吸收(在特定的频率处)。这种方法采用在740cm-1的-CH2CH2-吸收作为聚合物主链上的相对正丁烯含量的指标。它采用装配有DTGS检测器和CsI分光器的Nicolet 740 FTIR光谱仪。该光谱仪具有带有小部分切开的0.2毫米的Teflon(聚四氟乙烯)隔片的KBr窗口和一个合适的吸收池架。样品的光谱采用4cm-1分辨率得到。测得在800和700cm-1区域的两个最小基线界限之间的740cm-1频带的吸收峰高度。同样通过测量在基线界限4750和3650cm-1的吸收峰高度来表征4335cm-1频带。相对正丁烯含量计算如下：
Figure C9410956800061
这就是下面所列的计算结果所用的方法。
为了这一实验，具有相对低的正丁烯含量或几乎没有正丁烯的聚丁烯(聚异丁烯)由权利要求中所提出的和我们已公开的EP-A-0145235所叙述的工艺来制得，即采用预先制得的三氟化硼-乙醇配合物作为异丁烯聚合的催化剂，而且所叙述的方法列为本文的参考文献。该工艺可制得一种不仅是正丁烯含量低而且几乎没有氯的聚合物。该种工艺的产品是用于实例中的ULTRAVIS牌号聚丁烯(可从英国石油化学有限公司购得)。低正丁烯含量或几乎没有正丁烯的聚丁烯也可采用经仔细选择原料和/或工艺条件的其它工艺来制得。为了比较的目的，所使用的具有相对较高正丁烯含量的聚丁烯是市售的HYVIS牌号(也可从英国石油化学有限公司得到)。
从下表所列的数据可以看出各个吸收比实际上是存在很大的差别。
表1在740cm-1(正丁烯)/4335cm-1(聚异丁烯)的聚合物
                  红外吸收比
聚合物  粘度(100℃)     Mn   NB/PIB比
HYVIS5     104     764     0.278
PNB 07*     14.7     540     1.120
HYVISPB25     25.0     530     0.32
ULTRAVIS5     100     762     0.106
ULTRAVIS3     60     645     0.147
HYVIS10     223     962     0.203
ULTRAVIS10     225     966     0.049
ULTRAVISPB25     25.3     510     0.150
纯PIB 5**     101     775     0.0
*    PNB 07是一种由富含正丁烯和较低异丁烯的C4馏分制得的实验用聚合物。**  下文标为PPIB 5，它是一种从富含异丁烯且几乎没有正丁烯的C4馏分制得的聚合物。
从表1显而易见，大多数普通牌号的聚丁烯聚合物具有这种吸收比：在分子量(Mn)低于700时大大高于0.2，而在分子量(Mn)大于700时大大高于0.12。
本发明的再一个特点是目前所用的聚异丁烯聚合物也可以是几乎没有氯。在废气中，不希望氯或其衍生物存在，因此最希望采用无氯的聚异丁烯。已经发现由例如HYVIS5和HYVIS10配制的二冲程发动机润滑油各含～97和～45ppm氯，而由ULTRAVIS5和ULTRAVIS10配制的二冲程发动机润滑油的含氯量都小于5ppm。这是由于实际上在生产ULTRAVIS牌号的聚丁烯时采用了不含氯的化合物。因此，在后者中氯的含量低于可检测的水平，从而可以认为是几乎没有氯。
因此，按照另一个优选实施方案，本发明是一种含有数均分子量(Mn)为300～2000的聚丁烯聚合物或其混合物的二冲程发动机润滑油，其特征是在聚合物主链中正丁烯的比例：当聚丁烯的数均分子量(Mn)等于或小于700时为小于0.2，而当聚丁烯的分子量(Mn)大于或等于700时为小于0.12，该比例由聚合物在740cm-1与在4335cm-1的红外吸收的比值来定义，且所说的润滑油几乎没有氯。
用于本发明的二冲程发动机润滑油的聚异丁烯，当其分子量范围为310～1300时，粘度较好为2～670厘沲范围，更好为3～250厘沲，而且最适合用于生产低烟润滑油。
二冲程发动机润滑油配方中聚丁烯的用量范围较好为15～80％重量/重量，更典型的是25～50％重量/重量。通常存在于这类二冲程发动机润滑油中的其它组分是矿物油，其用量范围为20～70％重量/重量。
