CN1229099A - 制备丙烯酸酯和甲基丙烯酸酯聚合物的方法 - Google Patents
制备丙烯酸酯和甲基丙烯酸酯聚合物的方法 Download PDFInfo
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- CN1229099A CN1229099A CN99102324A CN99102324A CN1229099A CN 1229099 A CN1229099 A CN 1229099A CN 99102324 A CN99102324 A CN 99102324A CN 99102324 A CN99102324 A CN 99102324A CN 1229099 A CN1229099 A CN 1229099A
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- monomer
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- acrylic acid
- tubular reactor
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- 238000000034 method Methods 0.000 title claims abstract description 56
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- 239000000178 monomer Substances 0.000 claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
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- IRAPFUAOCHNONS-UHFFFAOYSA-N potassium;phenylmethylbenzene Chemical compound [K+].C=1C=CC=CC=1[CH-]C1=CC=CC=C1 IRAPFUAOCHNONS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical class CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
公开了通过丙烯酸单体的阴离子聚合,制备直链,支链和星形－聚合物的连续方法,以及该方法得到的直链,支链和星形－聚合物及其润滑油组合物。
Description
本发明涉及生产丙烯酸酯和甲基丙烯酸酯聚合物的连续方法，包括星形-支化的丙烯酸酯和甲基丙烯酸酯聚合物，以及用上述方法得到的丙烯酸酯和甲基丙烯酸酯聚合物及其润滑油组合物。发明的背景
星形-支化聚合物的制备是公知的，所说星形-支化聚合物包括连接聚合分支的核，上述聚合分支是共轭二烯非氢化的及氢化的均聚物或共聚物或者共轭二烯和单链烯基芳烃的选择性氢化的共聚物。这种聚合物的核包括聚(多乙烯基芳香基)偶联剂如聚(二乙烯基苯)，并且具有4-30个聚合分支。聚合分支是聚丁二烯或聚异戊二烯分支。
通常，有许多出版物和专利记载使用阴离子聚合作用制备丙烯酸酯和甲基丙烯酸酯，例如US4,927,703，US4,826,941和Fayt等人在Macromolecules Vol.20，1442-1444(1987)中的报道。这些引文公开了使用氯化锂和冠醚制备多分散性窄的聚(甲基)丙烯酸酯，例如在Fayt等人的论文P1442中可以看到，使用氯化锂可以制备多分散性为1.2-1.6的聚甲基丙烯酸酯，不使用氯化锂时多分散性是3.61。
WO96/23008公开了进行丙烯酸酯和甲基丙烯酸酯的阴离子聚合或共聚合的分批方法，在WO96/23008中，单体或共聚单体是一次或以快速连续的方法(但不是逐滴的)加入到阴离子聚合反应介质中的。这些参考文献没有教导本发明的连续管状反应器的方法。
EP0524054教导(甲基)丙烯酸单体的聚合方法，该方法包括在含有(1)至少一种引发剂和(2)碱金属醇盐的引发体系存在下聚合单体，该参考文献要求有碱金属醇盐存在，没有教导本发明的连续管状反应器的方法。
