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CN1035014C - 润滑油用的聚合物添加剂 - Google Patents

润滑油用的聚合物添加剂 Download PDF

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CN1035014C
CN1035014C CN93114478A CN93114478A CN1035014C CN 1035014 C CN1035014 C CN 1035014C CN 93114478 A CN93114478 A CN 93114478A CN 93114478 A CN93114478 A CN 93114478A CN 1035014 C CN1035014 C CN 1035014C
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methyl
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alkyl
polyamines
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CN1086535A (zh
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A·桑坦布罗吉奥
G·普里迈尼
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AIJEPU BERTROLI CORP
Agip Petroli SpA
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Abstract

经第一步的聚烯烃共聚物同(甲基)丙烯酸的C8-C25醇的酯和(甲基)烯酸的混合物反应，然后第二步，由所改性的共聚物同多胺缩合，可制得提高润滑油粘度指数的油溶性聚合物，此聚合物具有分散剂性质，并能降低倾点(“倾点下降剂”)。

Description

润滑油用的聚合物添加剂
本发明涉及一种改进润滑油粘度指数(粘度指数改进剂-V.I.I)的油溶性接收聚合物，它具有分散剂性能，并能降低倾点。
在有关润滑油技术方面，众所周知，加入油溶性聚合物可改进不同温度下的润滑油的流变性能(粘度指数改进剂-V.I.I)，例如，丙烯酸或甲基丙烯酸的烷基酯的聚合物或共聚物，其中在其烷基上的碳原子数目应多至使其可溶于油。
在技术上还知道，在所说的油溶性聚合物中加入可共聚或接枝含氮单体以使产品除了具有粘度指数改进剂的性能外还具有分散性能，由此而受益。这种可共聚的含氮单体一般选自乙烯基咪唑、乙烯基吡咯烷酮、乙烯基吡啶和甲基丙烯酸N，N-二烷基-氨基乙酯。
一种共聚的变通方法是将作为分散剂和倾点下降剂的一种或多种单体接枝于乙烯-丙烯共聚物(EPM)或乙烯-丙烯-二烯三元共聚物(EPDM)上，用此法可提高粘度指数，同时还具有分散剂和倾点下降剂性能。
例如，美国专利3,923,930号讨论了一种以聚甲基丙烯酸酯接枝的三元共聚物。该聚甲基丙烯酸酯是由长链醇的甲基丙烯酸酯和甲基丙烯酸二烷基氨基烷基酯构成的。
另一种方法是将能按顺序提供具有活性位置的作用物的酸性或碱性分子接枝于共聚物或三元共聚物。
美国专利4,144,181号讨论了以马来酸酐接枝，随之同多胺反应得到的EPM或EPDM聚合物，
美国专利4,146,489号讨论了以选自乙烯基吡啶和N-乙烯基吡咯烷酮单体接枝的EPM或EPDM共聚物。
仍然需要一种添加剂，只要改变操作条件就能方便地改进其倾点下降剂和分散剂的所需活性。这种添加剂在低浓度下是有效的，而且适应性强的。
