CN106590853B - 一种合成增压甲醇发动机油及其制备方法和应用 - Google Patents

一种合成增压甲醇发动机油及其制备方法和应用 Download PDF

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CN106590853B
CN106590853B CN201610916230.1A CN201610916230A CN106590853B CN 106590853 B CN106590853 B CN 106590853B CN 201610916230 A CN201610916230 A CN 201610916230A CN 106590853 B CN106590853 B CN 106590853B
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oil
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CN106590853A (zh
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向晖
王习光
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Guangzhou Guoji Lubrication Technology Co., Ltd
Guangzhou Machinery Research Institute Co., Ltd
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Guangzhou Jisheng Lubrication Technology Co Ltd
Guangzhou Mechanical Engineering Research Institute Co Ltd
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Abstract

本发明属于发动机润滑油领域，公开了一种合成增压甲醇发动机油及其制备方法和应用。本发明通过将95～97份合成基础油加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入0.5～1份胺型抗氧剂，1～1.5份极压抗磨剂，0.2～0.5份金属钝化剂，0.3～0.5份金属清净剂，0.1～0.5份无灰分散剂，0.1～0.2份抗泡剂搅拌，得到所述的合成增压甲醇发动机润滑油。本发明所述合成增压甲醇发动机油具有粘度指数高、剪切性好及低温性强、碱值高、润滑性强、抗氧化抗腐蚀性能好、清净分散效果好、制备工艺简单、成本低、应用范围广等诸多优点。