多官能的阴离子引发剂(Escwey et al.，Makromol.Chem.173(1973)235；Burchard et al.，Polymer 16(1975)180)已经被使用，并且用来控制双-不饱和单体(通常是二乙烯基苯)的数量(Worsfold etal.，Can.J.Chem.，47(1969)3379；Young et al.，Macromolecules，11(1978)899；Martin et al.，Anionic Polymerization：ACS Symp.Ser.，166(1981)557)。星形-支化聚合物领域的大部分工作使用聚苯乙烯或聚二烯进行，聚甲基丙烯酸酯星形-支化聚合物方面的工作相对较少。在储存期间粘度和分子量增加的多多分散性的材料是使用基团转移聚合的方法制备的(Simms等人，Chem.Technol.64(1991)139)。Zhu等人在Macromolecules，25(1992)7330，Tsitsilianis等人在Macromolecules，24(1991)5897和Zilliox等人在J.Polym.Sci.，Part C，22(1986)148中公开报道了由甲基丙烯酸酯制备的星形-聚合物。
US5,552,491(本文作为参考)教导了星形-支化的丙烯酸酯和甲基丙烯酸酯聚合物以及它们作为润滑油添加剂的用途。在上述专利中教导的丙烯酸单体和引发剂体系适用于本发明。但是上述专利是用分批的方法制备星形-支化的聚合物，没有教导本发明的连续聚合方法。发明概述
本发明涉及制备丙烯酸酯和甲基丙烯酸酯聚合物的连续方法，包括直链，支链和星形-支化的丙烯酸酯和甲基丙烯酸酯聚合物，其中所述的丙烯酸酯和甲基丙烯酸酯聚合物是在管状反应器中通过阴离子聚合反应被聚合。当需要星形-支化的聚合物时，聚合分支由丙烯酸和甲基丙烯酸单体得到，其核或芯是由多元醇的不饱和丙烯酸酯或甲基丙烯酸酯，例如二、三或四丙烯酸酯或甲基丙烯酸酯得到。另外，本发明还涉及由本发明方法得到的直链，支链和星形-支化的聚合物，以及含有本发明方法得到的直链，支链和/或星形-支化的聚合物的润滑油添加剂和含有上述润滑油添加剂的润滑油。
本发明涉及使用阴离子聚合反应，制备丙烯酸酯和甲基丙烯酸酯单体(可以带或不带有乙烯基共聚单体)的直链，支链和星形-支化的聚合物的连续方法。用于制备直链或支链聚合物或者星形-支化聚合物的分支的本发明的丙烯酸和甲基丙烯酸单体包括丙烯酸，丙烯酸酯，丙烯腈，丙烯酰胺，甲基丙烯酸，甲基丙烯酸酯，甲基丙烯腈和甲基丙烯酰胺。优选的丙烯酸和甲基丙烯酸单体是丙烯酸烷基酯或甲基丙烯酸烷基酯，其中的烷基含有1-30，优选1-18个碳原子，烷基可以是取代的或未取代的。这种丙烯酸酯和甲基丙烯酸酯的实例包括，但是不限于丙烯酸甲酯，甲基丙烯酸甲酯，丙烯酸乙酯，甲基丙烯酸乙酯，丙烯酸丁酯，甲基丙烯酸丁酯，丙烯酸异丁酯，甲基丙烯酸异丁酯，丙烯酸叔丁酯，甲基丙烯酸叔丁酯，甲基丙烯酸丙酯，丙烯酸2-乙基己基酯，甲基丙烯酸2-乙基己基酯，丙烯酸己基酯，甲基丙烯酸己基酯，甲基丙烯酸异丙基酯，丙烯酸十二烷基酯，甲基丙烯酸十二烷基酯，丙烯酸十八烷基酯，甲基丙烯酸十八烷基酯。
在本说明书中，除另有说明以外，术语“丙烯酸单体”是指包括丙烯酸和甲基丙烯酸单体两者。
非丙烯酸类乙烯基单体也可任意地包括在本发明的共聚物中，合适的乙烯基单体包括，但是不限于，丁二烯，异戊二烯，苯乙烯，α-甲基苯乙烯，乙烯基甲苯，叔丁基苯乙烯，氯苯乙烯，乙烯基萘，2-乙烯基吡啶，4-乙烯基吡啶等。
另外，在本发明的共聚物中还可以包括改进共聚物性质如多分散性，抗氧化性和耐磨性的单体，这种改进性能的典型的单体包括N，N-二甲基氨基丙基甲基丙烯酸酰胺，N，N-二乙基氨基丙基甲基丙烯酸酰胺，N，N-二甲基氨基乙基丙烯酸酰胺，N，N-二乙基氨基乙基丙烯酸酰胺，N，N-二甲基氨基乙基甲基丙烯酸酯，N，N-二乙基氨基乙基丙烯酸酯，N，N-二甲基氨基乙基硫代甲基丙烯酸酯，聚(乙二醇)乙基醚甲基丙烯酸酯，聚(乙二醇)4-壬基苯基醚丙烯酸酯和聚(乙二醇)苯基醚丙烯酸酯。
用于本发明的引发剂包括下式表示的引发剂：
R-M其中M是碱金属或碱土金属，R是直链或支链烷基，或优选具有1-6个碳原子的环烷基或芳基。这种引发剂的实例包括，例如烃基锂引发剂如烷基锂化合物，优选甲基锂，正丁基锂，仲丁基锂；环烷基锂化合物，优选环己基锂和芳基锂化合物，优选苯基锂，1-甲基苯乙烯基锂，对甲苯基锂，萘基锂和1，1-二苯基-3-甲基戊基锂。有用的引发剂还包括萘钠，1，4-二钠-1，1，4，4-四苯基丁烷，二苯基甲基钾和二苯基甲基钠。也可以使用锂的叔醇盐和含有三甲基甲硅烷基的化合物。
