CN1081692A - 油品添加剂及其组合物 - Google Patents

油品添加剂及其组合物 Download PDF

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Publication number
CN1081692A
CN1081692A CN93107715A CN93107715A CN1081692A CN 1081692 A CN1081692 A CN 1081692A CN 93107715 A CN93107715 A CN 93107715A CN 93107715 A CN93107715 A CN 93107715A CN 1081692 A CN1081692 A CN 1081692A
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application
oil
composition
polymkeric substance
alkyl
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CN1092217C (zh
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B·W·戴维斯
T·伊布拉海姆
D·G·戈伯汉
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Abstract

用含有乙烯与至少三个碳原子的羧酸之不饱和 醇酯的共聚物构成的组合物来改进燃料油的低温性 质。

Description

本发明涉及油品组合物，主要是燃料油组合物，特别是在低温下易生成蜡的燃料油组合物，并涉及在这类油品组合物中使用添加剂组合物以改进其低温性质。
取暖用油及其他石油馏份燃料，比如柴油，含有烷烃，低温下烷烃趋向于沉出大的蜡结晶，以致于形成使燃料失去其流动能力的胶冻结构。燃料仍能流动的最低温度叫倾点。
随着燃料温度降低并接近其倾点，用管线及泵输送燃料就发生了困难。蜡结晶倾向于在其倾点温度之上就堵塞燃料管线、滤网和过滤器，实践中人们认识到这些问题。已建议用各种添加剂降低油的倾点，其中许多已在工业上应用。类似地，还提出用其他添加剂，而且实际上已用了这些添加剂，来减小已形成的蜡结晶的大小和改变其形状。人们希望结晶颗粒较小，因小结晶不大可能堵塞过滤器。某些添加剂能抑制蜡结晶成片状而使其成为针状，所产生的针状结晶比片状更易通过过滤器。添加剂还可具有将生成的结晶以悬浮状态保持在燃料油中的作用，沉淀减少的结果也有助于防止堵塞。
有效的蜡结晶改进作用（可用冷滤点和其他适用性试验以及模拟和现场试验来测量）可用乙烯-醋酸或丙酸乙烯酯共聚物（EVAC或EVPC）为基础的流动性改进剂来实现。用于本说明书的冷滤点CFPP可用（石油学会杂志）“Journal  of  the  Institute  of  Petroleum”52（1966），173中记述的方法测量。
EP-A-45342中记述了一种低温流动性改进剂，该剂以用2-乙基己酸、丙烯酸和邻苯二甲酸酯化改进的EVAC为基础。
M.Ratsch  b.M，Gebauer在“Wissenschaft  und  Te  Chnik”42（6），238（1989）中记述了低温流动性改进剂，其中包括特别是用正-己酸酯化的EVAC。
U.S.P.3961916记述了中间馏份流动性改进剂，它由蜡生长制止剂及成核剂构成，前者最好是一种较低分子量的乙烯-乙烯酯共聚物而且酯含量较高，后者最好是分子量较高酯含量较低的共聚物。二者的酯最好是，但也不一定必须是醋酸乙烯酯。
DE-AS-2407158中记述了中间馏份油流动性改进剂，它由低分子量的乙烯-乙烯酸和乙烯-丙烯酸酯两种共聚物的混合物构成，二者的酯组份至少都是40%（摩尔）。
然而已经证明，处理某些油以降低它们的冷滤点是困难的，特别是那些蜡含量高，譬如超过2.5%（在浊点以下10℃测量），更特别的是高于2.9%，尤其是蜡含量3.0%或更高的油。特别困难的是那些得自高蜡含量原油而终馏点又低比如最高370℃，尤其是最高360℃的燃料。
本专利提供一种油品特别是燃料油添加剂来有效地改进高蜡含量油的低温流动性，这是基于观察到，对于这样的油品来说，某些乙烯与不饱和酯的共聚物是比过去建议的组合物更有效的低温流动性改进剂。
