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CN1047195C - 润滑油组合物 - Google Patents

润滑油组合物 Download PDF

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CN1047195C
CN1047195C CN94105387A CN94105387A CN1047195C CN 1047195 C CN1047195 C CN 1047195C CN 94105387 A CN94105387 A CN 94105387A CN 94105387 A CN94105387 A CN 94105387A CN 1047195 C CN1047195 C CN 1047195C
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lubricating oil
ester
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alcohol
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P·甘比尼
P·科克
A·桑塔布罗吉
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Abstract

本发明涉及一种通式(I)的具有分散剂和抗氧化剂特性的润滑油粘度指数改进剂及其制备方法及含有该改进剂的润滑油组合物，式(I)各基团定义见说明书。

Description

润滑油组合物
本发明涉及具有分散剂和抗氧化剂性能的润滑油粘度指数改进剂(V.I.I)。加油溶性聚合物V.I.I到润滑油中能改进其温变时流变性能是本领域公知的，这样的聚合物的例子有丙烯酸的或甲基丙烯酸的烷基酯聚合物或共聚物，由于在烷基中含有大量的碳原子，使它们变得油可溶。将含氮可共聚单体引入到所述的油溶性聚合物中，以使得最终产品除了粘度指数得到改进外还改进了分散性，这也是本领域公知的。公知的作为分散剂单体的所述含氮可共聚单体通常选自：乙烯基咪唑，乙烯基吡咯烷酮，乙烯基吡啶和N，N—二烷基—氨基乙基—甲基丙烯酸酯。这样的实施描述在如英国专利1,272,161和1,333,733，美国专利3,732,334和比利时专利874,068。
用于内燃机中以便在发动机运转期间降低油泥生成和润滑油氧化的V.I.I共聚物同时具有分散剂和抗氧化剂性能，这也是已知的。
例如，美国专利4,699,723描述了用含氮原子和硫原子的单体如4—甲基—5—乙烯基噻唑接技的乙烯—丙烯共聚物，除了具有粘度指数改进作用外还具有分散剂和抗氧剂特性。
使用这些聚合物(通常称为多功能聚合物)也改进了含在润滑油中的特定添加剂(例如抗磨剂如二硫代磷酸锌，分散剂如多异丁烯基琥珀酰亚胺，降解剂如磺酸钙，抗氧化剂如空间位阻酚等)的性能且可能降低其所需用量。
本发明提供用于润滑油的无硫聚合物添加剂，它能有效地改进润滑油粘度指数同时具有分散剂和抗氧化剂性能。也发现了制备所述添加剂的简单且方便的方法。
因此，本发明首先提供衍生自不饱和酯共聚的通式如下的具有分散剂和抗氧化剂性能的聚合物粘度指数改进添加剂。
Figure C9410538700051
所述的通式(I)代表反应的单体的类型和量但不表示其在最终聚合物链中的排列。其中，R′可相同或不同为氢原子或烷基；Ra是烷基或具有6到25个碳原子的直链或支链的一种混合烷基；Rb是具有1到4个碳原子的烷基或与Ra相同；Rc为有1或2个氮原子和4到20个碳原子的一个或多个直链、支链或环状烷基；x，y，z代表各种可聚合单体单元的重量百分数。x在80～95％之间，y在0到12％之间和z在2到8％之间。
按照本发明优选的实施方案：
x在85～95％(重量，下同)之间，y在3到7％之间和z在4到6％之间；
R′是甲基，因此由通式(I)所表示的所有的可聚合酯都是甲基丙烯酸酯；Ra是衍生自具有10到20个碳原子的天然或合成的直链或支链伯醇混合物的烷基；
Rb是甲基；
Rc是2，2，6，6—四甲基—
Figure C9410538700061
啶—4—醇基，因此可紧合单体CH2＝CR′—COORc是2，2，6，6—四甲基— 啶—4—醇甲基丙烯酸酯。
在本发明另一个优选的实施方案中，甲基丙烯酸酯Rc是如下物质组成的混合物：
50—85Wt％的2，2，6，6—四甲基—哌啶—4—醇的甲基丙烯酸酯。
15—50Wt％的N，N—二甲基—氨基乙醇的甲基丙烯酸酯，或N-(3—羟基丙基)—N′—甲基—哌嗪的甲基丙烯酸酯或其混合物。
本发明还提供一种制备通式(I)的多功能添加剂的方法。该方法包括聚合(甲基)丙烯酸Ra，Rb，和Rc酯的混合物，(甲基)丙烯酸Ra酯的量为80—95％(重量，下同)，(甲基)丙烯酸Rb酯为0—12％和(甲基)丙烯酸Rc酯为2—8％。
在本发明优选的实施方案中，聚合混合物由下列物质组成：
85—90wt％的(甲基)丙烯酸Ra酯，即具有10到20个碳原子的天然或合成直链或支链伯醇混合物的(甲基)丙烯酸脂，
3—7wt％(甲基)丙烯酸Rb酯，即甲醇的(甲基)丙烯酸酯，
(甲基)丙烯酸Rc酯，即2，2，6，6—四甲基—哌啶—4—醇的(甲基)丙烯酸酯或50—85wt％的2，2，6，6—四甲基—
Figure C9410538700072
啶—4—醇的(甲基)丙烯酸酯，余下的15—50wt％的是由N，N—二甲基—氨基乙醇的(甲基)丙烯酸酯或N—(3—羟基丙基)—N′—甲基