本申请人现在发现一种含氮接枝共聚物，可以克复或至少会基本上减少影响现有技术的缺点。
而且发现一种简单而有利的方法，可制备上述的接枝聚合物。
因此，本发明的第一个方面涉及一种粘度指数改进剂，具有分散剂和倾点下降剂的性能，其制法分两步，
(a)在第一步中，
使选自乙烯-丙烯或乙烯-丙烯-二烯的共聚物在自由基聚合条件下同下面的组合物反应，该组合物由(甲基)丙烯酸和通式(I)的(甲基)丙烯酸酯组成。
CH2＝C(R)-COOR′                   (I)其中R选自氢和甲基，R′为基本上直链烷基或具有含8-25碳原子的支链异构体低于20％重量的基本上直链烷基的混合物；
(b)在第二步中，使在第一步(a)得到的产物同通式为(II)的多胺反应：
NH2-(CH2)b-(-NH-Ch2b-)-NH2               (II)其中，b可以是2或3，n为0-5范围内一个整数，直到羧基全部或实际上全部转换成酰胺基。
用于本发明的乙烯-丙烯共聚物(EPM)是可溶于油的，重均分子量(Mw)5,000-500,000，优选的为10,000-200,000，更为优选的为20,000-100,000。用重均分子量(Mw)与数均分子量(Mw)比值测定得到的相当窄的分子量分布是优选的。事实上，Mw/Mn比值低于7是优选的，更为优选的是比值低于或等于4。在所说聚合物中乙烯的含量在15-90％重量范围内，优选的则为30-80％重量。
乙烯-丙烯-二烯三元共聚物含少量(优选的为低于10％重量)的非共轭二烯，例如1，4-己二烯、二环戊二烯、乙基-降冰片烯。相反，乙烯则占45-65％重量。重均分子量在10,000-200,000范围内，Mw/Mn比值低于8。
当实施本发明时，除EPM和EPDM外，还可用少量的(优选30％以下)的其它橡胶类的聚烯烃材料，如加氢的苯乙烯-丁二烯、苯乙烯-异戊二烯共聚物、无规聚丙烯、低密度聚乙烯。
“(甲基)”丙烯酸和(甲基)丙烯酸酯”可理解为丙烯酸或甲基丙烯酸和酯，或它们的混合物。
在通式(I)的(甲基)丙烯酸酯中，R′基本上是直链烷基，或基本上直链烷基的混合物，其中支链异构体含量低于20％重量，且烷基的碳原子数为8-25，优选10-20。
根据本发明的优选的具体实施方案，使用C10-C15(甲基)丙烯酸酯和C16-C20(甲基)丙烯酸酯的混合物，更为优选的是C12-C18(甲基)丙烯酸酯。两种成分相互重量比在6∶1-0.5∶1范围内，优选的为3∶1-1∶1。
为实施本发明，可以使用通式(II)的任何多胺，例如三亚乙基甲胺(n＝2，b＝2)，二亚乙基三胺(n＝1，b＝2)，三亚丙基四胺(n＝2，b＝3)，五亚乙基己胺(n＝4，b＝2)，二亚丙基三胺(n＝1，b＝3)。
根据本发明的优选的具体实施方案，通式(II)多胺中的“n”值在1-4范围内，更为优选的是2。
根据本发明，聚合物添加剂的制备可以在惰性溶剂中进行，也可在无溶剂下进行，优选惰况是在惰性溶剂中；更为优选的是在矿物油中进行。在其中，要被接枝的聚合物或三元共聚物溶解量为2-50％重量，优选的是5-20％重量。
用(甲基)丙烯酸衍生物(第一个反应步骤)共聚和接枝反应需要一自由基引发剂。用于此目的为烷基过氧酯、烷基过氧化物、烷基过氧化氢、二酰基过氧化物等，例如，过苯甲酸叔丁酯、二叔丁基过氧化物、叔丁基过氧化氢、氢过氧化枯烯、过氧化苯甲酰、过辛酸叔丁酯，优选的是过辛酸叔丁酯。当然，也可使用上述引发剂的混合物。
引发剂用量为相对于反应物(不包括多胺)总重量的2-12％重量，优选的为3-9％重量。
为进行接枝和共聚反应必须的温度范围为70-150℃，优选90-130℃。本技术领域专业人员都知道，所要求的温度决定了自由基引发剂的选择。