首先，本发明提供了使用一种油溶性乙烯共聚物来改进在浊点下10℃用差示扫描量热法测量的含蜡量最少2.5%（重）的油的低温性能，该共聚物除了乙烯衍生的单元外还含有下式的单元：
-CH2CROOCR′-或-CH2CRCOOR′- （Ⅰ）
其中R代表H或CH3，R1代表含有至少2个碳原子的烃基。
其次，本发明提供了一种组合物，它由在浊点下10℃用差示扫描量热法测得蜡含量至少2.5%的油和少量除乙烯衍生的单元外还含有上述式Ⅰ的单元的乙烯共聚物构成。
本发明特别适用于蜡含量最低2.9%（重）的油，尤其适用于蜡含量至少3.0%（重）的油。本发明还特别用于终馏点达370℃，尤其是终馏点达360℃的油品。
式Ⅰ在乙烯共聚物中的克分子分数可达35%是有益的。在本发明的一个实施方案中，该克分子分数是1-25%，优选的是10-20%，最优选的是11-16%。在此实施方案中，用凝胶渗透色谱法测定的共聚物的数均分子量最高为14000，特别是在1400-7000的范围内，优选的是2000-5500，最优选的是约4000。
在第二个实施方案中，该聚合物按照本发明可含多至10%摩尔），优选的是1-7.5%（摩尔）的酯单元，其数均分子量可达20000，最好是3000-10000。
聚合物的线性度为1-15是有益的，线性度用氢谱核磁共振测量，用每100个亚甲基单元中的甲基单元数来表示。
用于本说明书中的术语“烃基”代表具有与分子其他部份直接相连的碳原子并具有烃或主要是烃特性的基团。此处可提及的烃基团中包括：脂肪基（例如烷基或烯基）、脂环基（例如环烷基或环烯基）、芳香基、脂肪基或脂环基取代的芳香基和芳香基取代的脂肪基和脂环基。脂肪基宜是饱和的。这些基还可含有非烃取代基，若它们的存在不改变具有压倒优势的烃特性的话。其例子包括酮基、卤素、羟基、硝基、腈基、烷氧基和酰基。若烃基是取代的，则最好是单取代，取代烃基的例子包括2-羟乙基、3-羟丙基、4-羟丁基、2-酮丙基、乙氧乙基和丙氧丙基。这些基团还可在原由碳原子组成的链或环中含有非碳原子，合适的杂原子包括：譬如氮、硫和最好是氧。烃基至多含30个，优选者最多15个，更优选者最多10个，最优选者最多8个碳原子，而且烃基最少含3个碳原子。
R最好代表H，R1可代表烯基或如上所述最好代表线性烷基。若烷基或烯基是分支的，例如在2-乙基己基中，其α-碳原子最好是亚甲基的一部份。烷基或烯基含至多29个碳原子，优选的是2-14个碳原子，更优选的是3-9个尤其是3-7个碳原子。此处可提及的烷基或烯基的例子是：丙基、正-丁基、异丁基，以及戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基和二十烷基的异构体，最好是其线性异构体，还有它们相应的烯基，最好是烷基一端烯基。R1最好是代表戊基或己基，而且如上所述最好是线性异构体。
此处可提及的环烷基、烷基芳基和芳基的例子是环己基、苄基和苯基。
式Ⅰ的单元最好是式-CH2CROOCR1-单元。
共聚物也可含不同于以上提到的单元，例如式
-CH2-CRR2- Ⅱ
或式 -CCH3（CH2R3）-CHR4Ⅲ
代表的单元，其中R2代表-OH，R3和R4分别独立地代表氢或高达4个碳原子的烷基，单元Ⅲ最好是由异丁烯、2-甲基丁烯-2或2-甲基戊烯-2衍生的。
式Ⅰ单元可以是端单元，但更好是内单元。
用一种含有不同Ⅰ型单元的聚合物或两种或更多聚合物的混合物都在本专利的范围内。
油可以是一种润滑油，包括动物油、植物油或矿物油，例如从石脑油或绽子油到SAE30，40或50级的润滑油的石油馏份油，蓖麻油，鱼油或氧化矿油。根据其用途，这类油可含添加剂，诸如粘度指数改进剂（如乙烯-丙烯共聚物）丁二酸基分散剂，含金属的清净剂和二烷基二硫代磷酸锌抗磨添加剂。本发明的组合物可适用于在润滑油中作流动性改进剂、降凝剂或脱蜡助剂。
该油可以是原油或燃料油，特别是中间馏份燃料油。燃料油可包括常、减石馏份油，或裂化瓦斯油，或以任何比例调和的直馏和热裂化和/或催化裂化馏份油。最常见的石油馏份燃料是：煤油、喷气燃料、柴油、取暖用油和重质燃料油。取暖用油可为常压直馏馏份，或含少量，譬如至多35%（重）的减压瓦斯油或裂化瓦斯油或二者都有。柴油和取暖用油最常发生上述低温流动性问题。本发明也可应用于植物油基的燃料油，例如菜子油。
各种添加剂在室温下应至少以1000ppm的重量份数溶于1份重量的油。然而，至少某些添加剂可在油的浊点附近从油中析出，起改变形成的蜡结晶的作用。
乙烯共聚物可由任何已知工艺方法制备，例如可用自由基引发的溶液聚合，或用在压热釜或管式反应器中很方便进行的高压聚合来制备。
