CN108485761A - 一种半合成汽油机油及其制备方法 - Google Patents

一种半合成汽油机油及其制备方法 Download PDF

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CN108485761A
CN108485761A CN201810239443.4A CN201810239443A CN108485761A CN 108485761 A CN108485761 A CN 108485761A CN 201810239443 A CN201810239443 A CN 201810239443A CN 108485761 A CN108485761 A CN 108485761A
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parts
semi
gasoline engine
engine oil
synthetic gasoline
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王英奎
王文博
王广宇
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Jin Nuosi (beijing) Petrochemical Products Co Ltd
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Abstract

本发明涉及一种半合成汽油机油及其制备方法，属于润滑油技术领域，半合成汽油机油，其原料包括HVI150矿物基础油、HVI500矿物基础油、聚α‑烯烃合成基础油、粘度指数改进剂、复合功能添加剂、降凝剂、消泡剂；复合功能添加剂包括二烷基二硫代氨甲酸钼、纳米二硫化钼、二苄基二硫代氨基甲酸钠、聚异丁烯基丁二酰亚胺、植酸钙、三甲基羟戊醇异丁酸酯、丁基化羟基乙基苯，并通过依次混合搅拌、程序升温、程序降温的方法制备得到半合成汽油机油。本发明的半合成汽油机油，其不仅提高了纳米二氧化钼的分散性、减少纳米二氧化钼中的气泡，还具有良好的润滑、抗磨、抗氧化、消泡、节能减排的作用。

Description

一种半合成汽油机油及其制备方法
技术领域
本发明涉及润滑油技术领域，更具体的说，它涉及一种半合成汽油机油及其制备方法。
背景技术
当前在汽车工业的发展过程中，发动机内有许多相互摩擦运动的金属表面。特别对于新车出厂或旧车进行发动机大修后，各部件配合间隙不均或过紧，需要进行磨合调正。汽油机油作为润滑油中的一种，在减少发动机内的摩擦发挥着越来越重要的位置。纳米粒子常作为摩擦改进剂加入汽油机油中，纳米粒子会在摩擦副表面填补修复磨损金属表面，并形成润滑薄膜，有效降低发动机的磨损损失，但是纳米粒子难以分散均匀，易产生沉淀而达不到预期效果，影响其使用效果；而且由于纳米粒子孔道内集富有气体，在纳米粒子和汽油机油混合时，集富于孔道内的气体溢出，形成大量细小气泡，影响汽油机油的品质。
发明内容
本发明的目的在于提供一种半合成汽油机油，其不仅提高了纳米二氧化钼的分散性、减少纳米二氧化钼中的气泡，还具有良好的润滑、抗磨、抗氧化、消泡、节能减排的作用。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种半合成汽油机油，按重量份数计，其原料包括HVI150矿物基础油17～23份、HVI500矿物基础油53～72份、聚α-烯烃合成基础油1.7～2.5份、粘度指数改进剂6.8～9.2份、复合功能添加剂6.2～8.4份、降凝剂0.25～0.35份、消泡剂0.16～0.24份；所述复合功能添加剂包括二烷基二硫代氨甲酸钼35～49份、纳米二硫化钼4.5～6.1份、二苄基二硫代氨基甲酸钠10～13份、聚异丁烯基丁二酰亚胺18～25.5份、植酸钙0.68～0.92份、三甲基羟戊醇异丁酸酯16～22份、丁基化羟基乙基苯3.5～4.8份。
