CN112876625B - 一种聚（甲基）丙烯酸酯类粘度指数改进剂及其制备方法和应用 - Google Patents

一种聚（甲基）丙烯酸酯类粘度指数改进剂及其制备方法和应用 Download PDF

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CN112876625B
CN112876625B CN202110055411.0A CN202110055411A CN112876625B CN 112876625 B CN112876625 B CN 112876625B CN 202110055411 A CN202110055411 A CN 202110055411A CN 112876625 B CN112876625 B CN 112876625B
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魏观为
孔令杰
张东恒
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Dalian Tongkang New Material Technology Co ltd
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Abstract

本发明公开了一种聚(甲基)丙烯酸酯类粘度指数改进剂及其制备方法和应用。该制备方法包括：在保护气体和有机溶剂的存在下，将第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂、引发剂和任选的第一其他烯类单体进行接触反应；然后加入偶联剂，继续进行接触反应；最后加入第二(甲基)丙烯酸酯类单体混合物和任选的第二其他烯类单体，再进行接触反应，得到聚(甲基)丙烯酸酯类粘度指数改进剂。本发明的粘指剂能改变目前所有添加了粘指剂的润滑油在剪切工况中粘度和粘度指数总是不断下降的趋势，在很长的使用时间内，油品粘度和粘度指数(VI)上升或者基本不变。充分保持油品的粘度性能和粘温性能。