共聚物可选用而且最好选用皂化和再酯化乙烯-乙烯酯共聚物的方法来制备。
若进入的酸或醇挥发性比拟除去者低时，另一制备共聚物的方法是转移酯化。
或愿意，所有的或基本上所有的已存在的酯基都可被水解并完全被所期望的链取代基所代替。也可将一部份水解，结果得到的聚合物含醋酸酯侧链又含更长的侧链。
该添加剂组合物和油组合物可含其他改进低温性质和/或其他性质的添加剂，其中许多已得到应用或已有文献报导。
例如，该组合物也可含另一种乙烯-乙烯酯共聚物。如上所述并参考U.S.P.3961916，流动性改进剂组合物可包含蜡生长制止剂及成核剂。本申请人不想局限于任何理论，但相信若本发明的添加剂共聚物含有高于7.5%（摩尔）的酯单元，它们基本上起制止剂的作用，而且加入成核剂是有利的，成核剂譬如是乙烯-乙烯酯，特别是乙烯-醋酸乙烯酯，其数均分子量在1200-20000范围内，乙烯酯含量0.3-12%（摩尔），最好是其酯含量比上述确定的乙烯酯共聚物的酯含量低，优选的是低2%（摩尔），更优选的是低3%（摩尔）。
然而若本发明的共聚物含有少于10%（摩尔）的酯单元，则它基本上起成核剂的作用，而且加入具有相应的较低分子量和较高酯含量的乙烯/不饱和酯共聚物作为制止剂是有利的。
按照本发明，当然要使用其结构都是含上述Ⅰ单元的共聚物作制止剂和成核剂。
添加剂组合物也含有一种梳状聚合物。这类聚合物在N.A.Plate′和V.P.Shibaev，的“梳状聚合物，结构和性能”J.Poly.Sci.Macromolecular  Revs.，8，p117-253（1974）中有所记述。
该梳状聚合物最好是一具有至少6，最好是10个原子侧链的均聚物，或至少25%（摩尔），优选的是至少40%（摩尔），更优选的是至少50%（摩尔）的单元具有上述侧链的共聚物。
此处提出具有以下通式的梳状聚合物可作为该梳状聚合物的例子。
Figure 93107715X_IMG2
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，
K＝H、COOR12、OCOR12、COOR12、或COOH
L＝H、R12、COOR12、OCOR12、COOH或芳基
R11≥C10烃基，最好是C10-C30烷基。
R12≥C1烃基，最好是C1-C30烃基。
m、n代表摩尔比，m为1.0-0.4，n为0-0.6。
根据希望或要求，该梳状聚合物可含从其他单体衍生的单元。含两种或更多的不同梳状共聚物也包括在本发明范围内。
这些梳状聚合物可以是马来酸酐或富马来酸与另一种乙烯属不饱和单体（例如α-烯烃）或一种不饱和酯（如醋酸乙烯酯）的共聚物。最好是但不一定必须使用等摩尔量的共聚单体，尽管摩尔比在2∶1-1∶2范围内都是适用的。可与马来酸酐等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。
共聚物可用任何合适的技术酯化，最好但不一定至少将50%的马来酸酐或富马酸酯化。可用的醇的例子包括：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。醇亦可在每个链上含-甲基支链，例如1-甲基十五醇-1，2-甲基十三醇-1。也可以是正构醇及单甲基侧链醇的混合物。最好用纯的醇而不是市售混合醇，若用混合醇，则R12代表烷基中的平均碳数，若用在1或2位带有支链的醇，则R12代表该醇的直链骨架段。
这些梳状聚合物可以特别是富马酸酯式衣康酸酯的聚合物及诸如在欧洲专利申请153176、153177和225688以及WO91/16407中所记述的那些共聚物。
专门优选的富马酸酯梳状聚合物是含12-20个碳原子的烷基富马酸酯与醋酯乙烯酯的共聚物，特别是具有14个碳原子的烷基或14/16个碳原子的烷基混合物的富马酸酯与醋酸乙烯酯的共聚物，这些共聚物是由等摩尔的富马酸和醋酸乙烯酯通过溶液共聚，然后将产生的共聚物与最好是直链的醇或其混合物反应制备的。当用混合醇时，最好是正十四醇与十六醇的1∶1（重）混合物。更有甚者，可用C14酯与混合C14/C16酯的混合物。在这些混合物中，C14与C14/C16的重量比最好在1∶1-4∶1范围内，优选的是2∶1-7∶2，更优选的是约3∶1。
其他适用的梳状聚合物是α-烯烃的聚合物共聚物和苯乙烯和马来酸酐的酯化共聚物，及苯乙烯和富马酸的酯化共聚物;如上所述，按照本发明可使用两种或多种梳状聚合物的混合物，这使用可能是有利的。
