CN108484801B - 一类含卤素的合成基础油及其制备方法和用途 - Google Patents

一类含卤素的合成基础油及其制备方法和用途 Download PDF

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CN108484801B
CN108484801B CN201810436572.2A CN201810436572A CN108484801B CN 108484801 B CN108484801 B CN 108484801B CN 201810436572 A CN201810436572 A CN 201810436572A CN 108484801 B CN108484801 B CN 108484801B
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double bond
molecular weight
fluorine
base oil
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CN108484801A (zh
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魏东初
刘彬彬
李兵
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Abbott Science And Technology (hangzhou) Co Ltd
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Abstract

本发明提供了一类含卤素的合成基础油及其制备方法和用途。所述合成基础油的特点包括引入卤素基团形成含卤素尤其是氟的基础油，其中卤素基团的偶极运动导致了偶极‑偶极和偶极诱导的卤素基油分子，特别是其氟化基础油与其它成分的偶极相互作用，它比纯碳氢合成油分子之间的分散力更强而且更局部化，从而能够改善所述基础油应用的性能，包括解决了业界困扰着纯碳氢合成油的兼溶性问题，并且能够增强高抗氧化性和增强热稳定性。

Description

一类含卤素的合成基础油及其制备方法和用途
技术领域
本发明涉及一类新型的含卤素的合成润滑油基础油，特别是含氟原子的合成润滑油基础油。
背景技术
由乙烯，或丙烯，或丁烯，或异丁烯，或α-烯烃单体或其混合物聚合，或上述任何一种或几种的组合聚合生成的合成基础油是一种性能优异的润滑油基础油和基础油性能改进剂，是目前合成发动机油、齿轮油和其他工业用油、脂中最广泛应用的基础油料之一，由其调制的合成油极大地扩展了润滑油脂在高温、低温、高负荷及其他苛刻条件下的应用范围，提供了优异的粘温性能、热氧化安定性、润滑及抗磨损性能和清净性，因而大大地延长了换油期，减缓了设备的腐蚀和磨损，降低了设备的维修周期，大大地提高了设备的利用率和使用寿命，为用户创造了丰厚的经济效益，同时又在环保和节能方面实现了很大的社会效益。因此，在当今许多最高档的润滑油品中合成基础油已普遍被优选作为润滑油的基础油。
ExxonMobil公司是全世界生产合成基础油的主要公司之一，在上世纪八十年代就推出了使用α-烯烃合成了的新一代聚α-烯烃(PAO)合成基础油，这种新的PAO基础油在通常情况下PAO分子拥有突出的基干，从基干伸出长侧链。其分子结构可简示如下式，其独特的几何结构可得到很均一的化学产品，拥有梳状结构，不存在直立的侧链。与常规矿物油相比这种形状拥有改进的流变特性和流动特征，从而可更好地提供剪切稳定性、较低的倾点和较高的粘度指数，特别是由于有较少的侧链而具有比常规矿物油高得多的剪切稳定性。这些特性决定了矿物油的使用目标是高苛刻度的应用，包括动力传动系统和齿轮油、压缩机润滑油、传动液和工业润滑油。