根据对最终产物所要求的性能，要接枝的聚合物对通式(I)的(甲基)丙烯酸酯对(甲基)丙烯酸的重量比可以改变。换言之，如果希望获得的产物作为倾点下降剂具有卓越性能，并显示较低的分散能力，则应选高的(甲基)丙烯酸酯对(甲基)丙烯酸比值。如果希望产物具有较高的分散力应选用高的(甲基)丙烯酸对(甲基)丙烯酸酯的比值。在任何惰况下，要接枝的聚合物∶通式(I)的(甲基)丙烯酸酯∶(甲基)丙烯酸通常为40∶20∶1-10∶2∶1，优选为25∶16∶1-14∶3∶1。
进行接枝和共聚反应，优选地是将(甲基)丙烯酸逐步加入到含聚合物、通式(I)的(甲基)丙烯酸酯和第一等份的自由基引发剂的反应混合物中。其余的引发剂在随后等份地加入，以完成(甲基)丙烯酸和(甲基)丙烯酸酯的反应。
反应时间随所选温度和(甲基)丙烯酸和引发剂加入速率而变化。
为说明起见，当操作温度约70-150℃，在2-4小时内，接枝和共聚反应完成。
当(甲基)丙烯酸衍生物同聚合物和其相互之间接枝和共聚反应结束时，(甲基)丙烯酸的羧基，同通式(II)的多胺之间的反应开始，产生相应的酰胺。
将通式(II)的多胺或多胺混合物加到接枝聚合物中，加入的摩尔量约为羧基的1/2。当然也可以比此值高，但这时需从最终产物中去除未反应的多胺。多胺∶COOH基之摩尔比值低于1/2是不适宜的，因为在最终产物中会含不需要的自由羧基。
通式(II)的多胺可在任何温度下加入到接枝聚合物中，然而，优选的是在接枝和共聚反应之后不久将多胺加到反应混合物中。即是说，这时的温度为70-150℃，优选的是90-130℃。
由接枝的聚合物和通式(II)的多胺组成的上述混合物需要在温度130-190℃下加热。这是为了将羧基和多胺的-NH2基相互反应的产物转变成酰胺。事实上可以假定，由于-COOH和-NH2基之间的相互反应，首先形成相应的盐，例如-COO-RNH3 +，后者随后，特别是由于温度升高的影响，产生相应的-CONHR酰胺，同时排出水。
铵盐的消失可以用分光度方法，特别是红外分析来证实。
根据不同的参数，特别是温度的不同，第二步可持续不同的时间间隔。在温度170-180℃范围内操作，则第二步可认为在2-4小时内完成。反应完成之后，反应混合物优选地应进行处理，以去除所有的形成的水、痕量的任何未反应产物和引发剂分解物。为此，应将反应混合物在高温、减压或在惰性气流下保持几分钟。
在上述过程结束时获得的接枝聚合物，由于(甲基)丙烯酸量和多胺类型不同，可有不同的氮含量。为说明起见，通过本发明方法制得的接枝聚合物含氮量为0.3-4％的重量，优选为0.6-2％重量。因为分散力是含氮量的函数，显然，本发明方法制得的产品可具有不同的分散力，只要改变(甲基)丙烯酸的量和“n”和“b”即可。
通过改变C10-C15(甲基)丙烯酸酯的比值，可以改变倾点下降剂的性能。事实上，随着C16-C20(甲基)丙烯酸酯量的增加，在高粘度油品中倾点下降剂的性能提高。
在上述过程结束时，获得具有粘度指数改进剂、分散剂和倾点下降剂性能的聚合物添加剂在惰性溶剂中的溶液。
聚合物添加剂可通过已知方法去除溶剂，如当溶剂具有足够挥发性时，通过减压蒸发，即可分离出纯聚合物添加剂。
本发明的聚合物添加剂可与其它普通添加剂如分散剂、洗涤剂、抗磨添加剂、抗氧剂等等一起用于成品润滑剂。
根据一优选的具体实施方案，添加剂可以此方式加到润滑油中，或通过使用将添加剂溶于溶剂-增充剂中制得的含5-30％重量，优选为10-20％的溶液，很容易地将添加剂加到润滑油中。根据本发明的优选的情况，上述的溶剂-增充剂和在制备聚合物添加剂时使用的惰性溶剂是相同的矿物油。
本发明的另一方面是提供含大部分的矿物油或半合成油和有效量的上述含氮的聚合物添加剂(作为粘度指数改进剂、分散剂和倾点下降剂)的润滑油组合物。以净聚合物添加剂计，这样的有效量一般为0.4-6％，优选为0.6-40％重量。
下列报导的实施例是为了更详细地说明本发明。
            实施例1(“A”添加剂)