Description

一种合成增压甲醇发动机油及其制备方法和应用
技术领域
本发明属于发动机润滑油领域，公开了一种合成增压甲醇发动机油及其制备方法和应用。
背景技术
目前，随着经济的发展和技术的进步，甲醇作为一种新型的绿色燃料，越来越多的被应用到发动机上。但是，甲醇作为一种替代能源，在实际的使用过程中仍然有很多问题：
(1)甲醇在燃烧过程中会产生甲醛和甲酸，会降低润滑油的使用效果并腐蚀合成增压发动机；
(2)合成增压发动机在工作中不可避免的会使少部分甲醇进入到润滑油中，从而稀释润滑油；
(3)甲醇吸水性强，会造成合成增压发动机的磨损，导致发动机发生故障。
发明内容
为了克服现有技术中的缺点和不足之处，本发明的首要目的在于提供一种合成增压甲醇发动机油。本发明采用全新技术合成基础油1-已烯、1-辛烯和1-十二烯的三元共聚物，其粘度指数、剪切性及低温性远远优于传统的普通聚α-烯烃，本发明具有碱值高、润滑性强、抗氧化抗腐蚀性能好、清净分散效果好、制备工艺简单、成本低、应用范围广等诸多优点。
本发明的再一目的在于提供一种上述合成增压甲醇发动机油的制备方法。
本发明的又一目的在于提供一种上述合成增压甲醇发动机油的应用。
本发明目的通过以下技术方案实现：
一种合成增压甲醇发动机润滑油，该润滑油由以下按质量份数组成：
所述合成基础油是1-已烯、1-辛烯、1-十二烯的三元共聚物。
所述合成基础油为合成基础油A、合成基础油B、合成基础油C中的一种；
所述合成基础油A是由摩尔比为1～1.5:3.5～4:4.5～5的1-已烯、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s；
所述合成基础油B是由摩尔比为0.5～1:5～5.5:3.5～4的1-已烯、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s；
所述合成基础油C是由摩尔比为1.5～2:4.5～5:3～3.5的1-已烯、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s。
所述合成基础油按照以下步骤制备而成：将1-已烯、1-辛烯和1-十二烯置于带有抽真空、送样及搅拌装置的高压反应器中，抽真空后通入氮气，加入质量比为1～3:1的催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1％～1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得合成基础油。
所述胺型抗氧剂为N-苯基-2-萘胺、4,4’-二辛基二苯胺和二异辛基二苯胺的一种以上；
所述极压抗磨剂为伯醇二烷基二硫代磷酸锌、二硫化磷酸盐和二硫化二苄中的一种以上；
所述金属钝化剂为苯并三唑、甲苯基三唑和噻二唑衍生物的一种以上；
所述金属清净剂为碱值在300-500mgKOH/g之间的高碱值磺酸钙、高碱值磺酸钡和高碱值烷基水杨酸钙中的一种以上；
所述无灰分散剂为聚合丁二酰亚胺、丁二酸酯和双丁二酰亚胺中的一种以上；
所述抗泡剂为聚二甲基硅氧烷、有机硅酸酯和二甲基硅油中的一种以上。
上述合成增压甲醇发动机润滑油的制备方法，包括以下步骤：将95～97质量份合成基础油加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入0.5～1质量份胺型抗氧剂，1～1.5质量份极压抗磨剂，0.2～0.5质量份金属钝化剂，0.3～0.5质量份金属清净剂，0.1～0.5质量份无灰分散剂和0.1～0.2质量份抗泡剂，搅拌后在0.2MPa下进行过滤，得到合成增压甲醇发动机润滑油。
所述搅拌的速度为60～100rpm，搅拌的时间为2～3小时。
上述合成增压甲醇发动机润滑油在合成增压甲醇汽油机、合成增压甲醇柴油机领域中的应用。
本发明中三元共聚物的原理是：
1.本发明以1-已烯、1-辛烯、1-十二烯作为单体，合成三元共聚物1-已烯-1-辛烯-1-十二烯。使用1-已烯而不是1-戊烯或1-丁烯等，是因为当碳原子数Cn中n＜6时，得到的共聚物的粘温性差，运动粘度对温度的变化十分敏感；使用1-十二烯而不是1-十八烯等，是因为当碳原子数Cn中n＞12时，得到的共聚物的流动特性不好。
2.本发明中，当1-辛烯单体的摩尔占比过多时，粘度指数低，粘温性差粘度，随温度变化大；当1-十二烯单体的摩尔占比过多时，倾点变高，低温流动性差；当1-已烯单体的摩尔占比过多时，润滑性差。
3.本发明中，当单体摩尔比发生变化时，所得三元共聚物的100℃运动粘度不在50～200mm2/s范围内。当三元共聚物的100℃运动粘度小于50mm2/s时，则以此三元共聚物作为基础油所生产出的合成增压甲醇发动机润滑油，其粘附性降低，油膜变薄，影响发动机的使用寿命；当三元共聚物的100℃运动粘度超过200mm2/s，则以此三元共聚物作为基础油所生产出的合成增压甲醇发动机润滑油，粘度过高，耗油升高，节能性差。
4.本发明中，当MAO金属催化剂双环戊二烯基二氯化锆总质量占催化剂的总质量过多时，所制备的三元共聚物形态差；当助催剂三异丁基铝总质量占催化剂的总质量过多时，反应速度快，过程不易控制。
本发明相对于现有技术具有如下的优点及效果：
本发明具有粘度指数高、剪切性好及低温性强、碱值高、润滑性强、抗氧化抗腐蚀性能好、清净分散效果好、制备工艺简单、成本低、应用范围广等诸多优点。
具体实施方法
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
将97质量份合成基础油A(将1-已烯、1-辛烯和1-十二烯按照1:4:5的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，抽真空后通入氮气，加入质量比为3:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油A的100℃运动粘度为60.4mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份N-苯基-2-萘胺，1质量份伯醇二烷基二硫代磷酸锌，0.3质量份苯并三唑，0.3质量份高碱值磺酸钙，0.3质量份聚合丁二酰亚胺和0.1质量份聚二甲基硅氧烷，100rpm搅拌2小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
实施例2
将96.5质量份合成基础油A(将1-已烯、1-辛烯和1-十二烯按照1.5:4:4.5的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为3:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油A的100℃运动粘度为82.7mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份4,4’-二辛基二苯胺，1质量份二硫化磷酸盐，0.5质量份伯醇二烷基二硫代磷酸锌，0.3质量份甲苯基三唑，0.3质量份高碱值烷基水杨酸钙，0.3质量份丁二酸酯和0.1质量份聚二甲基硅氧烷，60rpm搅拌3小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
实施例3
将97质量份合成基础油B(将1-已烯、1-辛烯和1-十二烯按照0.5:5.5:4的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为2:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油B的100℃运动粘度为101.3mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份二异辛基二苯胺，1质量份伯醇二烷基二硫代磷酸锌，0.3质量份噻二唑衍生物，0.3质量份高碱值磺酸钙，0.3质量份丁二酸酯和0.1质量份有机硅酸酯，80rpm搅拌2.5小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
实施例4
将95.8质量份合成基础油B(将1-已烯、1-辛烯和1-十二烯按照0.8:5.2:4的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为2:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油B的100℃运动粘度为94.2mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入0.5质量份N-苯基-2-萘胺，0.5质量份4,4’-二辛基二苯胺，1.5质量份伯醇二烷基二硫代磷酸锌，0.5质量份苯并三唑，0.5质量份高碱值磺酸钙，0.5质量份聚合丁二酰亚胺和0.2质量份聚二甲基硅氧烷，60rpm搅拌3小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
实施例5
将95.7质量份合成基础油C(将1-已烯、1-辛烯和1-十二烯按照1.5:5:3.5的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为1:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油C的100℃运动粘度为76.90mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份N-苯基-2-萘胺，1.5质量份伯醇二烷基二硫代磷酸锌，0.5质量份苯并三唑，0.5质量份高碱值磺酸钙，0.5质量份聚合丁二酰亚胺，0.1质量份聚二甲基硅氧烷和0.1质量份有机硅酸酯，100rpm搅拌2小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
实施例6
将97质量份合成基础油C(将1-已烯、1-辛烯和1-十二烯按照2:5:3的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为1:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油C的100℃运动粘度为96.30mm2/s)加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份4,4’-二辛基二苯胺，1质量份伯醇二烷基二硫代磷酸锌，0.3质量份甲苯基三唑，0.3质量份高碱值磺酸钙，0.3质量份聚合丁二酰亚胺和0.1质量份聚二甲基硅氧烷，90rpm搅拌2小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
对比实施例
将1-已烯、1-辛烯和1-十二烯按照1:7:2的摩尔比置于带有抽真空、送样及搅拌装置高压反应器中，多次抽真空后通入氮气，加入质量比为1:1催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-已烯、1-辛烯、1-十二烯总质量的1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得，所得合成基础油的100℃运动粘度为34.3mm2/s。
将97质量份合成基础油加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入1质量份4,4’-二辛基二苯胺，1质量份伯醇二烷基二硫代磷酸锌，0.3质量份甲苯基三唑，0.3质量份高碱值磺酸钙，0.3质量份聚合丁二酰亚胺和0.1质量份聚二甲基硅氧烷，60～100rpm搅拌2～3小时，再在0.2MPa下进行过滤，得到均匀透明的合成增压甲醇发动机润滑油。
上述实施例1-6获得的合成增压甲醇发动机润滑油，经测试结果如表1所示：
表1本发明合成增压甲醇发动机润滑油的性能检测数据
市售普通合成增压甲醇发动机润滑油，经测试结果如表2所示：
表2市售普通增压甲醇发动机润滑油的性能检测数据
由表1可以看出，实施例1～6在粘度指数、倾点及旋转氧弹等实验数据上均优于对比实施例。
由表1和表2可看出，在粘温性、低温性、氧化安定性、高温抗磨性及抗压性方面，合成增压甲醇发动机润滑油均高于市售普通增压甲醇发动机润滑油。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (5)

