CN1159823A - 油添加剂、组合物和其中使用的聚合物 - Google Patents

油添加剂、组合物和其中使用的聚合物 Download PDF

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CN1159823A
CN1159823A CN95195355A CN95195355A CN1159823A CN 1159823 A CN1159823 A CN 1159823A CN 95195355 A CN95195355 A CN 95195355A CN 95195355 A CN95195355 A CN 95195355A CN 1159823 A CN1159823 A CN 1159823A
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oil
composition
terpolymer
acid
group
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CN1046546C (zh
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B·W·戴维斯
R·J·布罗德
J·伯克
T·伊布拉海姆
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Abstract

包括乙烯/醋酸乙烯酯或丙酸乙烯酯/线性羧酸乙烯酯三元共聚物的组合物可用于改进石蜡含量至少3wt％的油的低温性能。

Description

油添加剂、组合物和其中使用的聚合物
本发明涉及油组合物，主要涉及燃料油组合物，更特别涉及在低温下容易形成石蜡的燃料油组合物，涉及与这些燃料油组合物一起使用的共聚物和它们的制备方法。
燃料油，无论衍生自石油或衍生自植物原料，都含有在低温下趋于以石蜡大晶体或球晶形式沉淀的组分如链烷，通过这种方式形成使燃料丧失其流动性能的凝胶结构。将燃料仍然会流动的最低温度称为倾点。
随着燃料温度降低并接近倾点，通过管线和泵输送燃料就造成了困难。同时，石蜡晶体趋于在高于倾点的温度时堵塞燃料管线、筛网和过滤器。这些问题在本领域已被充分认识到，并已提出了用于降低燃料油倾点的各种添加剂，其中很多已在工业上使用。类似地，还提出了其它一些添加剂并在工业上用于减少石蜡晶体的尺寸和改变石蜡晶体的形状。较小尺寸的晶体是合适的，因为它们堵塞过滤器的可能性较低。来自柴油的石蜡(它主要是链烷石蜡)以小片状形式结晶。某些添加剂可阻止这种结晶形成使石蜡形成针状晶型，与片状晶体相比，产生的针状晶体更容易通过过滤器。添加剂还具有使形成的晶体保持悬浮于燃料中的效果，导致的减少沉降也有助于防止堵塞。
石蜡晶体的有效改进(通过冷流动堵塞点(CFPP)和其它可操作性试验测量，以及模拟的和场性能)可通过基于乙烯-乙酸乙烯酯(EVAC)或丙酸乙烯酯共聚物的流动性改进剂达到。
在“Wissenschaft und Technik”42(6)，238(1989)中，M.Ratsch& M.Gebauer描述了一些冷流动性添加剂，其中包括已进行水解并特别用丙酸、正戊酸和正己酸再酯化的EVAC，用于酯化的酸为直链酸是优选的；带有支链的3-甲基丁酸酯化共聚物与用正戊酸酯化物料制得的共聚物相比产生明显差的结果。
在JP-A-58129096中，公开了包括乙烯-羧酸乙烯酯的冷流动性添加剂，酯化酸具有的总碳原子数为4至8个，这些添加剂特别适用于窄沸点柴油燃料油。据说通过质子NMR测量的主链支化程度为每100个亚甲基基团至少6个烷基支链。
在WO94/00536中，公开了包括乙烯与两种不同不饱和酯的三元共聚物的冷流动性添加剂。这些三元共聚物还公开于EP-A-493769中(起始单体为乙烯、乙酸乙烯酯和新壬酸或新癸酸乙烯酯)和该申请的检索报告中引用的参考文献中。
在英国专利说明书No.913715中，提出乙烯-乙烯酯共聚物作为柴油燃料油的倾点降低剂；对于酯化酸，提及在其烷基基团中含有4至10、12和18个碳原子的饱和脂族羧酸，其例子包括正辛酸。