当需要星形-支化的聚合物时，星形-支化聚合物的芯优选从多元醇的不饱和丙烯酸酯或甲基丙烯酸酯制备。
典型的这种酯例如是乙二醇二丙烯酸酯，乙二醇二甲基丙烯酸酯，二乙二醇二丙烯酸酯，二乙二醇二甲基丙烯酸酯，丙三醇二丙烯酸酯，丙三醇三丙烯酸酯，甘露糖醇六丙烯酸酯，1，4-环己基二醇二丙烯酸酯，1，4-苯基二醇二甲基丙烯酸酯，季戊四醇四丙烯酸酯，1，3-丙二醇二丙烯酸酯，1，5-戊二醇二甲基丙烯酸酯，分子量200-4000的聚乙二醇的双丙烯酸酯和双甲基丙烯酸酯，ω，β-聚己内酯二醇二丙烯酸酯，季戊四醇三丙烯酸酯，1，1，1-三羟甲基丙烷三丙烯酸酯，季戊四醇四丙烯酸酯，三乙二醇二丙烯酸酯，三乙二醇二甲基丙烯酸酯，1，1，1-三羟甲基丙烷三甲基丙烯酸酯或六亚甲基二醇二丙烯酸酯和甲基丙烯酸酯。
在优选的实施方案中，本发明使用的阴离子聚合引发剂体系使用其它的化合物帮助调节阴离子聚合反应，优选的其它的化合物包括1，1-二苯基乙烯。1，1-二苯基乙烯具有相对高的电子亲和性，可以防止均聚合反应。
阴离子聚合生产直链或支链丙烯酸聚合物的连续方法包括以下步骤：(A)至少一种丙烯酸单体，并且可任意有至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，以及(B)阴离子聚合介质，所述阴离子聚合介质含有阴离子聚合引发剂体系和溶剂；在管状反应器中以连续方式接触足够的时间，使(A)和(B)进行反应达到所需的转化率，其中管状反应器的温度保持在30℃到-78℃，生产直链或支链的丙烯酸聚合物。
在制备直链或支链的丙烯酸聚合物的方法中，可以使用一个以上的容器存放组份(A)和(B)。例如对于每种要加入到管状反应器中的单体需要有分别的容器。通过控制单体加入管状反应器中的位置，使用另外的容器可以控制聚合物的结构和形成例如嵌段共聚物。
通过核-前法(core-first method)或核-后法(core-last method)，本方法还可以用于制备星形-支化的丙烯酸聚合物。
在本发明的核-前法中，星形-支化的丙烯酸聚合物的阴离子聚合生产包括以下步骤：(A)至少一种丙烯酸单体，并且可任意有至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，和(B)含有阴离子聚合引发剂体系，形成芯的单体和任意有溶剂的混合物；在管状反应器中以连续方式接触足够的时间，使(A)和(B)进行反应达到所需的转化率，其中管状反应器的温度保持在30℃到-78℃，产生星形-支化的丙烯酸聚合物。
在核-前法中，多元醇的丙烯酸酯或甲基丙烯酸酯是在阴离子聚合介质中进行阴离子聚合，并通过丙烯酸单体和任意的非丙烯酸乙烯基单体和/或改进性能的单体与含有预先形成的芯的阴离子聚合介质接触，形成星的聚合分支。
任意地可形成嵌段星形-聚合物。如上所述的核-前法还包括(C)选自丙烯酸单体，非丙烯酸类乙烯基单体和改进性能的单体的至少一种单体，和任意地可以加入的溶剂。往管状反应器中加入(C)的时间是在(A)和(B)接触并进行反应以后，但这时阴离子聚合物仍然是“活的”。该方法产生含有嵌段共聚物分支的星形-聚合物。
在核-后法中，星形-支化的丙烯酸聚合物的阴离子聚合生产包括以下步骤：(A)至少一种丙烯酸单体，和任意地有至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，以及(B)含有阴离子聚合引发剂体系和溶剂的混合物；在管状反应器中以连续方式接触足够的时间，使(A)单体聚合达到所需的转化率。
随后往管状反应器中加入(C)形成芯的单体，并且任意地可以加入溶剂；在(A)已经聚合，但阴离子聚合物还是“活的”的时候将(C)加入到管状反应器中，以便形成星形-支化的共聚物。
其中管状反应器的温度保持在30℃到-78℃。
在核-后法中，首先通过丙烯酸单体和任意地加入的非丙烯酸类乙烯基单体和/或改进性能的单体聚合，然后在管状反应器中以连续方式和阴离子聚合介质接触得到聚合分支。得到聚合物分支以后，以连续方式将多元醇的丙烯酸酯或甲基丙烯酸酯加入到管状反应器中，和与“活的”分支接触，使反应进行到形成星形-支化的聚合物。
