CN1050629C - 二相发动机用低烟润滑组合物 - Google Patents

二相发动机用低烟润滑组合物 Download PDF

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CN1050629C
CN1050629C CN94114926A CN94114926A CN1050629C CN 1050629 C CN1050629 C CN 1050629C CN 94114926 A CN94114926 A CN 94114926A CN 94114926 A CN94114926 A CN 94114926A CN 1050629 C CN1050629 C CN 1050629C
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F·伯蒂
F·雷沃蒂
U·罗曼诺
Ｕ·斯加姆巴托
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Euron SpA
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Abstract

本发明涉及一种脂族三元醇或四元醇的碳酸酯，它具有式(Ⅰ)的结构，还涉及含碳酸酯和选自溶剂、重质高粘度润滑油或其它抗咬添加剂、常用添加剂的润滑组合物，用于二相内燃机的低烟量润滑剂的底基。

Description

二相发动机用低烟润滑组合物
本发明涉及用低烟量的特殊的碳酸酯作二相(two phase)内燃机的润滑基以及含所说碳酸酯的组合物。
二相发动机广泛用于如摩托车和小型摩托车的二轮车辆领域、外装发动机领域和农业、园艺设备。在这类发动机中，润滑剂是与燃料混合进入燃烧室以润滑气缸壁，然后与燃料一起燃烧。因此，与相程发动机润滑有关的主要技术问题关系到要有良好的润滑，这种润滑要最大限度地减少积炭的形成和废气中的浓烟。在不久的过去，与使用以生物降解的油为基底的组合物的需要的同时，废气中浓烟的问题是特别的，并且是在增加。
现存技术中用于二相发动机的大多数润滑组合物由矿物油基、重质高粘度润滑油(高粘度、再制无蜡润滑油的混合物)、添加剂，以及在局部润滑的发动机的情况下也用轻质烃作为稀释剂以促进在燃料中的混合。最近介绍了使用高分子量的聚异丁烯以代替重质高粘度润滑油，它降低了废气中的含烟量和发动机中的残留碳，但并没有达到完全满意的结果。再者，聚异丁烯象矿物油一样，是不能生物降解的。
浓烟问题和可降解性在使用农业和园艺设备时是特别感受到的，操作人员常常是非常接近排气管的(例如用油锯的伐木者)，并且油的扩散对工作环境是有害的；在外装发动机领域也是这样。
申请人深入研究了这一问题，发现在这些润滑组合物中使用有特殊结构的碳酸酯组成的合成基底就可达到限制烟量和可生物降解的目的。
应注意的是，现存技术中已在不同领域的润滑和增塑组合物中使用了各种碳酸酯，例如U.S.P.2,758,975叙述了将碳酸的酯用作润滑剂的底基；化学文摘 71，1969，5288f叙述了一组有特殊热稳定性的碳酸酯，用作润滑剂和高温功能流体；U.S.P.2,739,127叙述了用有机碳酸酯作润滑脂的基底，特别是低温润滑脂，此美国专利叙述了用碳酸酯作为有改进的抗极压性的润滑组合物的基底；U.S.P.2,651,657叙述了用于有低滑点和高粘度指数润滑剂的碳酸酯；德国专利1,006,565叙述了用于有改进特性的润滑剂作为基底的碳酸酯，特别是在高、低温时使用和有高的气缸清洁作用的润滑剂；比利时专利764,900叙述了齿轮和纺织机器的润滑以及金属加工中作为润滑剂和传压液体的碳酸酯的应用，它因摩擦系数的极大降低和易于生物降解而有一些优点；欧洲专利申请No.89,709叙述了用碳酸酯作为具有改进的热、水解和氧化稳定性的润滑剂的合成基底；欧洲专利申请No.393,749叙述了在钢的冷辊润滑液中用的碳酸酯；欧洲专利申请No.482,693叙述了在汽车的四冲程汽油和柴油发动机的润滑组合物中使用碳酸酯；欧洲专利申请No.421,298和No.426,152叙述了特别是在用氟里昂R-134a的致冷体系中的润滑组合物中使用的碳酸酯，其特点是它有极好的润滑和清洗特性，并有与氟里昂134a的互溶性；化学文摘 116，1992，63269d叙述了用碳酸酯作为合成润滑剂用于致冷系统；欧洲专利申请No.452,816叙述了用碳酸酯作为致冷系统润滑剂的组分。
上述现存技术文献中都没有指出在二相发动机中使用下面所述的特殊碳酸酯在所产生的废气中使烟量减少的任何可能性。
过去试图在二相发动机用的油—燃料混合物中加入特别的添加剂来解决减少烟量的问题。这些添加剂可包括例如胺、苯甲酸或硫代苯甲酸衍生物的酰胺盐、磷酸衍生物的胺盐或各种季铵的氢氧化物，如国际专利申请WO 92/12224中所述。