英国专利说明书No.1,314,855公开了由乙烯、乙酸乙烯酯和长链羧酸的乙烯酯制备的三元共聚物。合适的长链羧酸包括C8-C30饱和羧酸，例如月桂酸、肉豆蔻酸、棕榈酸和硬脂酸。描述了这些三元共聚物可在润滑油组合物中作为粘度指数改性剂。
英国专利说明书No.1,244,512公开了乙烯、C2至C4单羧酸的乙烯酯和具有C10至C22烷基基团的可共聚不饱和酯的三元共聚物。后一类酯可以是(例如)C10至C22单羧酸如月桂酸、肉豆蔻酸、棕榈酸或硬脂酸的乙烯酯。描述了这些三元共聚物可用作柴油燃料油的倾点降低剂和过滤性改进剂。
目前不断需要特别在较高石蜡含量(例如在低于浊点10℃时高于约3％(重量))的油中显示比现有添加剂性能更好的添加剂。
现在，我们已令人吃惊地发现，具有特定线性度(聚合物主链的烷基支化程度)和(优选)不同单体的特定相对比例的三元共聚物可对较高石蜡含量的油提供石蜡晶体改性。
在第一方面，本发明提供一种油组合物，它包括在低于浊点10℃时具有至少3％(重量)石蜡含量的油和含有油溶性乙烯三元共聚物的流动性改进剂组合物，所述三元共聚物除衍生自乙烯的单元外，还具有如下通式的单元
Figure A9519535500051
和如下通式的单元
Figure A9519535500061
其中R1和R2可以是相同或不同的，各自代表H或甲基，R3代表含至多4个碳原子的烷基，R4代表具有3至15个碳原子的直链烷基，R3和R4是不同的；通过质子NMR谱测量的三元共聚物的支化程度(在下面更详细地描述)低于每100个CH2单元6个CH3基团。
这里使用的术语“三元共聚物”要求具有至少三种不同的重复单元(即衍生自三种不同单体的单元)和包括衍生自四种或多种单体的聚合物。例如，该聚合物可含有两种或多种通式I或II的不同单元和/或可含有如下通式的单元：其中R5代表具有3个或更多个碳原子烃基(与对R4定义的不同)。
本说明书中的术语“烃基”是指具有一个直接与主体结构相连的碳原子并具有烃或主要为烃特性的基团。在这些烃基中，可以提及的烃基团包括脂族(例如烷基)、环脂族(例如环烷基)、芳族、脂族和环脂族取代的芳族及芳族取代的脂族和环脂族基团。脂族基团为饱和基团是有利的。这些基团可含有非烃取代基，只要它们的存在不改变基团的主要的烃特性即可。这些基团的例子包括酮基、卤素、羟基、硝基、氰基、烷氧基和酰基。若烃基是被取代的，则单取代是优选的。取代的烃基团的例子包括2-羟乙基、3-羟丙基、4-羟丁基、2-酮丙基、乙氧基乙基和丙氧基丙基。这些基团在链中或包括碳原子的环中还可含有除碳原子外的原子。合适的杂原子包括(例如)氮、硫和优选氧。该烃基有利地含至多30个，优选至多15个，更优选至多10个和最优选至多8个碳原子。
这种三元共聚物还可含有不同于上述通式的单元，例如可含有如下通式的单元-CH2-CHR6        V其中R6代表-OH，或如下通式的单元 - CCH 3 ( CH 2 R 7 ) - CHR 8 - . . . . . . . . . VI 其中R7和R8各自代表氢或具有至多4个碳原子的烷基，单元VI有利地衍生自异丁烯、2-甲基丁烯-2或2-甲基戊烯-2。
在通式I中，R1有利地代表氢，R3有利地代表乙基或更优选甲基。在通式II的单元中，R2有利地代表氢。R4可代表丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基或十三烷基，有利地代表庚基。
如上所述，含有不同类型的R3和/或R4的混合物的三元共聚物属于本发明范围内。含有两种或多种三元共聚物的组合物也属于本发明范围内。
这种三元共聚物的含酯单元，特别是通式I和II的单元有利地为三元共聚物的0.3至35mol％。三元共聚物优选为类型(i)，其中酯基团有利地构成7.5至35mol％，优选10至25mol％，更优选13至17mol％。通式I的单元有利地为1至4mol％，优选1至2mol％，而通式II的单元有利地为12至15mol％，优选13至15mol％。此外，三元共聚物还可为类型(ii)，其中酯基团有利地为至多10mol％，更有利0.3至7.5mol％，优选3.5至7.0mol％。