Figure C9410538700073
嗪，或其混合物组成的物质，
(甲基)丙烯酸Rc酯的总量占所有(甲基)丙烯酸酯混合物的4—6wt％。
本发明也提供一种通式(II)的新的丙烯酸酯或甲基丙烯酸酯：其中R′是氢原子或甲基，它属于(甲基)丙烯酸Rc酯类，因此当它与其它丙烯酸酯或丙烯酸烷酯聚合时可作为有用的分散剂功能的单体，它可通过通常的有机化学反应制备。为有效地聚合，这些单体可脱气(既可单独进行也可一起进行)，然后混合并用惰性有机溶剂稀释，该溶剂优选矿物油(如在100℃下为5.4CSt的溶剂中性油(SN))。然后该反应混合物在无氧和游离基引发剂(加热前或加热后加入)存在下加热到70—130℃，直到6O—100％的(甲基)丙烯酸酯转移到相应的共聚物中。适宜于这一目的的游离基催化剂通常选自：过辛酸叔丁基酯，过(2—乙基)己酸叔丁基酯，过异壬酸叔丁基酯，过苯甲酸叔丁基酯，偶氮一双—异丁腈，过氧化二苯(甲)酰，过氧化月桂酰和过氧二羧酸双(4—叔丁基环己基)酯且它的用量相对于每100份重量甲基丙烯酸酯为0.2到3份(重量)。
在反应混合物中可有硫化物如脂肪族硫醇，硫代甘醇和硫代酚(如叔十二烷基硫醇和乙二硫醇)，它们的目的在于调节共聚物的分子量。当这些硫化物在反应混合物中相对于100份(重量)的(甲基)丙烯酸酯以0.01到0.5份(重量)存在时，通常呈现其活性。反应的进度可用红外分析来监测。在上述温度及其它条件下，注0.5到4小时内，单体转化通常达到所述值。用这样的方法，可获得通式(I)的添加剂在惰性溶剂中的溶液。共聚物可通过已知方法如除去溶剂(减压下)来分离。
这样的添加剂可加到润滑油中，但这种添加最好使用含25—95％(重量)且优选40—70的溶在稀释溶剂中的添加剂浓缩物更方便。在本发明优选的实施方案中可使用与制备通式(I)的添加剂相同的惰性溶剂。
本发明也提供一润滑油组合物，它含主要量的润滑油和某一有效量的所述添加剂作为V.I.I.，分散剂和抗氧化剂。相对于这样的聚合物，这一有效量通常在0.5到10％(重量)之间，优选在1.2到6％之间。本发明的添加剂可与其它常规的添加剂如分散剂、降解剂，抗磨剂、抗氧化剂等一起用于最终的润滑油中(如机动车使用的润滑油)。下列实施例旨在说明本发明。
实施例1
向一带导热油加热套和锚式搅拌器，测温热电偶及氮气注射器的反应器中加入148gSN150矿物油，130.31gC12-C18直链甲基丙烯酸醇单体和1.7g2，2，6，6—四甲基
Figure C9410538700091
啶—4—醇的甲基丙烯酸酯，该系统在注入氮气的同时搅拌l小时。在反应进行的同时，将5gN—(3—羟基丙基)—N′—甲基— 嗪的甲基丙烯酸酯，15g甲基丙烯酸甲酯和0.9g作为聚合引发剂的过辛酸叔丁基酯(TBPO)分别进行脱气。然后将脱气的单体加到反应器中，将其温度升到100℃并加入引入剂。聚合立即开始并急剧放热。因此温度控制系统必须维持这一温度不变直到反应完全(2—3小时)。反应进度用红外分析跟踪，甲基丙烯单体双键的谱带在1320—1340Cm-1处消失。
在SN150中的聚合物终溶液在100℃下运动粘度为783.83厘沲。
对作为粘度指数改进剂的添加剂的评价
在100℃下，在SN150中10％溶液的运动粘度：l4.77厘沲。
在40℃下，在SN150中10％溶液的运动粘度：84.74厘沲。
在-20℃下，在SN150中10％溶液的运动粘度：2900厘泊粘度指数：184。分散剂性能的评价
添加剂的分散剂性能用所谓沥青质试验评价
沥青质是在作为催化剂的环烷酸铜存在下环烷烃油氧化而产生的。试验万法如下：将50mg欲测定其分散剂性能的共聚物在微热和搅拌下加到20gSN150中。另外将30mg沥青质溶在10ml二氯甲烷中制备一溶液并将其加到溶解的聚合物中。将溶液在150℃的烘箱中放置1小时以除去挥发性物质，然后冷却。将其移到浊度计的小池中并从仪器上读出浊度值，该值随聚合物分散能力的下降而上升。第一次读完后，将溶液在7500rpm下离心分离10分钟，然后再用浊度计进行第二次测量。分散指数由下列方程给出：
D.I＝(离心分离后浊度值/离心分离前浊度值)×100。绝对浊度值也被认为是一个品质因数，对于相同的D.I.值的添加剂，绝对浊度低的添加剂是优选的。
用这种方法制备的共聚物的分散指数为100，绝对浊度为25/25。市售添加剂的分散指数为100和绝对浊度为73/73。抗氧化剂性能的评价
使用在SN450中形成20％的添加剂溶液，该溶液含0.38％的环烷酸亚铁作催化剂。得到的该溶液控制在165℃下并保持16.5升/小时的空气流中。每隔1小时取样一次，并检测其在1700cm-1处红外氧化吸收谱增大。结果与无添加剂的油试样比较如下：无添加剂试样：
2小时后的红外吸收＝14.59；20小时后＝83.93，有添加剂试样：
2小时后的红外吸收＝13.26；20小时后＝65.99。对所制备的添加剂再一次评价其抗氧化剂性能，差热分析用于确定与本底氧化物相应的放热峰起始温度。分析是对含0.38％环烷酸亚铁的20％的聚合物SN450溶液在10巴的氧气压力下并以5℃/分的加热速率在50～350℃范围内进行的。无添加剂的油的起始温度为174.7℃面有添加剂的油的起始温度为180.2℃。发动机试验
为评价在实施侧1中制备的聚合物A的发动机性能，使用SAE15W50级润滑剂，它含有6.5wt％的待测试的聚合物和10.5wt％的常规添加剂，该常规添加剂由二硫代磷酸锌，高碱性磺酸钙，多异丁烯基琥珀酰亚胺和空间位阻酚组成。还使用6.5％(以乙烯—丙烯共聚物为基)的常规粘度指数改进剂。