将300克的乙烯-丙烯共聚物橡胶(重量/重量的比值为54-46％)(Mw＝200,000，分散性＝2.3)在SN130矿物油溶液，装入1升的4颈烧瓶的反应器中。上述溶液在100℃的动力学粘度(KV)约为1,200厘沲。
将烧瓶内容物在氮气流(约40升/小时)下加热一小时，使温度达107℃。
然后在反应器中加入甲基丙烯酸的高级醇酯，醇的碳原子数为C12-C18，其中C12-C14∶C16-C18等于60∶40(重量/重量)。
同上述的甲基丙烯酸酯一起，加入第一份(总数四份中)的0.5克的过辛酸丁酯。
然后在反应器中开始加入1.6克的丙烯酸。加入时利用一计量泵，以使加入受到调节，使加入在约60分钟内完成。在上述的加入计量酸过程中，温度应保持在约107℃。
在计量加酸开始后30分钟，第二次加入0.5克过氧化物，随后，再经30分钟后，进行再次加入过氧化物。在加酸结束后半小时，将第四，和最后一份过氧化物加入。
约每30分钟从反应烧瓶中收集试样进行红外分析，以监测反应的进展，通过检查红外吸收光谱，可以监测属于(甲基)丙烯酸单体的吸收峰的消失。
当甲基丙烯酸酯和丙烯酸接枝和共聚物的第一反应期(持续约3小时)结束时，同三亚乙基四胺(TETA)反应而使丙烯酸的酰胺化的第二反应步骤开始。
反应温度控制系统的温度现置于180℃；反应混合物在约60分钟中达到此温度。
当系统达到约140℃时，进行加入TETA(1.6克，相当于丙烯酸1/2)。通过检查红外光谱，最初可观测到丙烯酸和胺之间形成盐加合物；然后，可看到生成酰胺键，这发生在约180℃。
为完全转化为酰胺，并随后去除形成的水，大约需要反应3小时。
将反应混合物最后冷至约100℃，从反应器中取出反应混合物，并用红外光谱检查。
总反应时间约9小时，分配如下：
      —加热和排出：        1小时
—接枝和共聚：        3小时
—从107加热到180℃：  1小时
—酰胺化和洗涤：      3小时
—冷却和卸料：        1小时产品监定。
通过“沥青质试验”评价了分散剂性能。在环烷酸铜作为催化剂存在下氧化环烷油制得沥青质。试验方式如下：取100毫克的要测定分散剂性能物体，用SN150矿物油将其调节成总重量20克，轻微加热并搅拌；另外，制备30毫克沥青质溶于10毫升二氯甲烷的溶液，随后加到溶解的聚合物中。将此溶液在150℃的炉中保持60分钟，以去除任何挥发物，然后使之冷却。
将溶液转移到浊度计池中，在仪器上读取浊度值，浊度值随聚合物分散力降低而增加。在第一次读取后，将溶液在7,500rpm(每分钟转数)离心10分钟，在浊度计上进行第二次读数。由下成方程式可得到分散性指数：
        I.D＝离心后的浊度/离心前的浊度
浊度的绝对值构成一重要因素，I.D值相同时，具有低的浊度绝对值的添加剂是优选的。
接枝添加剂在矿物油中的溶液，如在上述反应中得到的，含14.6％重量的接枝聚合物(通过渗析相同溶液测定的)。
溶液显示下述特性：
—100℃下的动力学粘度(KV)：       1120厘沲
—浊度：                          22N.T.U
分散性指数：                      100/100
氮的百分含量：                    0.19％
上述溶液在SN150中被稀释成10％。
所得到的溶液显示下列特性：
100℃的KV                         10.6厘沲
40℃的KV                          67.63厘沲
剪切稳定性(CEC-C-L-14-A88试验)：  14.24％
动态粘度(DV)(-20℃)：             3000厘泊
倾点：                            -33℃