这种三元共聚物的数均分子量Mn(通过凝胶渗透色谱测量)有利地为至多20,000。若聚合物为类型(i)，则其分子量通常为至多14,000，有利地至多10,000，更有利地为1,400至7000，优选为3,000至6,000，最优选3,500至5,500。若聚合物为类型(ii)，则其数均分子量有利地为至多20,000，优选至多15,000，更优选1,200至10,000，最优选3,000至10,000。
本发明三元共聚物的一个重要特点是它的线性度，即聚合物主链上的较小比例的烷基支链。这种支化度可表示为每100个亚甲基单元甲基基团个数，如上所述，该甲基基团个数(通过质子NMR测量)低于6，更有利地在1.0至4.5范围内，更特别为2.5至4.0，例如2.6至3.6。
在计算线性度时，每100个亚甲基基团中CH3基团的比例通过质子NMR测量，并基于数均分子量对其进行末端甲基基团校正(相当小的校正值)，更重要的是对其进行羧酸酯侧链的R3和R4烷基基团中的甲基和亚甲基基团数校正。
图1表示下述实施例4的乙烯-乙酸乙烯酯-辛酸乙烯酯三元共聚物样品的质子NMR谱。
如图1所示，将与计算有关的峰标注b、c、d和e，其中b源于位于羧酸酯基侧链R4上的羰基基团α位碳原子(本实施例中为亚甲基碳原子)上的氢原子；c表示R3(本实施例中为甲基)上相应的氢原子；d源于聚合物主链和羧酸酯侧链的亚甲基和次甲基(连接羧酸酯侧链的主链次甲基除外(其中通式1中的R1和/或R2代表H))上的氢原子；e源于聚合物主链和羧酸酯侧链的甲基的氢原子。
将b、c、d和e各峰下面的面积分别表示为B、C、D和E，为得到三元共聚物的支化程度，进行羧酸酯侧链甲基和亚甲基基团校正的每100个亚甲基基团中的CH3基团数按如下方式计算： E - 3 B / 2 3 × 2 D - 5 B × 100 然后通过减去下式所示的项进一步进行聚合物链末端甲基基团校正： 200 × ( 100 + MoleE ) 其中Mole E表示聚合物中的乙烯mole％，X表示： Mn ( D / 4 + E / 4 - 11 B / 8 + C / 6 ) 100 ( 65 B / 2 + 24 C + 7 D + 7 E )
三元共聚物可通过本领域公知的任何方法，例如通过用游离基引发的溶液聚合，或通过高压聚合，方便地在高压釜或管式反应器中制备。
聚合有利地在引发剂和(若需要或要求)分子量调节剂存在下在高压、例如90至125巴(9至12.5Mpa)和高温、但优选低于约130℃(例如90至125℃范围内)进行。保持温度低于上述限制可制得具有所需线性度的聚合物；也可以使用本领域已知的其它控制线性度的方法。
本发明第一方面所述的流动性改进剂组合物有利地还包括乙烯-不饱和酯共聚物。对于不饱和酯组分，尤其可提及饱和羧酸的乙烯酯或饱和醇与不饱和羧酸的酯。该共聚物除了衍生自乙烯的单元外，还可含有如下通式的单元：-CH2CR1R9-         III其中R1具有与上述相同的含义，且有利地为氢，R9表示通式COOR10或OOCR10基团，其中R10表示烃基。
共聚物有利地为乙烯-乙酸乙烯酯或丙酸乙烯酯共聚物或乙烯-丙烯酸酯共聚物。这种共聚物可以是与类型(i)或(ii)相同的三元共聚物或其它类型的共聚物。正如US3961916中公开的，流动性改进剂组合物可包括石蜡生长抑制剂和成核剂。在不希望受到任何理论限制的情况下，本申请人相信若本发明的三元共聚物为类型(I)的共聚物并具有多于约7.5mol％的酯单元，则它主要起到抑制剂的作用，并且得益于加入成核剂，例如数均分子量为1200至20000、乙烯基酯含量0.3至17mol％、和与三元共聚物组合物中的酯含量相比有利地酯含量较低(优选低至少2mol％，更优选低至少3mol％)的乙烯-乙烯酯、特别是乙酸乙烯酯共聚物。
然而，若本发明的三元共聚物为类型(ii)的共聚物并含有低于约10mol％的酯单元时，则相应主要起到成核剂的作用并得益于存在抑制剂，它可以是具有相应较低分子量和较高酯含量的乙烯/不饱和酯共聚物。