正如前面所指出，本发明基本上是基于这一发现的，即将特殊的脂族三醇或四醇的碳酸酯作为润滑剂与二相内燃机用的常规燃料混合是能够基本上减少废气中的烟量的。
按照上述原理，本发明涉及选自由下述式(1)所限定的碳酸酯式中：
R1为含1-20个碳原子的直链或支链烷基；
R2为氢原子，含1-20个碳原子的直链或支链烷基或
Figure C9411492600071
R’为乙烯基-(CH2)2或丙烯基-CH2-CH(CH3)；
p为0-10的数，据其用作二相内燃机的低烟量润滑基底而定。
本发明所用的碳酸酯(I)是粘稠液体，100℃时的粘度为5-50cSt；具体的例子有：
季戊四醇的四(丁基酯碳酸酯)和
三羟甲基的三(2-乙己基酯碳酸酯)。
碳酸酯的制备方法是用碳酸烷基酯和多元醇在酯交换反应条件和酯交换催化剂存在下进行反应。适合的碳酸烷基酯的例子有碳酸二甲酯、碳酸二乙酯、碳酸二丁酯和碳酸二(2-乙基己酯)；适合的多元醇有三羟甲基丙烷和季戊四醇；适合的催化剂的例子有氢氧化钠，甲醇钠，有机铝酸三烷酯、钛酸四烷酯、钖酸二烷酯和盐，钖的氧化物和烷氧化物。在酯交换反应中，所用的碳酸烷基酯与多元醇的比最好是约5∶1至20∶1，并有较高的操作温度，例如100℃至250℃，反应终止后，用常用的已知方法将碳酸酯从混合物中回收。
本发明也涉及二相内燃机用的含有下列(a)、(b)、(c)和(d)的低烟量润滑组合物；(a)碳酸酯和一种或多种(b)溶剂、(c)重质高粘度润滑油或另一抗咬剂(anti-gripping agent)和(d)常用添加剂。
本发明润滑组合物中常用的溶剂(b)是轻质烃溶剂，应基本有与燃料混溶的功能。
组分(c)是重质高粘度润滑油，即高粘度再制无蜡润滑油或由另一抗咬剂组成，例如高分子量聚异丁烯；当然也可用上述抗咬剂的混合物。
常用的添加剂(d)包括溶解剂、抗磨剂、抗氧化剂、阻蚀剂、清洁剂、凝点降低剂、摩擦改良剂等。
可以加入的其他添加剂是抗爆剂、抗铅剂、染料、辛烷数改良剂、抗氧化剂、防锈剂、抑菌剂、橡胶缓蚀剂、金属减活剂、消乳剂、活塞上部润滑剂和抗凝剂。
本发明的组合物一般含：(a)30-95wt％的碳酸酯(I)，(b)5-20wt％的溶剂，(c)0-15wt％的重质高粘度润滑油或另一抗咬剂和(d)0-15Wt％的常用添加剂。在最佳实施方案中，润滑组合物将含(a)65-70wt％的碳酸酯(I)，(b)约10wt％的溶剂，(c)5-10wt％的重质高粘度润滑油或另一抗咬剂和(d)5-15wt％的常用添加剂。
本发明的润滑组合物可以用于分别润滑的二相发动机，它是独立于燃料的注入而注入的，它也可以作为与燃料的混合物而用于二相发动机。
因此，本发明的另一方面是涉及用于二相内燃机的含有燃料和上述润滑组合物的低烟量混合物。
适合于上述目的燃料通常来自石油蒸馏的烃燃料，例如ASTM-D-439-73汽油。这些燃料也可含烃物质，如醇和醚，以及植物源衍生的燃料，但汽油是优选的燃料，即具有ASTM沸点60℃(10％分馏点)至约205℃(90％分馏点)。
本发明的润滑剂—燃料混合物通常含1-5wt％、一般约为2wt％量的上述润滑组合物。
下面的实验实例将给予本发明以更好的说明。
实例1
三羟甲基丙烷三(2-乙基己酯碳酸酯)的制备
将87.2g(0.65mol)三羟甲基丙烷、1.859g(6.5mol)碳酸二(2-乙己基)酯和0.5g甲醇钠的30％的甲醇溶液加入一三升烧瓶，烧瓶装有具有20个多孔板的蒸馏柱，冷却器，液体分流头和收集器，电磁搅拌器，并将其连接于真空泵。
酯交换反应条件如下：
残压：10-12托
柱底温度：157-206℃
柱顶温度：70-79℃
回流比：1/1
在1.5小时内收集到262g的2-乙基己醇
沉淀物(1.685g)经用二氧化碳处理后过滤，多余的碳酸二(2-乙己基)酯在一小的玻璃薄膜蒸发器中在200℃浴温和1托残压下蒸发。
按以上方法得到三羟甲基丙烷的三(2-乙基己酯)碳酸酯沉淀：其中86％是单体形状，其余的百分数基本上由低聚产物组成。
所得到的产品的特性如下：
40℃粘度           191cSt
100℃粘度          14.8cSt
粘度指数           69
滑点               -30℃
实施例2
烟量的评定是用Yamaha CE 50S发动机进行的，首先以6500rpm作热运转循环并全负载30分钟，然后冷却30分钟，然后以2000rpm再无负载加热30分钟，最后停机30分钟。在标准条件下进行10次加速，其间测定放出的烟的浊度。
将发动机中加入无铅汽油，RON值为91；分别加入润滑组合物，其量为燃料—润滑剂混合物重量的1-5％，根据转数和负载而定。
具体进行试验的润滑组合物如下，第一个是本发明的组合物，其余是用作比较的已知技术：
润滑组合物1：含67wt％的实例1的碳酸酯和33wt％的添加剂、抗咬剂和溶剂；
—润滑组合物2：含67wt％商品供应的碳酸酯润滑剂和33wt％的与实例1中相同种类和量的添加剂、抗咬剂和溶剂；