Description

一种聚（甲基）丙烯酸酯类粘度指数改进剂及其制备方法和 应用
技术领域
本发明属于粘度指数改进剂技术领域，更具体地，涉及一种聚(甲基) 丙烯酸酯类粘度指数改进剂及其制备方法和应用。
背景技术
粘度指数改进剂(VII)是指用于润滑油当中，能提高油品粘度，并改善成品油的粘温性能的高分子油溶性聚合物，主要产品有以下几种：聚异丁烯(PIB)、聚甲基丙烯酸酯(PMA)、乙丙共聚物(OCP)、氢化苯乙烯双烯共聚物(HSD)、苯乙烯聚酯、聚正丁基乙烯基醚。目前市场上，OCP、PAMA、HSD的用量占绝大多数。粘度指数改进剂的分子量与组成差异较大，分子量范围10000～800000。加入粘指剂形成多级油的目的主要是提高油品粘度以降低磨损、省油、实现油品通用化、增产高粘度油品等。评价粘度指数改进剂的指标主要有以下5个方面：
(1)增稠能力，是指加入粘度指数改进剂后，提高油品粘度的大小的能力。增稠能力越强，加入量越少，越经济。增稠能力主要与粘指剂的化学组成和相对分子质量大小有关，相对分子质量越大，增稠能力越强。
(2)改善粘温性能的能力，指加入粘指剂之后的油品相比相同级别的基础油，高低温的粘度差异较小。改善粘温性能的能力常用提高粘度指数 (VI)的大小来标定，一般认为提高的粘度指数越大，改善粘温性能的能力越强。主要也与粘指剂的化学组成和相对分子质量大小有关，相对分子质量越大，提高粘度指数的能力也越强。
(3)剪切稳定性，指添加粘指剂的油品使用中被机械剪切后保持粘度的能力。一般来说，在有机械剪切的工况下使用，油品粘度有一定程度和速度的下降。以特定剪切方法下的剪切稳定指数(SSI)表示剪切稳定性，SSI 越小，剪切稳定性越好，粘指剂分子越不容易被剪断，最直观的表现就是造成使用后的油品的粘度下降得较小较慢。一般来说，组成结构相同的粘指剂，分子量越大，高分子链越容易被剪断，使用后的油品的粘度下降得较大较快。另外，相同平均分子量的粘指剂，分子量分布越窄抗剪切越好，即SSI越低。
(4)低温性能，主要指倾点、在内燃机油中的低温起动性和泵送性、低温动力粘度、扫描布氏粘度等低温粘度指标。低温性能取决于在其使用温度和剪切条件下的粘度，后者又与所用的粘度指数改进剂有密切关系。粘指剂的种类、加入量、与基础油的溶度参数、与降凝剂的配伍等因素都影响油品的低温性能。
(4)热氧化安定性，主要指粘度指数改进剂在经受热氧化分解后导致粘度下降，酸值增加，环槽积碳增多和粘环等系列问题。
最理想的粘度指数改进剂，不仅要求增粘能力高，改善粘温性能的能力强，剪切稳定性好，同时还要求具有良好的低温性能和热氧化安定性。但至今为止还没有一种粘度指数改进剂能满足上述全部要求。黏指剂的选择，主要是根据不同种类油品的实际工况，对于粘指剂功能要求的侧重点不同来选择。
目前为了提高粘指剂的剪切稳定性，目前的粘指剂产品都是通过降低聚合物产品的相对分子量、降低分子量分布、调整分子组成和结构等手段，来减缓润滑油的粘度下降，但是添加了粘指剂的润滑油，在剪切工况下使用，粘指剂的高分子链或多或少被剪断，总体趋势都是油品粘度和粘度指数(VI)不断下降的。
发明内容
本发明的目的是提供一种特殊性能的聚(甲基)丙烯酸酯类粘度指数改进剂结构，能改变目前所有添加了粘指剂的润滑油在剪切工况中粘度和粘度指数总是不断下降的趋势，在很长的使用时间内，油品粘度和粘度指数(VI)上升或者基本不变。充分保持油品的粘度性能和粘温性能。
为了实现上述目的，本发明的第一方面提供了一种聚(甲基)丙烯酸酯类粘度指数改进剂的制备方法，该制备方法包括：在保护气体和有机溶剂的存在下，将第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂、引发剂和任选的第一其他烯类单体进行接触反应；然后加入偶联剂，继续进行接触反应；最后加入第二(甲基)丙烯酸酯类单体混合物和任选的第二其他烯类单体，再进行接触反应，得到所述聚(甲基)丙烯酸酯类粘度指数改进剂。
本发明的制备方法采用可逆加成断裂链转移(RAFT)自由基聚合，反应分3步，第一步，先将含有不同碳数侧基的丙烯酸酯单体和/或甲基丙烯酸酯单体的混合物(第一(甲基)丙烯酸酯类单体混合物)以一定比例共聚，得到聚(甲基)丙烯酸烷基酯大分子RAFT试剂；第二步，再加入偶联剂形成聚(甲基)丙烯酸烷基酯星型聚合物；最后一步，加入一定比例的(甲基)丙烯酸酯单体混合物(第二(甲基)丙烯酸酯类单体混合物)，继续反应，最终形成多个星型结构聚合物分子连接而成的聚(甲基)丙烯酸烷基酯产品，称之为多联星型聚(甲基)丙烯酸酯粘指剂。以多联星型聚甲基丙烯酸酯粘指剂的制备方法为例，本发明的多联星型聚甲基丙烯酸酯粘指剂制备方法示意图如图1所示。
本发明中，聚(甲基)丙烯酸酯类粘度指数改进剂为聚甲基丙烯酸酯类粘度指数改进剂和/或聚丙烯酸酯类粘度指数改进剂；第一(甲基)丙烯酸酯类单体混合物为第一甲基丙烯酸酯类单体混合物和/或第一丙烯酸酯类单体混合物；第二(甲基)丙烯酸酯类单体混合物为第二甲基丙烯酸酯类单体混合物和/或第二丙烯酸酯类单体混合物。
根据本发明，优选地，所述第一(甲基)丙烯酸酯类单体混合物和第二(甲基)丙烯酸酯类单体混合物各自独立的选自式Ⅰ所示单体中的至少两种，其中，R1为-H或-CH3，R2为C1-C36的直链烷基、C1-C36的支链烷基或C1-C36的带有芳香基团的烷基；
Figure BDA0002900446950000041
本发明中，所述第一(甲基)丙烯酸酯类单体混合物和第(甲基)二丙烯酸酯类单体混合物的混合物组成可以完全相同，也可以不完全相同；优选地，以第一(甲基)丙烯酸酯类单体混合物的总重量计，所述第一(甲基)丙烯酸酯类单体混合物中R2为C6-C18的(甲基)丙烯酸酯类单体为 20-90wt％；以第二(甲基)丙烯酸酯类单体混合物的总重量计，所述第二(甲基)丙烯酸酯类单体混合物中R2为C6-C18的(甲基)丙烯酸酯类单体为50-100wt％。
根据本发明，优选地，所述第一其他烯类单体和第二其他烯类单体各自独立的为甲基丙烯酸酰胺、苯乙烯和乙烯基吡咯烷酮中的至少一种。
本发明中，所述甲基丙烯酸酰胺优选为甲基丙烯酸甲酰胺。
根据本发明，优选地，所述偶联剂为双烯和/或多烯类偶联剂；
所述引发剂为偶氮二异丁腈；
所述可逆链转移剂为二硫代苯甲酸异丁腈酯；
所述有机溶剂为甲苯；
所述保护气体为氮气。
根据本发明，优选地，所述偶联剂为多烯类偶联剂，所述多烯类偶联剂优选为二乙烯基苯、二甲基丙烯酸乙二醇酯和三甲基丙烯酸三羟甲基丙烷酯中的至少一种。
本发明中多烯类偶联剂为至少含有两个碳碳双键的烯类偶联剂。
根据本发明，优选地，所述第一(甲基)丙烯酸酯类单体混合物的总物质的量与所述可逆链转移剂的物质的量的比为10～1000:1，优选为 50～300:1；