当需要嵌段星形-聚合物时，可以将上述核-后法进行改进。加入选自丙烯酸单体，非丙烯酸类的乙烯基单体和改进性能的单体中的至少一种另外单体(D)，以及任意地加入溶剂。在(A)被聚合之后，并且(C)被加入到管状反应器之前和/或之后，将(D)加入到管状反应器中。该方法也产生含有嵌段共聚物分支的星形-聚合物。
在制备星形-支化的丙烯酸聚合物的方法中，可以使用一个以上的容器存放组份(A)，(B)，(C)和(D)。例如对于每种要加入到管状反应器中的单体需要有分别的容器。通过控制单体加入管状反应器，使用另外的容器可以控制聚合物的结构，和形成例如嵌段共聚物。
本发明制备直链，支链或星形-支化的聚合物的方法优选在无湿气及氧的情况下和至少在一种惰性溶剂中进行。聚合反应优选在无有害于阴离子催化剂体系的杂质的情况下进行。惰性溶剂优选烃类如异丁烷，戊烷，环己烷，苯，甲苯，二甲苯，四氢呋喃，二乙二醇二甲醚，四乙二醇二甲醚，邻-三联苯化合物，联苯，十氢化萘，四氢化萘或乙醚。
管状反应器的聚合或共聚合温度可以在约30℃到约-78℃之间变化，优选0℃到-50℃。包含单体和阴离子聚合介质的容器在聚合过程中维持于室温。
对通过管状反应器的流速和反应器的直径没有特别限制，只要能够控制聚合反应放出的热量以及使反应温度维持在30℃到约-78℃和反应滞留时间能够控制。一般反应器的直径约1/8英寸到约5英寸，太小难于使足够的物料排出，太大难于控制反应温度，管状反应器用适于低温操作的材料制造。
本发明方法得到的聚合物具有狭窄的多多分散性指数(重均分子量/数均分子量Mw/Mn)，范围在约1-2，优选约1-1.5。具有狭窄多多分散性指数的直链，支链和星形-聚合物作为粘度指数改进剂对于润滑油组合物是特别有用的，因为和具有宽的多多分散性指数的类似聚合物比较，它们显示出具有改进的剪切稳定性。
用凝胶渗透色谱法测定，本发明方法通常形成数均分子量500-1,000,000，优选500-500,000的直链或支链的聚合物。本发明的方法一般也可以形成数均分子量1,000-1000,000,000，优选100,000-10,000,000的星形-聚合物。
在生产本发明的聚合物的方法中，聚合反应通常在惰性气氛中，例如在氮气、氩气气氛中进行。聚合反应使用的设备应该仔细干燥，溶剂和试剂也应该仔细干燥。例如假如使用四氢呋喃(THF)作为聚合介质，THF应该是用Na-二苯酮新蒸馏的，或者使用无水THF。丙烯酸单体或使用的其它单体或共聚单体应该是通过吸附材料如氧化铝提纯过的单体。二苯基乙烯可以用分子筛干燥，通常应该使用标准的金属引发剂。
本发明的丙烯酸聚合物主要在润滑油组合物中用作粘度指数改进剂，润滑油组合物使用溶解或分散添加剂的基础油。本发明的丙烯酸聚合物也可以用作倾点下降剂。上述基础油可以是天然油，合成油或其混合物。适于制备本发明润滑油组合物的基础油包括作为曲轴箱润滑油通常使用的那些基础油，用于电火花打火和压缩打火的内燃机，例如汽车和卡车引擎，轮船和铁路的柴油机引擎等。使用本发明的共聚物作为通常使用和/或采纳的基础油中的粘度指数改进剂对于用作动力传送流体，，重负荷水利系统流体和动力转向流体等也是很有好处的，齿轮润滑油，工业油，泵油和其它润滑油组合物，由于加入本发明的星形-聚合物也是有利的。
这些润滑油配方通常还含有提供配方所需要的特性的其它添加剂，这些添加剂包括其它粘度指数改进剂，其它倾点下降剂，抗氧化剂，腐蚀抑制剂，去污剂，分散剂，防水剂，抗泡沫剂，破乳剂和摩擦改进剂。
本发明的丙烯酸聚合物用作润滑油的粘度指数改进剂时，所使用的丙烯酸聚合物的用量以有效成分为基础(即除了溶剂，稀释剂和杂质以外)，相应的比例是被处理的润滑油的约0.1-约20重量％，优选约0.1-约10重量％。
本发明的丙烯酸聚合物用作润滑油的倾点下降剂时，所使用的丙烯酸聚合物的用量以有效成分为基础(即除了溶剂，稀释剂和杂质以外)，相应的比例是被处理的润滑油的约0.01-约1重量％，优选约0.05-约0.5重量％。
本发明的丙烯酸聚合物可以直接加入到被处理的润滑油中，但是通常是以添加的浓缩物形式使用本发明的丙烯酸聚合物。浓缩物含有本发明方法得到的丙烯酸聚合物和以通常的液体有机稀释剂如天然油，矿物油或其混合物的任何另外的添加剂，或者其它合适的溶剂。按照本发明添加的浓缩物通常包括约10-80重量％的至少一种共聚物和任选的其它添加剂，其余为通常的液体有机稀释剂，构成100重量％。当然使用浓缩物的目的是减少处理各种材料的困难和在最终的混合物中容易形成溶液或分散液。