然而，已意想不到地发现，当乙烯-不饱和酯共聚物与三元共聚物基本为相同类型时，在性能上可得到另一些优点。因此，根据本发明第一方面油组合物包括特定的三元共聚物与相同于类型(i)或(ii)的乙烯-不饱和酯、特别是乙酸乙烯酯或丙酸乙烯酯的共聚物和不同于类型(i)或(ii)的乙烯-不饱和酯、特别是乙烯酯共聚物的混合物。在这种情况下，有利的是，三元共聚物和共聚物(特别是乙酸酯或丙酸酯共聚物)与另一共聚物的酯的摩尔比例和数均分子量不同，较高的酯比例优选与较低的分子量一致。乙烯/不饱和酯、特别是乙酸乙烯酯或丙酸乙烯酯共聚物与三元共聚物在组合物中的重量比有利地为9∶1至1∶9，更有利3∶1至1∶3，优选约1∶1。
本发明第二方面进一步提供添加剂母料，包括本发明第一方面的流动性改进剂组合物与油或可与油混溶的溶剂的混合物。
本发明第三方面还提供本发明第一方面的流动性改进剂在改进油的低温性能，特别是油的CFPP中的用途，和上述母料在改进油的相同性质中的用途，该油低于浊点10℃时具有至少约3％(重量)石蜡。
在本发明的含油组合物中，油可以为原油，即直接来自钻井和精制前的油。
该油可以为润滑油，它可以是动物、植物或矿物油，例如从石脑油或锭子油至SAE30、40或50润滑油等级的石油馏分，蓖麻油、鱼油或氧化矿物油。这种油可含有添加剂(取决于其预定的用途)；所述添加剂的例子是粘度指数改进剂如乙烯-丙烯共聚物、基于丁二酸的分散剂、含金属的分散剂添加剂和二烷基二硫代磷酸锌抗磨添加剂。本发明的三元共聚物可适合用于润滑油中作为流动性改进剂、倾点降低剂或脱蜡助剂。
该油可以为燃料油，例如石油基燃料油、特别是中间馏分燃料油。这些燃料油的沸点通常为110℃至500℃，例如150℃至400℃。这种燃料油可包括常压蒸馏或真空蒸馏裂化气油，或直馏馏分与热和/或催化裂解馏出液以任何比例的掺混物。最常见的石油馏出物燃料为煤油、航空煤油、柴油、燃料油和重燃料油。燃料油可为常压直馏馏分，或可含有少量、例如至多35wt％的真空气油或者裂化气油或真空气油和裂化气油。柴油和燃料油通常最可能遇到上述低温流动性问题。本发明还适用于单独使用的植物基燃料油(例如菜籽油)或其与石油馏分油的混合物。
本发明的三元共聚物可用于具有较高石蜡含量(例如在低于浊点10℃测量时具有大于3wt％的石蜡含量)。其中在低于浊点10℃时石蜡含量为3.3至6wt％，特别是3.4至5wt％的燃料是特别合适的。
三元共聚物优选应在室温下以每单位重量油至少1000ppm的量溶于油中。然而，至少一些三元共聚物可在接近油的浊点时从溶液中游离出来并起到改进形成的石蜡晶体的作用。
为改进低温和/或其它性能，本发明添加剂母料、流动性改进剂组合物和油组合物可含有其它添加剂，其中很多已在本领域中使用或从文献上已知。这些组合物可包括另一些冷流动性改进剂，包括(A)梳型高聚物。
梳型高聚物(A)是其中含烃基支链为聚合物骨架的侧基的聚合物，并已在“梳型聚合物，结构和性能”，N.A.Plate和V.P.Shibaev，聚合物科学杂志高分子综述，8，p117至253(1974)中进行了讨论。
通常梳型高聚物具有一个或多个长链烃基支链，例如一般具有10至30个碳原子的羟烃基支链(聚合物骨架的侧链)，所述支链直接或间接与骨架键合。间接键合的例子包括通过插入的原子或基团键合，所述键合包括共价键和/或(例如)盐中的电子键键合。
梳型聚合物有利地为具有至少25mol％、优选至少40mol％、更优选至少50mol％的具有侧链的单元的均聚物或共聚物，所述侧链含有至少6个、优选至少10个原子。
对于优选的梳型聚合物的例子，可提及具有如下通式的那些聚合物：
Figure A9519535500111
其中D＝R11、COOR11、OCOR11、R12COOR11或OR11，
E＝H、CH3、D或R12，
G＝H或D，
J＝H、R12、R12COOR11、或芳基或杂环基团，
K＝H、COOR12、OCOR12、OR12或COOH，
L＝H、R12、COOR12、OCOR12、COOH或芳基，
R11＞C10烃基，