用于评价润滑剂操作特性的发动机试验是：VE序列(ASTMSTP315H  PTIII方法)，IIIE序列(ASTMSTP315H PTII方法)，Mercedes M102E黑色油泥试验(CECL—41—T—88方法)和Petter WI(CECL—02—A—78方法)。这些试验是众所周知的，结合官方CCMC技术规范，评价润滑剂的分散剂和抗氧化剂特性，如果在实验结束后，发动机各部件的评价结果落在技术规范所规定的范围内，则认为是令人满意的。
对所述润滑剂的实验结果和对G4类润滑剂的CCMC技术规范限定值给出在下表中。表1—VE序列(Seguence)
            有添加剂润滑油的    技术规范限结果发动机平均油泥        9.14              9最小往复杆盖油泥          8.10              7最小活塞裙平均积炭              6.58    6.5最小发动机平均积炭              6.01    5最小护油环阻塞％                0       15最大油隔网阻塞％                2       20最大压缩环的碰撞次数            0       0凸轮平均磨损量，微米        130     130最大凸轮最大磨损量，微米        335.3   380最大表2—IIIE序列
                  有添加剂润滑油的    技术规范限
                         结果在40℃时粘度增加％           144         300最大活塞裙积炭                   8.9         8.9最大活塞环区积炭                 3.67        3.5最小油泥                         9.51        9.2最小活塞环撞击                   0           0活塞挑撞击                   0           0凸轮和活套挑平均磨损量，微米 9.3         30最大凸轮和活套挑最大磨损量，微米 49          60最大表3—MERC    M102E(黑色油泥)
            有添加剂润油的    技术规范限
                结果发动机油泥品质      9.3             9最小表4—PETTER WI
           有添加剂润滑油的    技术要求限
                结果轴承损失量，mg     19.8             25最大在40℃下粘度增加％   87             没规定
实施例2
向一装有导热油夹套、锚式搅拌器，测温热电偶和氮气注射器的反应器中加入148gSN150矿物油，125.09gC12—C18直链甲基丙烯酸醇单体和I1.8g2，2，6，6—四甲基—
Figure C9410538700131
啶—4—醇的甲基丙烯酸酯，在氮气注入的同时，将该导流搅拌1小时。将15g甲基丙烯酸甲酯和作为聚合引发剂的0.9g过辛酸叔丁基酯分别脱气。然后加入甲基丙烯酸甲酯并将反应混合物升温到100℃。在该温度下加入催化剂。聚合立即开始并急剧放热，因此应开动温度控制导流以维持这一温度不变直到反应完成(2—3小时)。反应进度用红外分析跟踪，与甲基丙烯酸单体双键有关的谱带的消失在1320—1340Cm-1处观察到了。
所得产品的特性按实施例l所述的万式测定。结果如下：在100℃下未稀释的粘度：1100厘沲在100℃下在SN150中10％的溶液的粘度：13.93厘沲在40℃下在SN150中10％的溶液的粘度：78.92厘沲粘度指数：183在—20℃下在SN150中10％的溶液的粘度：3000厘泊分散指数(D.I)：100％绝对浊度值：118/118氧化稳定性，无添加剂润滑油试样：2小时后的红外吸收14.59，20小时后为83.93。含20wt％的聚合      2小时后的红外吸收7.20，润滑油试样：        20小时后71.40。差热分析：起始温度＝189.2℃
实施例3
N—(3—羟基丙基)—N′—甲基
Figure C9410538700141
嗪的甲基丙烯酸酯的制备将N—(3—羟基丙基)—N′—甲基
Figure C9410538700142
嗪和甲基丙烯酸甲酯以1∶2的摩尔比引入到一个装有导热油加热夹套、锚式搅拌器，测温热电偶和带有回流头的蒸馏塔的园筒形玻璃反应器中，将作为聚合引发剂的0.05％(重量，以反应物料为基)吩噻嗪与碱性催化剂如二月桂酸二丁基锡酯一起加入反应器中.该催化剂与原料醇的摩尔比为l∶135。通过联到塔顶冷凝器的真空泵使压力降到560mmHg，且将系统逐渐升温至95℃。反应物料在该温度下沸腾，在塔顶冷凝的甲醇一甲基丙烯酸甲酯共沸物的重量比为85∶15。当塔顶温度稳定在约54—55℃即共沸点时，这可通过回流分离器抽出。反应急剧完成，反应进度可通过气相色谱分析跟踪。在反应9小时后，当转化的醇起过98％，过量的甲基丙烯酸甲酯、未反应的醇和其余的残留的甲醇通过减压蒸馏除去，蒸馏用这种方法获得的甲基丙烯酸酯。沸点：116℃/2mmHg蒸馏后的产率：95％元素分析(括号内为理论值)：C＝63.4(63.6)；H＝10.1(9.8)；N＝12.1(12.3)I.R(液膜)：特征吸收在1720Cm-1(羰基)处和在1640Cm-1(C＝C双键)处