本发明方法得到的丙烯酸聚合物通常以与含有润滑粘性油的润滑油基本油料的混合物形式使用。合适的粘性油包括天然油如动物油，植物油(例如蓖麻油，猪油)，液体石油，和加氢精制油，严格加氢精制油，iso-脱蜡油，溶剂处理的或酸处理的石蜡类，萘类或混合的石蜡-萘类的矿物润滑油。由煤和页岩得到的润滑粘性油也是有用基础油。用于本发明中的合成油包括，但不限于，聚α-烯烃，合成酯，烷基化的芳香化合物，烯化氧聚合物，共聚体(intepolymers)，共聚物及其衍生物(其中的末端羟基已通过酯化或醚化等修饰)，二羧酸的酯和含硅的基础油。
以下实施例用于说明本发明，但不以任何方式构成对本发明范围的限制。
以下实施例说明，和使用同样的丙烯酸单体和同样的阴离子聚合引发剂体系的分批方法比较时，本发明方法制备的星形-聚合物具有的优点。比较例1-7是US5,552,491的实施例1-7给出的分批方法制备的星形-聚合物；实施例1-5是本发明的连续方法得到的星形-聚合物，所有星形-聚合物都是采用核-前法制备的。
| 星形Mn(g/mole) | Mw/Mn星形 | |
| 比较例1 | 136,800 | 1.8 |
| 比较例2 | 464,500 | 7.4 |
| 比较例3 | 191,700 | 2.4 |
| 比较例4 | 228,900 | 1.9 |
| 比较例5 | 315,700 | 2.5 |
| 比较例6 | 658,500 | 4.5 |
| 比较例7 | 276,900 | 2.3 |
| 实施例1 | 524,600 | 1.5 |
| 实施例2 | 1,231,000 | 1.3 |
| 实施例3 | 733,900 | 1.8 |
| 实施例4 | 764,300 | 1.4 |
| 实施例5 | 1,547,000 | 1.5 |
上表清楚地说明，和分批方法制备的星形-聚合物比较，本发明方法得到的星形-聚合物呈现狭窄的多分散性指数(Mw/Mn)。当用作润滑油组合物的粘度指数改进剂时，狭窄的分子量分布是有利的，这有许多原因，其中包括能够改进星形-聚合物的剪切稳定性。
本发明允许考虑实践中的各种变化，因此本发明不限于上述指出的个别实施例，本发明不仅包括在其后的权利要求书的精神和范围之内，并且包括在法律意义上的等价物。
专利权人不打算向公众指出任何公开的实施方案，在任何程度上的任何公开的修改或变化都不可以落在本权利要求的范围之内，按照等价物的原则，它们都被认为是本发明的一部分。
Claims (23)
1.一种阴离子聚合生产星形-支化的丙烯酸聚合物的连续方法，包括以下步骤：(A)至少一种丙烯酸单体，和任意地有至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，和(B)含有阴离子聚合引发剂体系，形成芯的单体，和任意有的溶剂的混合物；在管状反应器中以连续方式接触足够的时间，使(A)和(B)进行反应达到所需的转化率，其中管状反应器的温度保持在30℃到-78℃，产生星形-支化的丙烯酸聚合物。
2.按照权利要求1的方法，其中引发剂体系含有至少一种通式为R-M的引发剂，其中M是碱金属或碱土金属，R是有1-6个碳原子的直链或支链烷基或环烷基或芳基。
3.按照权利要求2的方法，其中的引发剂体系除了含有至少一种式R-M的引发剂以外，还含有1，1-二苯基乙烯。
4.按照权利要求1的方法，其中还含有(C)选自丙烯酸单体，非丙烯酸类乙烯基单体和改进性能的单体中的至少一种单体，和任意地有溶剂，其中(C)是在(A)和(B)接触并反应之后，但阴离子聚合物还是“活的”时候加入到管状反应器中的，以便形成星形-支化的嵌段共聚物。
5.权利要求1的方法得到的星形-聚合物。
6.一种润滑油组合物，含有为主量的润滑粘性油和少量的权利要求5的星形-聚合物。
7.按照权利要求6的润滑油组合物，其中星形聚合物以浓缩物的形式加入到润滑粘性油中。
8.按照权利要求6的润滑油组合物，其中还含有选自粘度指数改进剂，倾点下降剂，抗氧化剂，腐蚀抑制剂，去污剂，分散剂，耐磨剂，抗泡沫剂，破乳剂和摩擦改进剂中的至少一种添加剂。
9.一种阴离子聚合生产星形-支化的丙烯酸聚合物的连续方法，包括以下步骤：(A)至少一种丙烯酸单体，和任意地有至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，和(B)含有阴离子聚合引发剂体系和溶剂的混合物，在管状反应器中以连续方式接触足够的时间，使(A)单体聚合达到所需的转化率，随后将(C)形成芯的单体和任意有的溶剂，在(A)已经聚合，但阴离子还是“活的”的时候加入到反应容器中，以形成星形-支化的共聚物；