现有工艺技术合成基础油PAO的生产工艺主要由α-烯烃聚合；催化加氢；分馏得到合成基础油PAO产品，如下式所示。
合成mPAO的生产工艺主要包括第一步：聚合，第二步：加氢，得到mPAO产品；具体流程图如图1所示。
α-烯烃聚合得到的聚α-烯烃是含有不饱和的双键容易氧化，还要进行进一步的加氢反应，如何处理端位双键使其生成更稳定的产物是我们研究的课题。
发明内容
针对聚α-烯烃合成中现有的问题，本发明人通过实验验证，可以在端位双键或其他位双键上引入卤素原子特别是引入氟原子，从而可以增加聚α-烯烃的极性，改进其与其他添加剂的相溶性，同时提高合成基础油的抗氧化性和增强热稳定性，从而增加耐高温，耐腐蚀性，耐辐射性，耐磨损等性能。
例如，乙烯聚合的多支链聚乙烯在端位双键或其他位双键加成卤素特别加成氟原子形成的合成基础油分子结构如下式所示。
本发明提供了一类新型的含卤素的合成润滑油基础油，尤其是其含氟原子的合成基础油及其制备方法和用途。
一方面，本发明提供了一类新型含卤素的合成基础油。为聚-α烯烃在端位双键或其他位双键加成卤素特别加成氟原子形成；α烯烃单体或混合α烯烃聚合物在端位双键或其他位双键加成卤素特别加成氟原子形成；乙烯聚合的多支链聚乙烯在端位双键或其他位双键加成卤素特别加成氟原子形成；乙烯和丙烯共聚物在端位双键或其他位双键加成卤素特别加成氟原子形成；乙烯，α烯烃与其共聚单体的聚合物在端位双键或其他位双键加成卤素特别加成氟原子形成；异丁烯聚合物在端位双键或其他位双键加成卤素特别加成氟原子形成。
所述基础油包含合成产物FF-PAO和/或F-PAO，其结构和合成方法如下式所述：
其中：
所述合成产物FF-PAO或F-PAO的分子量在100-20000；
X为卤素；
n为整数2-30；
R为下述群组中的一种：
1)链长为4-20的聚-α烯烃基团，其分子量在100-20000，
2)链长为4-20的单体α-烯烃或链长为4-20的混合α烯烃的聚合物基团，其分子量在100-20000，
3)乙烯聚合的多支链聚乙烯基团，其分子量在100-20000，
4)乙烯和丙烯共聚物基团，其分子量在100-20000，
5)乙烯与链长为4-20的α烯烃共聚物基团，其分子量在100-20000，和
7)异丁烯聚合物基团，其分子量在100-20000。所述合成基础油中的所述卤素可以为氟、氯、溴或碘。优选地，所述卤素为氟。
所述合成基础油中的其中所述n为数字2-10，还可以是2-10聚加上共聚物；
所述合成基础油中所述n为数字2-10，还可以是2-10聚加上共聚物；或者所述n为数字2-30，还可以是2-20聚加上共聚物。
当卤素为氟的时候，所述基础油的结构和合成方法如下式所述：：
其中，n为数字2-30；所述合成润滑油基础油通常分子量在100-20000；
R为：
1)链长为4-20的聚-α烯烃；分子量在100-20000，
2)链长为4-20的α烯烃单体或链长为4-20的混合α烯烃聚合物；在分子量在100-20000，
3)多支链聚乙烯；分子量在100-20000，
4)乙烯和丙烯共聚物，分子量在100-20000，
5)乙烯，链长为4-20的α烯烃与其共聚单体的聚合物，分子量在100-20000，
7)异丁烯聚合物，分子量在100-20000。
另一方面，本发明提供了所述含卤素的合成基础油的制备方法。所述方法包括如下式所述的合成过程：
其中：
所述合成产物FF-PAO或F-PAO的分子量在100-20000；
X为卤素；
n为整数2-30；
R为下述群组中的一种：
1)链长为4-20的聚-α烯烃基团，其分子量在100-20000，
2)链长为4-20的单体α-烯烃或链长为4-20的混合α烯烃的聚合物基团，其分子量在100-20000，