Claims (4)

1.一种润滑油组合物，包含主要量的润滑油和0.5-10％(重量)的由不饱和酯共聚获得的下式(I)的添加剂其特征在于：
X为85％到90％(重量)；Y为3％到7％(重量)；Z为4％到6％(重量)；R’是甲基，因而共聚的酯为甲基丙烯酸酯；Ra是衍生自具有10到20个碳原子的天然或合成的直链或支链的伯醇混合物的烷基；Rb是甲基；Rc是2，2，6，6-四甲基-哌啶-4-醇基，因而单体CH2＝CR′-COORc是2，2，6，6-四甲基-哌啶-4-醇甲基丙烯酸酯。
2.按权利要求1所述的润滑油组合物，其中添加剂的量为1.2-6％(重量)。
3.按权利要求1或2所述的润滑油组合物，其中甲基丙烯酸的Rc酯是下列物质组成的混合物：
50-85％(重量)的2，2，6，6-四甲基-哌啶-4-醇甲基丙烯酸酯，
15-50％(重量)的N，N-二甲基氨基乙醇甲基丙烯酸酯，或N-(3-羟基丙基)-N′-甲基-哌嗪甲基丙烯酸酯或其混合物。
4.按权利要求1或2所述的润滑油组合物，其中甲基丙烯酸Rc酯是下式(II)的化合物，其R’是甲基。
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