—润滑组合物3：含67wt％的另一商品供应的碳酸酯润滑剂和33wt％的与实例1中相同种类和量的添加剂、抗咬剂和溶剂；
—润滑组合物4：含94.7wt％的中性溶剂150和5.3wt％的与实例1相同的那些添加剂；
—润滑组合物5：含94.7wt％的中性溶剂6000和5.3wt％的与实例1相同的那些添加剂；得到的烟浊度值如下：
   润滑组合物           烟(绝对值％)
        1                    7.8
        2                    12.4
        3                    14.1
        4                    32.1
        5                    29.8
每个试验进行10次，上示值是后5次的平均值，头5次因可靠性有限而弃之。
实例3
在发动机上进行实验以观察基于实例1的碳酸酯的不同配方。其结果与市场供应的常用碳酸酯为基础的平行配方的结果进行比较。
试验使用油锯发动机ALPINA，按与用Husqwarna相似的试验步骤进行。试验包括高功率运转发动机，并在运转5小时后评定活塞环区的状况(环粘滞)，活塞胶质的形成(总活塞胶质)、排气口堵塞、燃烧室沉积物的形成(燃烧室总沉积物)
第1系列的测定(表1)涉及只是所用的底基种类不同的配方之间的比较，表1中的CAL-1润滑组合物由7.5wt％多功能添加剂和92.5wt％的实例1产品组成，此配方与不同的商品配方进行比较，第1个配方为EST-2，由7.5wt％的用于CAL-1的多功能添加剂和92.5wt％商品酯(由碳酸和三羟甲基丙烷制得的第1酯(称为ESTER-2)组成)；第2配方为EST-1，含7.5wt％的相同多功能添加剂和92.5wt％商品酯(称ESTER-1)(由碳酸和三羟甲基丙烷形成的第2酯组成)。
有EST-2存在的试验重复2次。
                        表    1
                           CAL-1  EST-2  EST-2  EST-1
活塞裙             10分钟  10.0   9.8    9.23   9.37No1环凸(Land n°1)  ″″   6.16   2.07   1.14   3.78环槽胶质            ″″   7.0    1.91   0      4.23
顶部下端        ″ ″    9.80   8.65   4.50    5.75活塞总胶质      ″ ″    82.4   56.1   37.2    57.8排气口堵塞      ″ ″    10.0   9.7    9.0     10.0环粘附          ″ ″    10     3      1       1总燃烧室沉积    (gr.)    0      0.05   0.07    0
表1中的数据显示，含实例1产品的配方对于活塞环区直至试验完毕有正规的功能，对于活塞的清洁作用而言也有较好的结果，相反，用对比配方则有较多的胶质形成。
表2显示在也含有溶剂的配方存在下的发动机试验数据。
更具体的说，CAL-2是由7.5wt％的常用功能添加剂、10wt％的石油溶剂和82.5wt％的实例1产品组成的润滑组合物。
CAL-3是由8wt％的常用多功能添加剂、10wt％的石油溶剂、67wt％的实例1产品和15wt％的聚异丁烯组成的润滑组合物。
组合物EST-3是作为参数的(评定进行了二次)，由7.5wt％的常用多功能添加剂、10wt％的石油溶剂和82.5wt％的市售碳酸和多元醇形成的酯混合和物(称为ESTER-3)。
                 表    2
                     CAL-1   CAL-3   EST-3   EST-3
  活塞裙    10分钟   9.97    10.0    10.0    8.96No1环凸    ″ ″   3.90    6.1     4.24    2.12
  环槽胶质        ″ ″    6.28    7.55    1.56    1.25顶部下端        ″ ″    9.05    10.0    8.0     3.2活塞总胶质      ″ ″    73.0    84.1    59.5    38.8排气口堵塞      ″ ″    9.98    10.0    10.0    9.5环粘附          ″ ″    10.0    10.0    10.0    9.5总燃烧室沉积    (gr.)    0.0     0.0     0.07    0.0
从表2可知，含本发明产品的配方可产生极好的结果，特别是在胶质形成方面。