3)乙烯聚合的多支链聚乙烯基团，其分子量在100-20000，
4)乙烯和丙烯共聚物基团，其分子量在100-20000，
5)乙烯与链长为4-20的α烯烃的共聚物基团，其分子量在100-20000，和
7)异丁烯聚合物基团，其分子量在100-20000；
其中，所述产物的合成包括：
聚-α烯烃在端位双键或其他位双键加成卤素，
单体α烯烃或混合α烯烃聚合物在端位双键或其他位双键加成卤素，
乙烯聚合的多支链聚乙烯在端位双键或其他位双键加成卤素，
乙烯和丙烯共聚物在端位双键或其他位双键加成卤素，
乙烯与α烯烃共聚的聚合物在端位双键或其他位双键加成卤素，或
异丁烯聚合物在端位双键或其他位双键加成卤素。
在所述制备方法中，所述卤素可以为氟、氯、溴或碘。优选地，所述卤素为氟。
根据所用的亲电反应条件不同，生成不同的产物：
1)当使用卤素的时候，生成的产物在端位和alpha位以及非端位双键上卤化加成的双卤素取代的产物，即FF-PAO；
2)当使用卤化氢的时候，生成的产物为在alpha和beta位以及非端位双键上卤化加成的单卤素取代的产物F-PAO。
再一方面，本发明提供了所述含卤素的合成基础油用于配制润滑油的用途，其包括将所述合成基础油与添加剂混合形成组合物用作润滑油。
本发明所述的合成基础油的特点包括引进了的卤素基团尤其是氟原子，其中卤素基团的偶极运动导致了偶极-偶极和偶极诱导的卤素基础油分子，特别是氟化基础油与其它成分的偶极相互作用，比纯碳氢合成油分子之间的分散力更强而且更局部化，而这种特点直接影响到所述基础油应用的性能。卤素合成基础油特别是其氟化基础油类似于合成酯类基础油，增加了极性，解决了业界困扰着纯碳氢合成油的油溶性问题，使其与其他润滑油添加剂很好的溶合；同时提高抗氧化性和增强热稳定性，如耐高温，防水，耐腐蚀性，耐辐射性，耐磨损性好等特点。本发明所述的合成基础油可广泛运用于消防，铁路，原子能、航天、电子、电气、化工、机械、仪器、仪表、建筑、纺织等工业中的传动械具中。
附图说明
图1为合成mPAO的生产工艺流程图。
具体实施方式
(实施例1)聚-α癸烯FF-PAO6的合成
聚-α癸烯是由癸烯-1经催化聚合反应制成，将聚-α癸烯200mg和二氯甲烷2mL的混合液置于特氟龙的容器中，-78℃滴加二氟碘对甲苯200mg溶在Et3N-THF-CH2Cl2(1∶1∶2)溶液，滴加完毕后，升至0℃反应2小时。然后将反应液倾入饱和碳酸氢钠水溶液中。产物用乙醚洗3次，蒸干溶剂后，产物用分子蒸馏可获得含FF-PAO6 150mg。IR(neat)：1730cm-1，19FNMR(376MHz，CDCl3)：δ-189.64-198.23(m，1F)，-230.24，-230.58(m，1F)。
(实施例2)聚-α癸烯F-PAO6的合成
聚-α癸烯是由癸烯-1经催化聚合反应制成，将聚-α癸烯200mg置于特氟龙的容器中，冷至-20-30℃滴加HF的二甲基乙醚溶液10mL，滴加完毕后，升至室温反应3小时，然后冰水淬灭。产物用二氯甲烷提取3次，蒸除溶剂后，产物用分子蒸馏可获得含F-PAO6 130mg。IR(neat)：1730cm-1，19F NMR(376MHz，CDCl3)：δ--172(m，1F)。
(实施例3)多支链聚乙烯FF-PEO100的合成
多支链聚乙烯是由乙烯经催化聚合反应制成，将多支链聚乙烯200mg和二氯甲烷2mL的混合液置于特氟龙的容器中，-78℃滴加二氟碘对甲苯200mg溶在Et3N-THF-CH2Cl2(1∶1∶2)溶液，滴加完毕后，升至0℃反应2小时。然后将反应也倾入饱和碳酸氢钠水溶液中。产物用乙醚洗3次，蒸干溶剂后，产物用分子蒸馏可得含FF-PEO100 165mg。IR(neat)：1728cm-1，19F NMR(376MHz，CDCl3)：δ-188.94-196.43(m，1F)，-228.24，-228.58(m，1F)。