为改善此类二冲程发动机润滑油配方的去垢性，通常加入煤油之类的低灰分添加剂和稀释剂以改善该油剂的可处理性并提高与燃料的相溶性。
此类二冲程发动机润滑油配方也可含有合成酯、聚-α-烯烃和烷基苯以生产高性能的产品。
用于评价的标准试验方法是由日本自动化标准协会(JASO)制定的标准，用来分类二冲程发动机润滑油的性能。这些试验方法之一(M342)包括在部分试验循环期间测量形成废烟的方法。结果以烟点指数来表示，并且从内部参照烟点指数列为100的标准的二冲程发动机润滑油。烟点指数越高，排烟量的减少量就越大。试验采用70cc,Suzuki Generator SX 800 R。润滑油的烟点试验结果示于下表2。
本发明由参见下面的实例而进一步得到解释。
实例1
将ULTRAVIS5聚丁烯(38％重量/重量)与溶剂中性的500号矿物油(36％重量/重量)及添加剂ADX 3110(8％重量/重量，从英国石油化学添加剂公司购得)在60℃，于混合器中进行混合。然后加入煤油(18％重量/重量)，并测定混合的润滑油性质。
在不按照本发明的对比实验中，将同样数量的物料混合在一起，所不同的是用HYVIS5聚丁烯代替ULTRAVIS5聚丁烯。
上面两种配方的JASO烟点试验表明：在聚合物主链上具有低的正丁烯含量的ULTREVIS5聚丁烯比采用HYVIS5的相应配方的排烟量的减少更大。试验的结果列于下表3。
实例2
重复实例1的过程，但所用的溶剂中性的矿物油是SN500和SN150(19/81重量/重量)的混合物。同时，所用的聚丁烯为ULTRAVIS10(按照本发明)和HYVIS10(对比试验，不按照本发明)。所用的每种组分的各自数量并不严格相等，因为各种组分的这种严格和准确测定并不是切实可行的，它对于测定性能也是不重要的。所用的具体组分列于下表2。
JASO烟点试验表明：含有在聚合物主链上具有低的正丁烯含量的ULTREVIS10聚丁烯的配方比采用含有相对较高正丁烯含量的HYVIS10的相应配方的排烟量的减少更大。烟点试验的结果列于下表3。
                      表2
                二冲程润滑油配方
组分     HYVIS10  ULTRAVIS10
聚丁烯     30.6     30.0
矿物油SN500/SN150     42.8     44.0
添加剂ADX 3110     8.2     8.0
煤油  稀释剂     18.4     18.0
                              表3
                         烟点试验(JASO)
聚合物  NB/PIB比* 润滑油PIB含量 烟点指数
ULTRAVIS5  0.106     38.0     99
HYVIS5  0.278     38.0     90
ULTRAVIS10  0.049     30.0     81
HYVIS10  0.203     30.6     74
*-在740cm-1与在4335cm-1的吸收比。
实例3
将ULTRAVISPB25聚丁烯(36.6％重量/重量)与溶剂中性的500号矿物油(37.3％重量/重量)及添加剂ADX 3110(8.1％重量/重量，从英国石油化学添加剂有限公司购得)在60℃，于混合器中进行混合。然后加入煤油(18.6％重量/重量)，并测定混合的润滑油的性质。
在对比实验(不按照本发明)中，将同样数量的物料混合在一起，所不同的是用HYVISPB25聚丁烯代替ULTRAVISPB25聚丁烯。
这两种配方的组分示于下表4：
                   表4
             二冲程润滑油配方
组分 HYVISPB25 ULTRAVISPB25
聚丁烯     36.6     36.6
矿物油 SN500/SN150     37.3     37.3
添加剂 ADX 3110     8.1     8.1
煤油   稀释剂     18.0     18.0
对这些配方进行如前所述的JASO烟点试验，结果示于下表5：