R12＞C1烃基或亚烃基，m和n表示摩尔分数，m为有限的、优选为1.0至0.4，n小于1、其优选范围为0至0.6。R11有利地表示具有10至30个碳原子的烃基，R12有利地表示具有1至30个碳原子的烃基或亚烃基。
若需要或要求，梳型高聚物可含有衍生自其它单体的单元。
这些梳型高聚物可以为马来酸酐或富马酸或衣康酸与另一种烯属不饱和单体如α-烯烃(包括苯乙烯)或不饱和酯如乙酸乙烯酯的共聚物或富马酸或衣康酸的均聚物。虽然摩尔比例在2至1和1至2范围内是合适的，但优选(不是必须的)可使用等摩尔量共聚单体。可与(例如)马来酸酐共聚的烯烃的例子包括1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯和1-十八碳烯。
梳型高聚物的酸或酸酐基团可通过任何合适的工艺酯化，尽管马来酸酐或富马酸被酯化至少50％是优选的(但不是必须的)。可以使用的醇的例子包括正癸醇-1、正十二醇-1、正十四醇-1、正十六醇-1和正十八醇-1。该醇每个链还可包括至多一个甲基支链，例如1-甲基-十五醇-1或2-甲基-十三醇-1。该醇可以是正醇与单甲基支化的醇的混合物。使用纯醇而非市购的醇混合物是优选的，但若使用混合物，则R12是指烷基基团中的平均碳原子数；若使用在1或2位含支链的醇，则R12为醇的直链骨架片段。
这些梳型高聚物尤其可为富马酸酯或衣康酸酯的聚合物和共聚物，例如EP-A153176、-153177和-225688及WO91/16407中公开的。
特别优选的富马酸酯梳型高聚物是富马酸烷基酯与乙酸乙烯酯的共聚物(其中烷基基团具有12至20个碳原子)，特别是其中烷基基团具有14个碳原子或其中烷基基团为C14/C16烷基基团的混合物的聚合物，所述共聚物通过(例如)共聚富马酸与乙酸乙烯酯的等摩尔混合物并将制得的共聚物与醇或醇(优选直链醇)的混合物反应制备。当使用混合物时，使用1∶1(重量)的正C14和C16醇的混合物是有利的。同时，可有利地使用C14酯与混合C14/C16酯的混合物。在这类混合物中，C14与C14/C16的比例有利地为1∶1至4∶1，优选2∶1至7∶2，更优选约3∶1(重量)。特别优选的梳型高聚物是数均分子量(通过气相渗透压法测定)为1,000至100,000，特别是1,000至30,000的那些聚合物。
其它合适的梳型高聚物为α-烯烃的聚合物和共聚物、苯乙烯与马来酸酐的酯化共聚物以及苯乙烯与富马酸的酯化共聚物；根据本发明可使用两种或多种梳型高聚物的混合物，如上所述，这种用法是有利的。梳型高聚物的其它例子是烃聚合物，例如乙烯与至少一种α-烯烃的共聚物，α-烯烃优选具有至多20个碳原子，例子为正癸烯-1和正十二碳烯-1。这种共聚物的数均分子量通过GPC测定优选至少为30,000。烃共聚物可通过本领域已知的方法、例如使用Ziegler型催化剂制备。
用于改进低温性能的其它添加剂是：
(B)极性含氮化合物。
这些化合物是带有一个或多个、优选两个或多个通式＞NR13的取代基的含氮化合物，其中R13代表含有8至40个碳原子的烃基基团，其中取代基或取代基中的一个或多个可为从其中衍生的阳离子形式，该油溶性极性含氮化合物通常为能够在燃料中起到石蜡晶体生长抑制剂作用的物质，它包括(例如)下列化合物中的一种或多种：
通过至少1摩尔份烃基取代的胺与1摩尔份具有1至4个羧酸基团的烃基酸或其酸酐反应形成的胺盐和/或酰胺，通式＞NR13的取代基是通式-NR13R14的基团，其中R13为前面定义的，R14表示氢或R13，条件是R13和R14可以相同或不同，所述取代基构成化合物的胺盐和/或酰胺基团部分。
可以使用总共含30至300个、优选50至150个碳原子的酯/酰胺。这些含氮化合物描述于US4 211 534中。合适的胺主要为C12至C40伯、仲、叔或季胺或其混合物，但也可以使用较短链的胺，条件是制得的含氮化合物为油溶性的，通常总共含有约30至300个碳原子。含氮化合物优选含至少一个直链C8至C40、优选C14至C24烷基片段。