较优选地，其原料包括HVI150矿物基础油20份、HVI500矿物基础油62.4份、聚α烯烃合成基础油2份、粘度指数改进剂8份、复合功能添加剂7.3份、降凝剂0.3份、消泡剂0.2份，所述复合功能添加剂包括二烷基二硫代氨甲酸钼40份、纳米二硫化钼5.3份、二苄基二硫代氨基甲酸钠12份、聚异丁烯基丁二酰亚胺22份、植酸钙0.8份、三甲基羟戊醇异丁酸酯19份、丁基化羟基乙基苯4.2份。
较优选地，所述二烷基二硫代氨甲酸钼的结构通式为；
其中，R1、R2、R3、R4独立地选自C5-11直链或支链烷基。
较优选地，所述粘度指数改进剂为聚氢化苯乙烯异戊二烯共聚物、聚甲基丙烯酸酯、乙烯丙烯共聚物中的任意一种或几种。
较优选地，所述降凝剂为乙烯-醋酸乙烯酯共聚物、异丁烯-马来酸酐共聚物、烷基富马酸-醋酸乙烯酯共聚物中的任意一种或几种。
较优选地，所述消泡剂为疏水二氧化硅、二聚氧乙烯辛烷基苯酚醚、硼化聚异丁烯基丁二酰亚胺中的任意一种或几种。
较优选地，所述纳米二硫化钼为粒径80nm～1μm连续级纳米粒。
较优选地，所述二烷基二硫代氨甲酸钼采用以下方法制备：在反应器中依次加入二硫化碳和三氧化钼，剧烈搅拌，并逐滴滴加二烷基胺，控制温度为45℃，在二烷基胺滴加完毕后，继续剧烈搅拌8～9小时，之后经过冷却、水洗、萃取、干燥、减压蒸馏得到二烷基二硫代氨甲酸钼。
较优选地，所述复合功能添加剂采用以下方法制备：在混合釜内依次加入二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠、聚异丁烯基丁二酰亚胺，升温至50℃，搅拌20～30分钟，之后依次加入纳米二硫化钼、植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯，继续搅拌30～40分钟，静止5分钟，过滤冷却，得到复合功能添加剂。
本发明的目的二在于提供一种半合成汽油机油制备方法。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种半合成汽油机油的制备方法，包括如下步骤：
(1)在调和釜中依次加入HVI150矿物基础油、HVI500矿物基础油和聚α-烯烃合成基础油，升温至40℃搅拌0.5小时，继续升温至65℃，搅拌1～1.5小时；
(2)依次加入粘度指数改进剂、复合功能添加剂和降凝剂，温度控制在65℃，继续搅拌1.5～2小时；
(3)之后加入消泡剂，温度控制在65℃，搅拌1小时，冷却至40℃，继续搅拌0.5～1小时，静止10分钟，过滤冷却，得到半合成汽油机油。
综上所述，本发明具有以下有益效果：
第一、本发明的半合成汽油机油，在加入复合功能添加剂和消泡剂后，其不仅提高了纳米二氧化钼的分散性、减少纳米二氧化钼中的气泡，还具有良好的润滑、抗磨、抗氧化、消泡、节能减排的作用。
第二、半合成汽油机油采用依次混合搅拌、程序升温、程序降温可以明显改善半合成汽油机油中纳米二氧化钼的分散性，同时提高其抗磨、消泡性能。
第三、二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠和聚异丁烯基丁二酰亚胺三者之间的协同作用，提高了纳米二氧化钼的分散性，同时降低了纳米二氧化钼中的气泡，进而改善了半合成汽油机油的抗磨性能。
第四、植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯三者之间的协同作用，改善了半合成汽油机油的抗氧化性能，提高了其品质和使用寿命。
具体实施方式
以下结合实施例对本发明作进一步详细说明。应该理解的是，本发明实施例所述制备方法仅仅是用于说明本发明，而不是对本发明的限制，在本发明的构思前提下对本发明制备方法的简单改进都属于本发明要求保护的范围。
实施例1
制备二烷基二硫代氨甲酸钼：在反应器中依次加入30Kg二硫化碳和30Kg三氧化钼，剧烈搅拌，并逐滴滴加65Kg二正十一烷基胺，控制温度为45℃，在二正十一烷基胺滴加完毕后，继续剧烈搅拌9小时，之后经过冷却、水洗、萃取、干燥、减压蒸馏得到二烷基二硫代氨甲酸钼。