(实施例4)多支链聚乙烯F-PEO100的合成
多支链聚乙烯是由乙烯经催化聚合反应制成，将多支链聚乙烯200mg置于特氟龙的容器中，冷至-20-30℃滴加HF的二甲基乙醚溶液10mL，滴加完毕后，升至室温反应3小时，然后冰水淬灭。产物用二氯甲烷提取3次，蒸除溶剂后，产物用分子蒸馏可得含F-PEO100132mg。IR(neat)：1728cm-1，19F NMR(376MHz，CDCl3)：δ-170(m，1F)。
(实施例5)FF-PAO6和F-PAO6的基础油调配试验
FF-PAO6和F-PAO6的基础油调配及检测的试验结果如表1所示。
表1、针对FF-PAO6和F-PAO6的基础油调配实例及检测结果
备注：(1)PAO6为市售的普通PAO产品；(2)FF-PAO6和F-PAO6为本发明合成的双取代F和单取代F的PAO产品。
将上述基础油按照上表中的配比进行调和，然后各自分别与下述添加剂进行混合，制得配方型润滑油组合物：
(1)0.4wt％的受阻酚和二苯胺类抗氧剂，加料比例为1∶1；
(2)1.5wt％的磷酸丁基化三苯酯类抗摩擦剂；
(3)0.1wt％的无灰防锈剂。
将上述组合物在100℃下放置16周，其中调和实验例1，4，5，6，7，8，9没有浑浊和沉淀现象发生，这说明本发明实施例的产品FF-PAO6和F-PAO6有效改善了上述三种类型的功能添加剂在润滑油组合物中的溶解性和分散性。
调和实验例2，3则出现了痕迹浑浊和中度的絮凝。浑浊和絮凝的出现，则说明上述润滑油组合物中发生了添加剂的不溶解现象。
通过对上述调和实验例进行ASTM-D1401的抗乳化性能测试，结果发现，由FF-PAO6和F-PAO6调制出的润滑油组合物可以在8分钟内与水完全分离(试验例配方中显然并不含抗乳化剂)。这说明，通过本专利方法制成的含氟PAO具有较好的分水性。
(实施例6)FF-PEO100和F-PEO100的基础油调配试验
FF-PEO100和F-PEO100的基础油调配及检测的试验结果如表2所示。
表2、针对FF-PEO100和F-PEO100的基础油调配实例及检测结果
备注：(1)PEO100为市售的普通PEO产品；(2)FF-PEO100和F-PEO100为本发明合成的双取代F和单取代F的PEO产品。
将上述基础油按照上表中的配比进行调和，然后各自分别与下述添加剂进行混合，制得配方型润滑油组合物：
(1)0.4wt％的受阻酚和二苯胺类抗氧剂，加料比例为1∶1；
(2)1.5wt％的磷酸丁基化三苯酯类抗摩擦剂；
(3)0.1wt％的无灰防锈剂。
将上述组合物在100℃下放置16周，其中调和实验例4，5，6，7，8，9没有浑浊和沉淀现象发生，这说明本发明实施例的产品FF-PEO100和F-PEO100有效改善了上述三种类型的功能添加剂在润滑油组合物中的溶解性和分散性。
调和实验例1，2，3则出现了痕迹浑浊和中度的絮凝。浑浊和絮凝的出现，则说明上述润滑油组合物中发生了添加剂的不溶解现象。
通过对上述调和实验例进行ASTM-D1401的抗乳化性能测试，结果发现，由FF-PEO100和F-PEO100调制出的润滑油组合物可以在8分钟内与水完全分离(实施例配方中显然并不含抗乳化剂)。这说明，通过本专利方法制成的PEO具有较好的分水性。
综上，通过对聚α烯烃的端位或其他位置的双键进行加成反应，引进极性基团，改善了聚α烯烃与其它添加剂的相溶性，同时得到了一系列新型的具有耐高温，防水，耐腐蚀性，耐辐射性，耐磨损性好的含卤素基团的合成基础油。