合适的胺包括伯、仲、叔或季胺，但优选仲胺。叔胺和季胺仅形成胺盐。胺的例子包括十四烷基胺、椰子胺和氢化的动物脂胺。仲胺的例子包括二-十八烷基胺和甲基山萮基胺。
胺混合物如衍生自天然物质的那些胺也是合适的。优选的胺为氢化的仲动物脂胺。衍生自氢化动物脂的烷基基团由约4％C14、31％C14和59％C18组成。
用于制备含氮化合物的合适羧酸和它们的酸酐的例子包括乙二胺四乙酸和基于环骨架的羧酸，例如环己烷-1，2-二羧酸、环己烯-1，2-二羧酸、环戊烷-1，2-二羧酸和萘二羧酸，及1，4-二羧酸(包括二烷基螺双内酯)。这些酸通常在环部分具有约5至13个碳原子。用于本发明的优选酸是苯二酸，如邻苯二甲酸、间苯二甲酸和对苯二甲酸。邻苯二甲酸和其酸酐是特别优选的。特别优选的化合物是通过1摩尔份邻苯二甲酸酐与2摩尔份二氢化动物酯胺反应形成的酰胺-胺盐。另一种优选的化合物是通过使这种酰胺-胺盐脱水形成的二酰胺。
其它例子是长链烷基或亚烷基取代的二羧酸衍生物如取代丁二酸的单酰胺的胺盐，其例子是本领域已知的并描述于(例如)US 4 147 520中。合适的胺可以是上面描述的那些胺。
其它例子为缩合物，例如EP-A-327427中公开的那些缩合物。
(C)含环体系的化合物，在环体系上带有至少两个如下通式的取代基：
     -A-NR15R16其中A为非必要地被一个或多个杂原子间隔的线性或支化链脂族亚烷基基团，R15和R16是相同或不同的，各自独立地为被一个或多个杂原子非必要地隔开的含有9至40个原子的烃基基团，取代基可以相同或不同，化合物可非必要地为其盐形式。有利的是，A具有1至20个碳原子，并优选为亚甲基或多亚甲基基团。这些化合物描述于WO93/04148中。
(D)烃聚合物
合适的烃聚合物的例子是如下通式表示的那些聚合物：
Figure A9519535500151
其中T＝H或R21，其中
R21＝C1至C40的烃基，
U＝H、T或芳基v和w表示摩尔分数，v为1.0至0.0，w为0.0至1.0。
烃聚合物可直接由单烯烃不饱和单体直接制备，或通过氢化多不饱和单体(如异戊二烯和丁二烯)的聚合物间接制备。
烃聚合物的例子公开于WO91/11488中。
优选的共聚物是具有数均分子量至少30,000的乙烯α-烯烃共聚物。α-烯烃优选具有至多28个碳原子。这些烯烃的例子是丙烯、1-丁烯、异丁烯、正辛烯-1、异辛烯-1、正癸烯-1和正十二碳烯-1。该共聚物还可包括少量、例如至多10％(重量)的其它可共聚单体，例如除α-烯烃之外的烯烃和非共轭二烯烃。优选的共聚物是乙烯-丙烯共聚物。
如上所述，乙烯-α-烯烃共聚物的数均分子量通过凝胶渗透色谱(GPC)相对于聚苯乙烯标准测量为至少30,000，有利地为至少60,000，优选至少80,000。虽然在功能上无上限，但分子量高于约150,000时粘度升高，混合困难，优选的分子量为60,000和80,000至120,000。
共聚物有利地具有约50至80％的乙烯摩尔含量，乙烯含量更有利地为57至80％，其含量优选范围为58至73％；更优选62至71％，最优选65至70％。
优选的乙烯-α-烯烃共聚物是乙烯摩尔含量为62至71％、数均分子量为60,000至120,000的乙烯丙烯共聚物；特别优选的共聚物是乙烯摩尔含量为62至71％，数均分子量为80,000至100,000的乙烯-丙烯共聚物。
共聚物可通过本领域已知的任何方法，例如用Ziegler型催化剂制备。聚合物应为基本上无定型的，原因在于高结晶度聚合物在低温下不溶于燃料油中。
其它合适的烃聚合物包括有利地具有数均分子量至多7500、有利地1,000至6,000(通过气相渗透压法测量)、优选2,000至5,000(通过气相渗透压法测量)的低分子量乙烯-α-烯烃共聚物。合适的α-烯烃是如上所述的或苯乙烯，同样丙烯是优选的。尽管可以使用乙烯含量至多86mol％的乙烯-丙烯共聚物，但乙烯含量有利地为60至77mol％。
(E)聚氧亚烷基化合物。例子是聚氧亚烷基酯、醚、酯/醚及其混合物，特别是那些含有至少一个、优选至少两个C10至C30线性烷基基团和分子量至多5,000、优选200至5,000的聚氧亚烷基二醇基团的那些聚氧亚烷基化合物，所述聚氧亚烷基二醇中的烷基基团含有1至4个碳原子。这些物质如EP-A 0 061 895中所述。其它这类添加剂描述于US 4 491 455中。优选的酯、醚或酯/醚为如下通式的那些物质