                            表5
                       烟点试验(JASO)
聚合物     NB/PIB比* 润滑油PIB含量 烟点指数
ULTRAVISPB25     0.150     36.6     97
HYVISPB25     0.320     36.6     95
*-在740cm-1与在4335cm-1的吸收比。
因此，这两种配方的JASO烟点试验表明：含有在聚合物主链上具有低的正丁烯含量的ULTRAVISPB25聚丁烯的配方比含有在聚合物主链上具有相对较高正丁烯含量的HYVISPB25聚丁烯的相应配方的排烟量的减少更大。
实例4
重复实例1过程，不同的是所用的聚丁烯各自是PPIB5(按照本发明)和HYVIS5(对比试验，不按照本发明)。配方中所用的每种组分的各自数量并不严格相等，因为各种组分的这种严格和准确测定对于测定性能是不重要的。这些配方的组分示于下表6。
                     表6
              二冲程润滑油配方
组分     PPIB5     HYVIS5
聚丁烯     38.0     38.0
矿物油 SN500/SN150     35.9     36.0
添加剂 ADX 3110     8.0     8.0
煤油   稀释剂     18.1     18.0
如同前述，对这些配方进行JASO烟点试验，得到的结果示于下表7：
                    表7
               烟点试验(JASO)
聚合物 NB/PIB比* 润滑油PIB含量 烟点指数
PPIB5     0.0     38.0     95
HYVIS5     0.278     38.0     90
因此，JASO烟点试验表明：含有在聚合物主链上几乎没有正丁烯含量的PPIB5聚丁烯的配方比含有在聚合物主链上具有相对较高正丁烯含量的HYVIS5聚丁烯相应的配方的排烟量的减少更大。

Claims (9)

1．一种含矿物油和具有分子量(Mn)为300-2000的聚丁烯聚合物或聚合物的混合物的二冲程发动机润滑油，其特征是在聚合物主链中正丁烯的比例：当聚丁烯的分子量(Mn)等于或小于700时为小于0.2，而当聚丁烯的分子量(Mn)大于或等于700时为小于0.12，该比例由聚合物中-CH2CH2-正丁烯单元在740cm-1的红外吸收与C-H在4315～4345cm-1之间的泛频吸收的红外吸收比值来定义。
2．按照权利要求1的含有数均分子量(Mn)为300-2000的聚丁烯聚合物或聚合物的混合物的二冲程发动机润滑油，其特征是在聚合合物主链中正丁烯的比例：当聚丁烯的分子量(Mn)等于或小于700时为小于0.2，而当聚丁烯的分子量(Mn)大于700时为小于0.12，该比例由聚合物在740cm-1与在4335cm-1的红外吸收的比值来定义。
3．按照权利要求1的二冲程发动机润滑油，其中聚丁烯聚合物中含有＜5ppm的氯。
4．按照权利要求3的二冲程发动机润滑油，其中聚丁烯聚合物中60％以上的不饱和键是亚乙烯基(……=CH2)型的。
5．按照上述任何一项权利要求的二冲程发动机润滑油，其中对于分子量为310-1300的的聚丁烯其粘度为2～670厘沲。
6．按照权利要求1的二冲程发动机润滑油，其中存在于所说的润滑油中的聚丁烯的数量在15～80％重量/重量的范围内。
7．按照权利要求1的二冲程发动机润滑油，其中所说的润滑油含有含量范围为20～70％重量/重量的矿物油。
8．按照权利要求1的二冲程发动机润滑油，其中还含有低灰分添加剂和烃类稀释剂以改善润滑油的可处理性并提高其与燃料的相溶性。
9．按照权利要求1的二冲程发动机润滑油，其中还含有合成酯、聚-α-烯烃和烷基苯以生产高性能的产品。
CN94109568A 1993-08-20 1994-08-19 二冲程发动机润滑油 Expired - Lifetime CN1045467C (zh)

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