现有市售的PAO型基础油为非极性，在使用添加剂，特别是增粘类聚合物时，存在溶解性问题，这对于配方的结果有很大的影响。通过对聚α烯烃的端位或其他位置的双键进行加成反应，引进极性基团，提高了PAO的极性，有助于改善添加剂的溶解问题，保证油品的品质。通过增加润滑油的极性，可以使其在金属表面形成的吸附油膜牢固程度随着分子的极性增强而增加，油品的润滑作用随着膜层厚度的增加而增强。润滑油极性越强，油品和添加剂中初级氧化产物以及油泥的溶解度越大，油泥的生成也获得减少。同时，极性键能的增加，也给生物攻击润滑油分子提供了活化点，使其更便于生物降解。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明。应当理解，以上所述仅为本发明的具体实施例而已，并不用于限制本发明。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (5)

1.一类含卤素的合成基础油，其特征在于：所述基础油包含从原料PAO制备的合成产物XXPAO和/或XPAO，其中：
所述PAO为
所述合成产物XXPAO或XPAO的分子量在100-20000；
X为氟；
n为整数2-30；
R为下述群组中的一种：
1)链长为4-20的聚-α烯烃基团，其分子量在100-20000，
2)链长为4-20的单体α-烯烃或链长为4-20的混合α烯烃的聚合物基团，其分子量在100-20000，
3)乙烯聚合的多支链聚乙烯基团，其分子量在100-20000，
4)乙烯和丙烯共聚物基团，其分子量在100-20000，
5)乙烯与链长为4-20的α烯烃共聚物基团，其分子量在100-20000，和
6)异丁烯聚合物基团，其分子量在100-20000；
其中，所述产物的合成包括：
聚-α烯烃在端位双键或其他位双键加成氟，
单体α烯烃或混合α烯烃聚合物在端位双键或其他位双键加成氟，
乙烯聚合的多支链聚乙烯在端位双键或其他位双键加成氟，
乙烯和丙烯共聚物在端位双键或其他位双键加成氟，
乙烯与α烯烃共聚的聚合物在端位双键或其他位双键加成氟，或
异丁烯聚合物在端位双键或其他位双键加成氟。
2.根据权利要求1所述的合成基础油，其中所述n为数字2-10。
3.权利要求1-2任一项所述合成基础油的制备方法，其中：
所述PAO为
所述合成产物XXPAO或XPAO的分子量在100-20000；
X为氟；
R为下述群组中的一种：
1)链长为4-20的聚-α烯烃基团，其分子量在100-20000，
2)链长为4-20的单体α-烯烃或链长为4-20的混合α烯烃的聚合物基团，其分子量在100-20000，
3)乙烯聚合的多支链聚乙烯基团，其分子量在100-20000，
4)乙烯和丙烯共聚物基团，其分子量在100-20000，
5)乙烯与链长为4-20的α烯烃的共聚物基团，其分子量在100-20000，和
7)异丁烯聚合物基团，其分子量在100-20000；
其中，所述产物的合成包括：
聚-α烯烃在端位双键或其他位双键加成氟，
单体α烯烃或混合α烯烃聚合物在端位双键或其他位双键加成氟，
乙烯聚合的多支链聚乙烯在端位双键或其他位双键加成氟，
乙烯和丙烯共聚物在端位双键或其他位双键加成氟，
乙烯与α烯烃共聚的聚合物在端位双键或其他位双键加成氟，或
异丁烯聚合物在端位双键或其他位双键加成氟。
4.根据权利要求3所述的制备方法，其中，根据所用的亲电反应条件不同，生成不同的产物：
1)当使用氟的时候，生成的产物在端位和alpha位以及非端位双键上氟化加成的双氟取代的产物，即XXPAO；
2)当使用氟化氢的时候，生成的产物为在alpha和beta位以及非端位双键上氟化加成的单氟取代的产物XPAO。
5.权利要求1-2任一项所述的合成基础油的用途，包括将所述合成基础油与添加剂混合形成组合物用作润滑油，其中所述基础油具有较好的分水性，并且能够与添加剂有较高的相溶性。
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