所述可逆链转移剂与引发剂的物质的量比为1:0.01～0.5；
所述第一其他烯类单体的物质的量与所述第一(甲基)丙烯酸酯类单体混合物的总物质的量比为0～0.3:1；
所述偶联剂与所述可逆链转移剂的物质的量的比为2～50:1；
所述第二(甲基)丙烯酸酯类单体混合物的总物质的量与所述可逆链转移剂的物质的量的比为5～500:1，优选为10～60:1；
所述第二其他烯类单体的物质的量与所述第二(甲基)丙烯酸酯类单体混合物的总物质的量比为0～0.3:1。
根据本发明，优选地，所述接触反应的温度为70-90℃；
所述第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂、引发剂和任选的第一其他烯类单体进行接触反应的时间为2～12h；所述继续进行接触反应的时间为2～24h；所述再进行接触反应的时间为10～72h。
本发明的第二方面提供上述制备方法制备的聚(甲基)丙烯酸酯类粘度指数改进剂。
根据本发明，优选地，所述聚(甲基)丙烯酸酯类粘度指数改进剂的数均分子量为20万至70万。
本发明的第三方面提供上述聚(甲基)丙烯酸酯类粘度指数改进剂在润滑油中的应用。
本发明的多联星型聚(甲基)丙烯酸酯类黏指剂能改变目前所有添加了粘指剂的润滑油在剪切工况中粘度和粘度指数总是不断下降的趋势，在很长的使用时间内，油品粘度和粘度指数(VI)上升或者基本不变。充分保持油品的粘度性能和粘温性能。具体的作用机理如下：以多联星型聚甲基丙烯酸酯黏指剂(PMA粘指剂)为例：多联星型PMA粘指剂用于润滑油中，在遭受机械剪切之后，分子中各星型结构连接的链段更易被剪断，一个多联星型PMA分子可能逐渐释放出多个星型结构的PMA分子和部分线型结构的PMA分子，多个星型结构的PMA分子和部分线型结构的PMA 分子总的流体力学体积大于单个多联星型PMA分子的流体力学体积，而且释放出的星型PMA仍保持高粘度指数的性质。反映在润滑油中的性能表现则是：随着润滑油的使用，油品粘度反而会上升，粘度指数保持的很好，甚至也上升。多联星型PMA粘指剂可能的作用机理如图2所示(图中n， m为≥0的任意整数)。
本发明的黏指剂改变了一般传统各种粘指剂在剪切工况下，粘度和粘度指数不断下降的趋势。可以针对润滑油具体的实际使用工况，通过分子量、组成和结构的设计，让多联星型聚(甲基)丙烯酸酯类粘指剂在润滑油的使用寿命内保持粘度和粘度指数增长或者基本不变。
本发明的技术方案具有如下有益效果：
本发明的粘指剂能改变目前所有添加了粘指剂的润滑油在剪切工况中粘度和粘度指数总是不断下降的趋势，在很长的使用时间内，油品粘度和粘度指数(VI)上升或者基本不变。充分保持油品的粘度性能和粘温性能。
本发明的其它特征和优点将在随后具体实施方式部分予以详细说明。
附图说明
通过结合附图对本发明示例性实施方式进行更详细的描述，本发明的上述以及其它目的、特征和优势将变得更加明显，其中，在本发明示例性实施方式中，相同的参考标号通常代表相同部件。
图1示出了根据本发明的一种多联星型聚甲基丙烯酸酯粘指剂(粘度指数改进剂)的制备方法示意图。
图2示出了根据本发明的一种多联星型聚甲基丙烯酸酯粘指剂(粘度指数改进剂)在润滑油中经机械剪切作用的作用机理示意图。
具体实施方式
下面将更详细地描述本发明的优选实施方式。虽然以下描述了本发明的优选实施方式，然而应该理解，可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。相反，提供这些实施方式是为了使本发明更加透彻和完整，并且能够将本发明的范围完整地传达给本领域的技术人员。
实施例1-4的具体配方见表1，具体制备方法如下：
将一定比例的第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂(二硫代苯甲酸异丁腈酯)、偶氮二异丁腈(引发剂)、甲苯和和任选的第一其他烯类单体加入反应瓶，通氮气抽真空除氧3次；把反应瓶放入80℃恒温水浴中，反应一段时间(具体见表1第一步反应时间)后；加入一定比例的偶联剂，继续反应一段时间(具体见表1第二步反应时间)；之后再加入一定比例的第二(甲基)丙烯酸酯类单体混合物和任选的第二其他烯类单体，再反应一段时间(具体见表1第三步反应时间)；将反应液加入甲醇中沉淀，沉淀物干燥得到多联星型聚甲基丙烯酸酯(PMA)粘指剂(不含稀释剂的干胶产品)。其中，制备各实施例加入的甲苯溶剂的质量都与相应实施例反应过程中反应单体的总加入质量相同。
表1
Figure BDA0002900446950000071
Figure BDA0002900446950000081
Figure BDA0002900446950000091
Figure BDA0002900446950000101
其中，表1中的对比例1和对比例2均为只进行第一步聚合，得到的线型常规PMA粘指剂。具体制备方法为将一定比例的第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂(二硫代苯甲酸异丁腈酯)、偶氮二异丁腈、甲苯和任选的第一其他烯类单体加入反应瓶，通氮气抽真空除氧3次；把反应瓶放入80℃恒温水浴中，反应一段时间(具体见表1第一步反应时间)后；将反应液加入甲醇中沉淀，沉淀物干燥得到线型常规PMA粘指剂 (不含稀释剂的干胶产品)。其中，加入的甲苯溶剂的质量与反应过程中反应单体的总加入质量相同。
测试例
将实施例1-4和对比例1-2的黏指剂溶于100N基础油，其中，以黏指剂(干胶)和基础油的总重量计，实施例1-4和对比例1-2的黏指剂(干胶) 的用量为7wt％；将上述配制好的黏指剂与100N基础油的混合物以SH/T 0103的实验方法做柴油喷嘴30循环和250循环的剪切安定性实验，对比剪切前后的油样的100℃运动粘度(KV100)的变化，100℃时的运动粘度 (KV100)，采用GB/T 265实验方法测定；具体测试结果见表2，其中表中刚调配时的KV100是指剪切前的100℃运动粘度(KV100)。
表2
Figure BDA0002900446950000111
由表2可知：对比例中，在柴油喷嘴30循环剪切和250循环剪切之后，添加了对比样品的油品的100℃运动粘度(KV100)是不断下降的。在实施例1、2、4中，在柴油喷嘴30循环剪切和250循环剪切之后，KV100持续升高，而所有实施例1-4中，在柴油喷嘴30循环剪切和250循环剪切之后的 KV100都比最初调制原油样的高。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。