其中管状反应器的温度保持在30℃到-78℃。
10.按照权利要求9的方法，其中引发剂体系含有至少一种式R-M的引发剂，其中M是碱金属或碱土金属，R是有1-6个碳原子的直链或支链烷基或环烷基或芳基。
11.按照权利要求10的方法，其中的引发剂体系除了含有至少一种式R-M的引发剂以外，还含有1，1-二苯基乙烯。
12.按照权利要求9的方法，其中还含有(D)选自丙烯酸单体，非丙烯酸类乙烯基单体和改进性能的单体中的至少一种单体，和任意有的溶剂，其中(D)是在(A)已被聚合到所需的转化率和(C)加入到管状反应器之前和/或之后加入到管状反应器中，以形成星形-支化的嵌段共聚物。
13.权利要求9的方法得到的星形-聚合物。
14.一种润滑油组合物，含有为主量的润滑粘性油和少量的权利要求13的星形-聚合物。
15.按照权利要求14的润滑油组合物，其中星形-聚合物以浓缩物的形式加入到润滑粘性油中。
16.按照权利要求14的润滑油组合物，其中还含有选自粘度指数改进剂，倾点下降剂，抗氧化剂，腐蚀抑制剂，去污剂，分散剂，耐磨剂，抗泡沫剂，破乳剂和摩擦改进剂中的至少一种添加剂。
17.一种阴离子聚合生产直链或支链的丙烯酸聚合物的连续方法，包括以下步骤：(A)至少一种丙烯酸单体，和任意有的至少一种溶剂，非丙烯酸类乙烯基单体和/或改进性能的单体，和(B)阴离子聚合介质，所述阴离子聚合介质含有阴离子聚合引发剂体系和溶剂，在管状反应器中以连续方式接触足够的时间，使(A)和(B)反应达到所需的转化率，其中管状反应器的温度保持在30℃到-78℃，形成直链或支链的丙烯酸聚合物。
18.按照权利要求17的方法，其中引发剂体系含有至少一种式R-M的引发剂，其中M是碱金属或碱土金属，R是有1-6个碳原子的直链或支链烷基或环烷基或芳基。
19.按照权利要求18的方法，其中的引发剂体系除了含有至少一种式R-M的引发剂以外，还含有1，1-二苯基乙烯。
20.权利要求17的方法得到的直链或支链聚合物。
21.一种润滑油组合物，含有为主量的润滑粘性油和少量的权利要求20的聚合物。
22.按照权利要求21的润滑油组合物，其中聚合物以浓缩物的形式加入到润滑粘性油中。
23.按照权利要求21的润滑油组合物，其中还含有选自粘度指数改进剂，倾点下降剂，抗氧化剂，腐蚀抑制剂，去污剂，分散剂，耐磨剂，抗泡沫剂，破乳剂和摩擦改进剂中的至少一种添加剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/023555 | 1998-02-13 | ||
| US09/023,555 US6013735A (en) | 1998-02-13 | 1998-02-13 | Process for the preparation of acrylate and methacrylate polymers |
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| Publication Number | Publication Date |
|---|---|
| CN1229099A true CN1229099A (zh) | 1999-09-22 |
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ID=21815821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99102324A Pending CN1229099A (zh) | 1998-02-13 | 1999-02-13 | 制备丙烯酸酯和甲基丙烯酸酯聚合物的方法 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6013735A (zh) |
| EP (1) | EP0936225B1 (zh) |
| JP (1) | JPH11286520A (zh) |
| KR (1) | KR19990072326A (zh) |
| CN (1) | CN1229099A (zh) |
| AU (1) | AU1007499A (zh) |
| BR (1) | BR9900574A (zh) |