制备复合功能添加剂：在混合釜内依次加入35Kg二烷基二硫代氨甲酸钼、10Kg二苄基二硫代氨基甲酸钠、18Kg聚异丁烯基丁二酰亚胺，升温至50℃，搅拌20分钟，之后依次加入6.1Kg纳米二硫化钼、0.92Kg植酸钙、22Kg三甲基羟戊醇异丁酸酯和3.5Kg丁基化羟基乙基苯，继续搅拌30分钟，静止5分钟，过滤冷却，得到复合功能添加剂。
制备半合成汽油机油：包括如下步骤：
(1)在调和釜中依次加入17Kg HVI150矿物基础油、53Kg HVI500矿物基础油和2.5Kg聚α-烯烃合成基础油，升温至40℃搅拌0.5小时，继续升温至65℃，搅拌1小时；
(2)依次加入6.8Kg聚氢化苯乙烯异戊二烯共聚物、8.4Kg复合功能添加剂和0.35Kg异丁烯-马来酸酐共聚物，温度控制在65℃，继续搅拌2小时；
(3)之后加入0.16Kg疏水二氧化硅，温度控制在65℃，搅拌1小时，冷却至40℃，继续搅拌0.5小时，静止10分钟，过滤冷却，得到半合成汽油机油。
实施例2
实施例2和实施例1的区别在于，制备二烷基二硫代氨甲酸钼方法不同；
制备二烷基二硫代氨甲酸钼：在反应器中依次加入30Kg二硫化碳和30Kg三氧化钼，剧烈搅拌，并逐滴滴加31.5Kg二叔戊基胺，控制温度为45℃，在二叔戊基胺滴加完毕后，继续剧烈搅拌8.5小时，之后经过冷却、水洗、萃取、干燥、减压蒸馏得到二烷基二硫代氨甲酸钼。
实施例3
实施例3和实施例1的区别在于，制备二烷基二硫代氨甲酸钼方法不同；
制备二烷基二硫代氨甲酸钼：在反应器中依次加入30Kg二硫化碳和30Kg三氧化钼，剧烈搅拌，并逐滴滴加53.4Kg二正壬基胺，控制温度为45℃，在二正壬基胺滴加完毕后，继续剧烈搅拌8小时，之后经过冷却、水洗、萃取、干燥、减压蒸馏得到二烷基二硫代氨甲酸钼。
实施例4
实施例4和实施例2的区别在于，制备复合功能添加剂方法不同；
制备复合功能添加剂：在混合釜内依次加入42Kg二烷基二硫代氨甲酸钼、12Kg二苄基二硫代氨基甲酸钠、22Kg聚异丁烯基丁二酰亚胺，升温至50℃，搅拌25分钟，之后依次加入5.3Kg纳米二硫化钼、0.8Kg植酸钙、19Kg三甲基羟戊醇异丁酸酯和4.2Kg丁基化羟基乙基苯，继续搅拌35分钟，静止5分钟，过滤冷却，得到复合功能添加剂。
实施例5
实施例5和实施例2的区别在于，制备复合功能添加剂方法不同；
制备复合功能添加剂：在混合釜内依次加入49Kg二烷基二硫代氨甲酸钼、13Kg二苄基二硫代氨基甲酸钠、25.5Kg聚异丁烯基丁二酰亚胺，升温至50℃，搅拌30分钟，之后依次加入4.5Kg纳米二硫化钼、0.68Kg植酸钙、16Kg三甲基羟戊醇异丁酸酯和4.8Kg丁基化羟基乙基苯，继续搅拌40分钟，静止5分钟，过滤冷却，得到复合功能添加剂。
实施例6
实施例6和实施例4的区别在于，制备半合成汽油机油方法不同；
制备半合成汽油机油：包括如下步骤：
(1)在调和釜中依次加入20Kg HVI150矿物基础油、62.4Kg HVI500矿物基础油和2Kg聚α-烯烃合成基础油，升温至40℃搅拌0.5小时，继续升温至65℃，搅拌1.5小时；
(2)依次加入8Kg乙烯丙烯共聚物、7.3Kg复合功能添加剂和0.3Kg乙烯-醋酸乙烯酯共聚物，温度控制在65℃，继续搅拌1.8小时；
(3)之后加入0.2Kg硼化聚异丁烯基丁二酰亚胺，温度控制在65℃，搅拌1小时，冷却至40℃，继续搅拌0.7小时，静止10分钟，过滤冷却，得到半合成汽油机油。
实施例7
实施例6和实施例4的区别在于，制备半合成汽油机油方法不同；
制备半合成汽油机油：包括如下步骤：
(1)在调和釜中依次加入23Kg HVI150矿物基础油、72Kg HVI500矿物基础油和1.7Kg聚α-烯烃合成基础油，升温至40℃搅拌0.5小时，继续升温至65℃，搅拌1.3小时；
(2)依次加入9.2Kg聚甲基丙烯酸酯、6.2Kg复合功能添加剂和0.25Kg烷基富马酸-醋酸乙烯酯共聚物，温度控制在65℃，继续搅拌1.5小时；