为了对用作润滑油添加剂的“A”添加剂进行评价，使用SAE10W40级的润滑剂，其中含：
—51.5％的矿物基油，
—24.0％的合成基油，
—14.5％通常的添加剂组合(由二硫磷酸锌、高碱性磺酸钙、聚异丁烯琥珀酰亚胺、邻磺基苯酚和芳香胺组成)，
—10％的“A”添加剂在矿物油中的溶液，如由上述接枝和共聚反应得到的。
第一个试验是为了检查由上面解释制备的配方与氟橡胶的相容性。
为此，进行了命名为“VW Test PV 3344-密封相容性”的试验的结果示于表1，其中，规格限制在括号内表明。
                表  1
抗强强度(百万帕斯卡)：       9.9(≥8.0)
破裂伸长率(％)：             186(≥160)
100％下的裂纹：    无裂纹    无裂纹
为评价发动机性能，SAE15W40级润滑油具有下列组成：
—矿物基油：                 81.15重量
—添加剂组合：               10.35％重量
—“A”添加剂在矿物油中的溶液(如由上述接枝和共聚反应得到的)：                  8.50％
为评价所配制的润滑剂的性能，进行发动机试验，此试验被称为“VE序列”(ASTM STP 315H PTIII方法)，结果示于表2，括号内为规格限制。
               表  2
平均发动机淤渣        9.24(最低9)
平均发动机涂漆        5.61(最低5)
活塞边缘涂漆          7.05(最低6.5)
平均凸轮摩损(密耳)    0.69(最大5.0)
最大凸轮摩损(密耳)    1.1(最大15)
倾点                  -30℃
                   实施例2-7
按照制造实施例1的“A”聚合物添加剂相同的方法，通过改变C12-C14对C16-C18甲基丙烯酸酯的比值、丙烯酸量和胺的类型和量，制得其它的聚合物添加剂(仍由300克乙烯-丙烯共聚物在矿物油中的10％的溶液出发)。
同时，第一步聚合时间、过氧化物量以及最后的洗涤时间也有变化。
                    实施例2
由20克甲基丙烯酸酯(C12-C14酯对C16-C18酯的比值等于75∶25)、1.6克丙烯酸和2.57克五亚乙基六胺(PEHA)出发制得“B”聚合物添加剂。聚合反应时间为4小时，使用3克过辛酸叔丁酯。洗涤步骤的时间为90分钟。
最终的聚合物溶液的100℃动力学粘度为1209厘沲，分散性指数(I.D)为158/155，在矿物油中100％的倾点为-24℃，浊度为26N.Y.U
                    实施例3
由10克甲基丙烯酸酯(C12-C14酯对C16-C18酯的比值等于75∶25)。1.6克丙烯酸和1.46克二亚丙基三胺(DDTA)出发制备了“C”聚合物添加剂。聚合反应时间为2小时，使用2克过辛酸叔丁酯。洗涤时间为90分钟。
得到的聚合物溶液的KV＝1286厘沲，浊度＝21N.T.U和I.D＝200/200。
                    实施例4
由20克甲基丙烯酸酯(C12-C14酯对C16-C18酯的比值等于75∶25)、2克丙烯酸和1.82克的DPTA出发制得“D”聚合物添加剂。聚合反应时间为2小时，使用2克过辛酸叔丁酯。洗涤时间为90分钟。
得到的聚合物溶液的KV＝1288厘沲，浊度＝19和I.D-150/150。
                    实施例5
由10克甲基丙烯酸酯(C12-C14酯对C16-C18酯的比值等于75∶25)、1.8克丙烯酸和1.64克DPIA出发制得“E”聚合物添加剂。聚合反应时间为2小时，使用2克过辛酸叔丁酯。洗涤时间为90分钟。