     R31-O(D)-O-R32其中R31和R32可以是相同或不同的，它们代表：
(a)正烷基-
(b)正烷基-CO-
(c)正烷基-O-CO(CH2)-或
(d)正烷基-O-CO(CH2)x-CO-x为(例如)1至30，烷基基团为线性的并含有10至30个碳原子，D代表其中亚烷基具有1至4个碳原子的二醇的聚亚烷基片段，如基本上线性的聚氧亚甲基、聚氧亚乙基或聚氧三亚甲基部分；可存在一定程度的具有烷基侧链(如聚氧丙二醇中的)的支化，但优选二醇是基本上线性的。D还可含有氮原子。
合适的二醇的例子是具有分子量100至5,000、优选200至2,000的基本上线性的聚乙二醇(PEG)和聚丙二醇(PPG)。酯是优选的，含10至30个碳原子的脂肪酸可用于与二醇反应形成酯添加剂。优选使用C18-C24脂肪酸，特别是山萮酸。这些酯可通过酯化聚乙氧基化的脂肪酸或聚乙氧基化的醇制备。
聚氧亚烷基二酯、二醚、醚/酯和其混合物适合用作添加剂，二酯当还存在少量单醚和单酯(它们经常在制备过程中形成)时对于在窄沸点馏分中使用是优选的。存在大量二烷基化合物是优选的。聚乙二醇、聚丙二醇或聚乙二醇/聚丙二醇混合物的硬脂酸或山萮酸二酯是特别优选的。
聚氧亚烷基的其它例子是描述于日本专利公开No.2-51477和3-34790中的那些化合物。酯化的烷氧基化胺描述于EP-A117,108和EP-A-326,356中。
在本发明范围内可有利地使用两种或更多种选自上述一种或多种不同类型的辅助流动性改进剂。
可有利地使用的辅助流动性改进剂比例按燃料的重量计为0.01％至1％，有利地为0.05％至0.5％，优选0.075至0.25％(重量)。
本发明的流动性改进剂组合物还可与一种或多种(例如)本领域已知的其它共添加剂组合使用，这些添加剂的例子如下：洗涤剂、颗粒辐射抑制剂、贮存稳定剂、抗氧剂、腐蚀抑制剂、消雾剂、抗乳化剂、消泡剂、十六烷值增进剂、助溶剂、封装相容剂和润滑添加剂。
本发明的油，特别是燃料油组合物按燃料重量计有利地含有0.0005％至1％、有利地0.001至0.1％、优选0.02至0.06％(重量)比例的本发明三元共聚物。在本发明特别适用的高石蜡燃料油中，该比例按燃料油的总重量计有利地为0.025至0.2％、优选约0.04％(重量)。
本发明的添加剂母料在油中或与油混溶的溶剂中有利地含有3至75％、优选10至65％的组合物或三元共聚物。
下列实施例用于说明本发明，其中所有份数和百分数都按重量计，数均分子量(Mn)通过凝胶渗透色谱以聚苯乙烯为标准进行测量。实施例1至4-制备三元共聚物实施例1
在一高压釜中加入782ml(610g)环己烷、190ml(168g)辛酸乙烯酯(VnO)和10ml(9g)乙酸乙烯酯(VAC)。将此反应器用乙烯加压至9.7MPa并将溶液的温度升至123℃，在整个反应中保持此压力和温度。将453ml辛酸乙烯酯和24ml乙酸乙烯酯在75分钟内注入高压釜中，同时加入溶于58.2ml环己烷中的9.1ml过-2-乙基己酸叔丁酯。在加料结束后将反应器在123℃保持10分钟，并从高压釜中倒出反应混合物。将未反应的单体和溶剂经真空蒸馏除去。得到450g不透明的粘稠聚合物。
另一些三元共聚物按上述一般步骤制备，变化单体比例制得表中所列的聚合物。三元共聚物可含有一些残余单体。
                              表1
  实施例  CH3/100CH2     Mn   VnO mol％   VAC mol％
    1234     5.0*5.2*5.0*2.91     ---3865     13.314.614.214.0     1.81.71.71.54
*未进行末端甲基基团校正-未测量。比较例1至4
在这些比较例中，用实施例1中描述的反应条件制备乙烯-辛酸乙烯酯、乙烯-2-乙基己酸乙烯酯和乙烯-乙酸乙烯酯-2-乙基己酸乙烯酯共聚物并列于下表2中。