(3)之后加入0.24Kg二聚氧乙烯辛烷基苯酚醚，温度控制在65℃，搅拌1小时，冷却至40℃，继续搅拌1小时，静止10分钟，过滤冷却，得到半合成汽油机油。
对比例1
对比例1和实施例6的区别在于，制备复合功能添加剂中未添加二烷基二硫代氨甲酸钼。
对比例2
对比例2和实施例6的区别在于，制备复合功能添加剂中未添加二苄基二硫代氨基甲酸钠。
对比例3
对比例3和实施例6的区别在于，制备复合功能添加剂中未添加聚异丁烯基丁二酰亚胺。
对比例4
对比例4和实施例6的区别在于，制备复合功能添加剂中未添加二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠和聚异丁烯基丁二酰亚胺。
对比例5
对比例5和实施例6的区别在于，制备复合功能添加剂中未添加植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯。
对比例6
对比例6和实施例6的区别在于，制备半合成汽油机油中未添加消泡剂。
对比例7
对比例7和实施例6的区别在于，制备半合成汽油机油中多种原料直接混合，并搅拌均匀。
半合成汽油机油的评价
对实施例1～7和对比例1～7制得的半合成汽油机油，进行下述性能检测，检测结果如表1和表2所示。
1、依照GB/11121-2006《汽油机油》的标准规定测定半合成汽油机油的运动粘度、低温动力粘度、低温泵送粘度、高温高剪切粘度、闪点、倾点、蒸发损失、泡沫性进行检测。
2、依照GB/T3142-1982《润滑剂承载能力测定法(四球法)》的标准规定测定半合成汽油机油的抗磨性能；
试验条件为：Ⅱ级钢球，直径硬度HRC59～61，材料GCr15，转速1450转/分钟，时间10s。
3、依照SH/T0193-2008《润滑油氧化安定性的测定-旋转氧弹法》的标准规定测定半合成汽油机油的抗氧化性能。
表1检测结果
表2检测结果
从表1和表2中可以看出，本发明制备得到的半合成汽油机油，在加入复合功能添加剂和消泡剂后，其不仅提高了纳米二氧化钼的分散性、减少纳米二氧化钼中的气泡，还具有良好的润滑、抗磨、抗氧化、消泡、节能减排的作用，尤其是实施例6。
通过对比实施例6和对比例1～4，对比例1和实施例6的区别之处在于半合成汽油机油中未添加二烷基二硫代氨甲酸钼；对比例2和实施例6和区别之处在于半合成汽油机油中未添加二苄基二硫代氨基甲酸钠；对比例3和实施例6和区别之处在于半合成汽油机油中未添加聚异丁烯基丁二酰亚胺；对比例4和实施例6和区别之处在于半合成汽油机油中未添加二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠和聚异丁烯基丁二酰亚。由此可以看出，二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠和聚异丁烯基丁二酰亚胺可以明显改善半合成汽油机油的抗磨性能，这主要是由于二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠和聚异丁烯基丁二酰亚胺三者之间的协同作用，提高了纳米二氧化钼的分散性，同时降低了纳米二氧化钼中的气泡，进而提高了半合成汽油机油的品质。
通过对比实施例6和对比例5，对比例6和实施例6的区别之处在于半合成汽油机油中未添加植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯。由此可以看出植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯可以明显改善半合成汽油机油的抗氧化性能，这主要是由于植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯三者之间的协同作用的影响。
通过对比实施例6和对比例6，对比例6和实施例6的区别之处在于半合成汽油机油中未添加消泡剂。由此可以看出，消泡剂可以明显改善半合成汽油机油的消泡性能。通过对比实施例6和对比例7，对比例7和实施例6的区别之处在于半合成汽油机油中多种原料直接混合，并搅拌均匀。由此可以看出，半合成汽油机油采用依次混合搅拌、程序升温、程序降温可以明显改善半合成汽油机油中纳米二氧化钼的分散性，同时提高其抗磨、消泡性能。