1.一种合成增压甲醇发动机润滑油，其特征在于：该润滑油由以下按质量份数组成：
所述合成基础油为合成基础油A、合成基础油B、合成基础油C中的一种；
所述合成基础油A是由摩尔比为1～1.5:3.5～4:4.5～5的1-己烯 、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s；
所述合成基础油B是由摩尔比为0.5～1:5～5.5:3.5～4的1-己烯 、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s；
所述合成基础油C是由摩尔比为1.5～2:4.5～5:3～3.5的1-己烯 、1-辛烯和1-十二烯反应合成，其合成物100℃运动粘度为50～200mm2/s；
所述合成基础油按照以下步骤制备而成：将1-己烯 、1-辛烯和1-十二烯置于带有抽真空、送样及搅拌装置的高压反应器中，抽真空后通入氮气，加入质量比为1～3:1的催化剂三异丁基铝和双环戊二烯基二氯化锆，催化剂的总质量是1-己烯 、1-辛烯、1-十二烯总质量的1％～1.5％，保持反应器在20℃下反应2h，待反应均匀除去不溶物后制得合成基础油。
2.根据权利要求1所述的一种合成增压甲醇发动机润滑油，其特征在于：所述胺型抗氧剂为N-苯基-2-萘胺、4,4’-二辛基二苯胺和二异辛基二苯胺的一种以上；
所述极压抗磨剂为伯醇二烷基二硫代磷酸锌、二硫化磷酸盐和二硫化二苄中的一种以上；
所述金属钝化剂为苯并三唑、甲苯基三唑和噻二唑衍生物的一种以上；
所述金属清净剂为碱值在300-500mgKOH/g之间的高碱值磺酸钙、高碱值磺酸钡和高碱值烷基水杨酸钙中的一种以上；
所述无灰分散剂为聚合丁二酰亚胺、丁二酸酯和双丁二酰亚胺中的一种以上；
所述抗泡剂为聚二甲基硅氧烷、有机硅酸酯和二甲基硅油中的一种以上。
3.根据权利要求1～2任一项所述的一种合成增压甲醇发动机润滑油的制备方法，其特征在于包括以下步骤：将95～97质量份合成基础油加入到带有搅拌装置和水浴装置的三口烧瓶中，水浴恒温60℃，然后加入0.5～1质量份胺型抗氧剂，1～1.5质量份极压抗磨剂，0.2～0.5质量份金属钝化剂，0.3～0.5质量份金属清净剂，0.1～0.5质量份无灰分散剂和0.1～0.2质量份抗泡剂，搅拌后在0.2MPa下进行过滤，得到合成增压甲醇发动机润滑油。
4.根据权利要求3所述的一种合成增压甲醇发动机润滑油的制备方法，其特征在于：所述搅拌的速度为60～100rpm，搅拌的时间为2～3小时。
5.根据权利要求1～2任一项所述的一种合成增压甲醇发动机润滑油在合成增压甲醇汽油机、合成增压甲醇柴油机领域中的应用。
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