得到的聚合物溶液的KV＝1278厘沲，浊度＝30，I.D＝154/150。
                    实施例6
由20克甲基丙烯酸酯(C12-C14酯对C16C18酯的比值等于65∶35)、2克丙烯酸和2.03克TETA出发制得“F”聚合物添加剂。聚合反应时间为3小时，使用2克过辛酸叔丁酯。洗涤时间为120分钟。
得到的聚合物溶液在矿物油中10％时的倾点为-36℃，I.D＝161/152。
                    实施例7
由15克甲基丙烯酸酯(C12-C14酯对C16C18酯的比值等于60∶40)、1.6克丙烯酸和1.62克TETA出发制得“G”聚合物添加剂。聚合物时间为3小时，使用2克过辛酸叔丁酯。洗涤时间为150分钟。
在矿物油中10％时的聚合物溶液的倾点为-33℃，I.D＝135/125。

Claims (8)

1.润滑油用的聚合物添加剂，其特征在于它是按照以下两步制得的：
a)第一步，在70-150℃及惰性溶剂中，使乙烯-丙烯或乙烯-丙烯-二烯共聚物在自由基聚合条件下同由(甲基)丙烯酸和通式(I)的(甲基)丙烯酸酯
    CH2＝C(R)-COOR′                   (I)组成的组合物进行反应，在通式(I)中，R′为具有8-25碳原子的基本上直链的烷基，或基本上直链的C10-C15和C16-C20的烷基的混合物，其支链异构体低于20％，
b)第二步，在130-190℃及惰性溶剂中，使从(a)步得到的产物同通式(II)的多胺：
NH2-(CH)b-(-NH-CH2b-)n-NH2          (ii)进行反应，(II)式中的b为2或3，n为0-5范围内的整数，直到羧基完全或实际上完全转变为酰胺基，其中共聚物：通式(I)的(甲基)丙烯酸的重量比为40∶20∶1-10∶2∶1。
2.权利要求1的添加剂，其特征是在通式(II)的多胺中，“n”是1-4范围内的整数。
3.权利要求1的添加剂，其特征是R′为一基本上直链的烷基，或具有10-20碳原子的支链异构体不超过20％重量的基本上直链的烷基混合物。
4.权利要求1的添加剂，其特征是R′由C12-C14和C16-C18烷基以6∶1-0.5∶1重量比构成。
5.权利要求4的添加剂，其特征是R′由C12-C14和C16-C18烷基以3∶1-1∶1重量比构成。
6.权利要求1的添加剂，其特征是共聚物∶通式(I)的(甲基)丙烯酸酯∶(甲基)丙烯酸的重量比为25∶16∶1-14∶3∶1。
7.权利要求1的添加剂，其特征是通式(II)的多胺与(甲基)丙烯酸的摩尔比为1∶2。
8.权利要求1的添加剂，其特征是所说的惰性溶剂是矿物油。
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EP0596567A1 (en) 1994-05-11
EP0596567B1 (en) 1998-03-11
US5425888A (en) 1995-06-20
ES2113479T3 (es) 1998-05-01
SG64293A1 (en) 1999-04-27
ATE163967T1 (de) 1998-03-15
GR3026509T3 (en) 1998-07-31
CN1086535A (zh) 1994-05-11
DK0596567T3 (da) 1998-10-07
DE69317355D1 (de) 1998-04-16
ITMI922552A0 (it) 1992-11-06
IT1258249B (it) 1996-02-22
DE69317355T2 (de) 1998-09-10
ITMI922552A1 (it) 1994-05-06

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