Claims (7)

1.一种含有选自下述式(I)所限定的碳酸酯的润滑组合物在二相内燃机中的用途，
式中：
R1为含1-20个碳原子的直链或支链烷基；
R2为氢原子，含1-20个碳原子的直链或支链烷基或者
Figure C9411492600022
R′为乙烯基-(CH2)2或丙烯基-CH2-CH(CH3)；
p为0-10的数。
2.权利要求1的用途，其特征在于所述润滑组合物含有：
季戊四醇的四(丁基酯碳酸酯)或三羟甲基丙烷的三(2-乙己酯碳酸酯)。
3.权利要求1的用途，其特征在于所述润滑组合物还包括选自溶解剂、抗磨剂、抗氧化剂、缓蚀剂、清洁剂、凝点降低剂和磨擦改良剂的一种或多种添加剂。
4.权利要求1的用途，其特征在于所述润滑组合物还包括一种或多种选自下列的添加剂：抗爆剂、抗铅剂、染料、辛烷数改良剂、抗氧化剂、防锈剂、抑菌剂、橡胶缓蚀剂、金属减活剂、消乳剂、汽缸上部润滑剂和抗凝剂。
5.权利要求1的用途，其特征在于所述润滑组合物含有(a)50-95wt％的所述碳酸酯(I)，(b)5-20wt％溶剂，(c)0-15wt％的重质高粘度润滑油或另一抗咬剂和(d)0-15wt％的常用添加剂。
6.权利要求5的用途，其特征在于所述润滑组合物含有(a)65-70wt％的碳酸酯(I)，(b)约10wt％的溶剂，(c)5-15wt％的重质高粘度润滑油或另一抗咬剂和(d)5-15wt％的常用添加剂。
7.权利要求1的用途，其中所述润滑组合物还包括溶剂。
CN94114926A 1993-07-29 1994-07-29 二相发动机用低烟润滑组合物 Expired - Fee Related CN1050629C (zh)

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