                          表2
    比较例    温度℃ CH3/100CH2    Mn   VnO   VAC     V2EH
      123     123123115     2.84.64.0   495035104030    -12.6-    --1.2     11.7-12.8
此外，为了对比，使用具有11.9mol％VA、Mn3000、CH3/100CH23.3的市购乙烯-乙酸乙烯酯共聚物作为比较例4。
在下列实施例中，使用具有表3中给出的特性的燃料油。燃料的CFPP按“石油会志(Journal of Institute of Petroleum)”，52(1966)，173中的描述测量。
                             表3
浊点，℃CFPP，℃IBP，℃FBP，℃90-20℃FBP-90℃在低于浊点10℃时的石蜡含量，wt％   燃料油1-6-815436180313.4   燃料油2-3-4174369110262
实施例5和比较例5测试油组合物-对CFPP的影响
在这些实施例中，测量本发明第一方面的油组合物的CFPP。
实施例5的油组合物含有实施例4的三元共聚物。比较例5含有作为流动性改进剂组合物的乙烯-乙酸乙烯酯共聚物(比较例4)。添加剂以所示的总活性组分处理比例使用，例如，若所示的处理比例为100ppm，则添加剂以100ppm活性组分处理比例使用。
结果列于下表4中。各实施例为至少两个实验的平均值。
                         表4
处理比例，ppm   实施例 三元共聚物的实施例                    CFPP，℃
                    燃料油
     1400     2100
    -5     -4      -8-17     -4-5
比较例5 比较例4     -11     -16.5
结果证明，仅三元共聚物在较高石蜡含量的燃料1中的有效性和其在较低石蜡含量的燃料油2中效果较差。

Claims (11)

1.一种油组合物，它包括在低于浊点10℃时具有至少3％(重量)石蜡含量的油和含有油溶性乙烯三元共聚物的流动性改进剂组合物，所述三元共聚物除衍生自乙烯的单元外，还具有如下通式的单元
Figure A9519535500021
和如下通式的单元
Figure A9519535500022
其中R1和R2可以是相同或不同的，各自代表H或甲基，R3代表含至多4个碳原子的烷基，R4代表具有3至15个碳原子的直链烷基，R3和R4是不同的；通过质子NMR谱测量的该三元共聚物的支化程度低于每100个CH2单元6个CH3基团。
2.如权利要求1的组合物，其中R1和R2各自代表氢，R3代表甲基。
3.如权利要求1或2的组合物，其中R4代表正庚基。
4.如权利要求1至3任何一项的组合物，其中三元共聚物的数均分子量Mn通过凝胶渗透色谱测量为至多20,000。
5.如前述权利要求任何一项的组合物，其中单元I和II的总摩尔比例为10至25％，Mn为3,000至6,000。
6.如权利要求1至4任何一项的组合物，其中单元I和II的总摩尔比例为3.5至7mol％，Mn为3,000至10,000。
7.如权利要求1至6任何一项的组合物，其中油为燃料油，并且其中流动性改进剂组合物的存在比例按燃料油的重量计为0.025至0.2％。
8.如权利要求7的组合物，其中燃料油的石蜡含量在低于浊点10℃时为3.3至6％(重量)。
9.一种添加剂母料，包括权利要求1至6任何一项中限定的流动性改进剂组合物和油或可与油混溶的溶剂。
10.如权利要求1至8的油组合物或权利要求9的母料，其中流动性改进剂组合物还包括乙烯-不饱和酯共聚物。
11.权利要求1至6或10任何一项限定的流动性改进剂组合物用于改进低于浊点10℃时石蜡含量至少3wt％的油的低温性能的用途。
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