| CA (1) | CA2258373A1 (zh) |
| DE (1) | DE69917093T2 (zh) |
| SG (1) | SG74693A1 (zh) |
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-
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- 1999-01-05 CA CA002258373A patent/CA2258373A1/en not_active Abandoned
- 1999-01-07 AU AU10074/99A patent/AU1007499A/en not_active Abandoned
- 1999-01-22 SG SG1999000146A patent/SG74693A1/en unknown
- 1999-01-29 KR KR1019990002872A patent/KR19990072326A/ko not_active Application Discontinuation
- 1999-02-10 JP JP11032744A patent/JPH11286520A/ja active Pending
- 1999-02-11 BR BR9900574A patent/BR9900574A/pt not_active Application Discontinuation
- 1999-02-12 EP EP99301025A patent/EP0936225B1/en not_active Expired - Lifetime
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| CN1984981B (zh) * | 2004-07-16 | 2010-11-17 | 可乐丽股份有限公司 | 含有丙烯酸系聚合物的润滑油添加剂及润滑油组合物 |
| CN101087823B (zh) * | 2004-10-25 | 2010-08-18 | 卢布里佐尔公司 | 星形聚合物及其组合物 |
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| CN104704014A (zh) * | 2012-08-20 | 2015-06-10 | 路博润公司 | 疏松核星型聚合物及其润滑组合物 |
| CN104704014B (zh) * | 2012-08-20 | 2017-11-03 | 路博润公司 | 疏松核星型聚合物及其润滑组合物 |
| CN105203648A (zh) * | 2014-06-04 | 2015-12-30 | 中国石油化工股份有限公司 | 一种测定添加剂合成过程中单体转化率的方法 |
| CN104672359A (zh) * | 2015-02-02 | 2015-06-03 | 华东理工大学 | 一种乙烯基极性单体实施阴离子加成聚合的方法 |
| CN113544242A (zh) * | 2019-03-07 | 2021-10-22 | 萨索尔化学品有限公司 | 聚合物作为润滑油组合物的添加剂的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6013735A (en) | 2000-01-11 |
| JPH11286520A (ja) | 1999-10-19 |
| DE69917093T2 (de) | 2004-10-28 |
| CA2258373A1 (en) | 1999-08-13 |
| AU1007499A (en) | 1999-08-26 |
| BR9900574A (pt) | 2000-03-21 |
| EP0936225B1 (en) | 2004-05-12 |
| KR19990072326A (ko) | 1999-09-27 |
| DE69917093D1 (de) | 2004-06-17 |
| EP0936225A1 (en) | 1999-08-18 |
| SG74693A1 (en) | 2000-08-22 |
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