Claims (4)

1.一种聚(甲基)丙烯酸酯类粘度指数改进剂的制备方法，其特征在于，该制备方法包括：在保护气体和有机溶剂的存在下，将第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂、引发剂进行接触反应；然后加入偶联剂，继续进行接触反应；最后加入第二(甲基)丙烯酸酯类单体混合物再进行接触反应，得到所述聚(甲基)丙烯酸酯类粘度指数改进剂；所述第一(甲基)丙烯酸酯类单体混合物是由0.1mol甲基丙烯酸甲酯、0.1mol甲基丙烯酸正辛酯、0.1mol甲基丙烯酸正癸酯、0.3mol甲基丙烯酸月桂酯、0.1mol甲基丙烯酸正十四烷基酯、0.1mol甲基丙烯酸正十六烷基酯、0.1mol甲基丙烯酸正十八烷基酯、0.1mol甲基丙烯酸正二十二烷基酯构成；所述第二(甲基)丙烯酸酯类单体混合物是由0.03mol甲基丙烯酸正辛酯、0.03mol甲基丙烯酸正癸酯、0.02mol甲基丙烯酸月桂酯、0.1mol甲基丙烯酸正十四烷基酯、0.01mol甲基丙烯酸正十六烷基酯、0.01mol甲基丙烯酸正十八烷基酯、0.01mol甲基丙烯酸正二十二烷基酯构成;所述接触反应的温度为70-90℃；所述第一(甲基)丙烯酸酯类单体混合物、可逆链转移剂、引发剂进行接触反应的时间为2～12h；所述继续进行接触反应的时间为2～24h；所述再进行接触反应的时间为10～72h。
2.根据权利要求1所述的制备方法，其特征在于，所述偶联剂为双烯和/或多烯类偶联剂；所述引发剂为偶氮二异丁腈；
所述可逆链转移剂为二硫代苯甲酸异丁腈酯；
所述有机溶剂为甲苯；
所述保护气体为氮气。
3.根据权利要求2所述的制备方法，其特征在于，所述偶联剂为多烯类偶联剂，所述多烯类偶联剂为二乙烯基苯、二甲基丙烯酸乙二醇酯和三甲基丙烯酸三羟甲基丙烷酯中的至少一种。
4.根据权利要求1所述的制备方法，其特征在于，所述第一(甲基)丙烯酸酯类单体混合物的总物质的量与所述可逆链转移剂的物质的量的比为10～1000:1；
所述可逆链转移剂与引发剂的物质的量比为1:0.01～0.5；
所述偶联剂与所述可逆链转移剂的物质的量的比为2～50:1；
所述第二(甲基)丙烯酸酯类单体混合物的总物质的量与所述可逆链转移剂的物质的量的比为5～500:1。
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