Claims (10)

1.一种半合成汽油机油，其特征在于：按重量份数计，其原料包括HVI150矿物基础油17～23份、HVI500矿物基础油53～72份、聚α-烯烃合成基础油1.7～2.5份、粘度指数改进剂6.8～9.2份、复合功能添加剂6.2～8.4份、降凝剂0.25～0.35份、消泡剂0.16～0.24份；所述复合功能添加剂包括二烷基二硫代氨甲酸钼35～49份、纳米二硫化钼4.5～6.1份、二苄基二硫代氨基甲酸钠10～13份、聚异丁烯基丁二酰亚胺18～25.5份、植酸钙0.68～0.92份、三甲基羟戊醇异丁酸酯16～22份、丁基化羟基乙基苯3.5～4.8份。
2.根据权利要求1所述的一种半合成汽油机油，其特征在于：其原料包括HVI150矿物基础油20份、HVI500矿物基础油62.4份、聚α烯烃合成基础油2份、粘度指数改进剂8份、复合功能添加剂7.3份、降凝剂0.3份、消泡剂0.2份，所述复合功能添加剂包括二烷基二硫代氨甲酸钼40份、纳米二硫化钼5.3份、二苄基二硫代氨基甲酸钠12份、聚异丁烯基丁二酰亚胺22份、植酸钙0.8份、三甲基羟戊醇异丁酸酯19份、丁基化羟基乙基苯4.2份。
3.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述二烷基二硫代氨甲酸钼的结构通式为；
其中，R1、R2、R3、R4独立地选自C5-11直链或支链烷基。
4.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述粘度指数改进剂为聚氢化苯乙烯异戊二烯共聚物、聚甲基丙烯酸酯、乙烯丙烯共聚物中的任意一种或几种。
5.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述降凝剂为乙烯-醋酸乙烯酯共聚物、异丁烯-马来酸酐共聚物、烷基富马酸-醋酸乙烯酯共聚物中的任意一种或几种。
6.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述消泡剂为疏水二氧化硅、二聚氧乙烯辛烷基苯酚醚、硼化聚异丁烯基丁二酰亚胺中的任意一种或几种。
7.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述纳米二硫化钼为粒径80nm～1μm连续级纳米粒。
8.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述二烷基二硫代氨甲酸钼采用以下方法制备：在反应器中依次加入二硫化碳和三氧化钼，剧烈搅拌，并逐滴滴加二烷基胺，控制温度为45℃，在二烷基胺滴加完毕后，继续剧烈搅拌8～9小时，之后经过冷却、水洗、萃取、干燥、减压蒸馏得到二烷基二硫代氨甲酸钼。
9.根据权利要求1所述的一种半合成汽油机油，其特征在于：所述复合功能添加剂采用以下方法制备：在混合釜内依次加入二烷基二硫代氨甲酸钼、二苄基二硫代氨基甲酸钠、聚异丁烯基丁二酰亚胺，升温至50℃，搅拌20～30分钟，之后依次加入纳米二硫化钼、植酸钙、三甲基羟戊醇异丁酸酯和丁基化羟基乙基苯，继续搅拌30～40分钟，静止5分钟，过滤冷却，得到复合功能添加剂。
10.一种半合成汽油机油的制备方法，其特征在于：包括如下步骤：
(1)在调和釜中依次加入HVI150矿物基础油、HVI500矿物基础油和聚α-烯烃合成基础油，升温至40℃搅拌0.5小时，继续升温至65℃，搅拌1～1.5小时；
(2)依次加入粘度指数改进剂、复合功能添加剂和降凝剂，温度控制在65℃，继续搅拌1.5～2小时；
(3)之后加入消泡剂，温度控制在65℃，搅拌1小时，冷却至40℃，继续搅拌0.5～1小时，静止10分钟，过滤冷却，得到半合成汽油机油。
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