该添加剂组合物还可含极性含氮化合物，例如在U.S.P.4211534中记述的那些化合物，尤其是邻苯二甲酸酐或邻磺基苯甲酸酐与两摩尔的氢化牛脂胺的酰胺一胺盐。
本发明的添加剂组合物还可含有乙烯与至少一种α-烯烃构成的共聚物，其数均分子量至少30000。最好该α-烯含至多20个碳原子。这类烯烃的例子是丙烯、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。共聚物也可含少量譬如直到10%（重）的其他可共聚的单体，例如非α-烯烃和非共轭双烯。优选的共聚物是乙烯-丙烯共聚物。含有两种或更多不同的这类乙烯-α-烯烃共聚物也包括在本发明的范围内。
如上所述，乙烯-α-烯烃共聚物的数均分子量至少30000（由凝胶渗透色谱GPC测定，相对于标准聚苯乙烯），最好至少60000，优选的是至少80，000。从性能上讲并无上限，但分子量高于约150000时粘度的增加会造成难于混合，故优选的分子量范围是60000和80000至120000。
共聚物的乙烯含量在50-85%（摩尔）是有益的，更有益的是57-80%（摩尔），优选的是58-73%（摩尔）。更优选的是62-71%（摩尔），最优选的是65-70%（摩尔）。
优选的乙烯-α-烯共聚物是乙烯摩尔含量为62-71%，数均分子量60000-120000的乙烯-丙烯共聚物，特别优选的共聚物是乙烯含量为62-71%，分子量为80，000-100，000的乙烯-丙烯共聚物。
共聚物可用任何已知的工艺方法制备，譬如用Zieglar催化剂。聚合物应是基本上无定形的，因为高度结晶的聚合物在低温下相对说不溶于燃料油。
添加剂组合物还可含有其他乙烯-α-烯共聚物，该共聚物的数均分子量最大7500，最好是1000-6000，优选的是2000-5000，数均分子量由汽相渗透压法测定。适当的α-烯上文已给出，或为苯乙烯，但丙烯仍是优选的。乙烯含量应为60-77%（摩尔），尽管对于乙烯-丙烯共聚物来说高达86%（摩尔）的乙烯也可用得较好。
该组合物也可含聚乙二醇酯，最好其脂肪酸链含18-22个碳原子。
此外，燃料组合物可含其他用途的添加剂，例如减少废气微粒排放或抑制贮存期间变色和生成沉淀的添加剂。
本发明的燃料油组合物可含总量为燃料重量的0.0005-1%，最好是0.001-0.1%，优选的是0.04-0.06%的本发明的共聚物。
以下的实施例对本发明加以说明，其中所有的份数及百分数都以重量计，数均分子量是用凝胶渗透色谱测定的。
实施例A
将10公斤（3.33摩尔）含35%（重）醋酸乙烯、数均分子量3000，支链度为4CH3/100CH2的乙烯-醋酸乙烯酯共聚物加入装有冷凝管的烧瓶中并在搅拌和氮保护下加热到60℃，小心地向聚合物中加入216克（4摩尔）甲醇钠于1.5升正-丁醇中之溶液，随后再加入4升正-丁醇。溶液从清亮变橙，温度降至46℃，再将混合物加热到90℃，颜色变为深红，在此温度下保持并搅拌2小时。
将反应混合物在370mmHg下加热到104℃以蒸出约4升的醋酸丁酯，将剩下的粘性聚合物在90℃下倒入用150毫升36%的盐酸酸化的由100升水和5升丙酮组成的溶剂中。将溶液搅拌3小时，在pH6下沉降过夜沉出固体，上层倒掉后将聚合物通过细筛布过滤并于70℃干燥。
20克产生的聚合物（数均分子量3300，用核磁法测定85%水解），溶于100毫升甲苯与10毫升吡啶的无水混合物中，滴加30毫升月桂酰氯溶于100毫升甲苯的溶液，在室温下搅拌1小时。滤出所产生的固定，减压脱溶剂，得到一粘性聚合物，在120℃下进一步真空干燥以除去挥发性物后得21克聚合物，其中R1代表正-十一基，产量21克，数均分子量5000。
实施例B
重复实施例A的第二部分，但用肉豆冠酰氯酯化50克皂化的聚合物，得到40克数均分子量5000的聚合物，其中R1代表正-十三烷基。
实施例C
重复实施例A的第二部份，但用己酰氯酯化，得到数均分子量为3700的聚合物，其中R1代表正-戊基。
实施例D
重复实施例A的第一部分的步骤，用47.5克甲氧基钠及总量为250克的正-丁醇皂化450克醋酸乙烯含量13.5（重），数均分子量5000，支链度为6CH3/100CH2的乙烯-醋酸乙烯酯共聚物。
将50克得到的聚合物（数均分子量4000，93%水解）溶于375毫升甲苯与8毫升吡啶构成的无水混合溶剂中。滴加14毫升己酰氯/250毫升甲苯，在室温下搅拌所得的混合物5小时，滤出固体并真空脱溶剂，得到粘性聚合物，再进一步在120℃真空干燥得到38克Mn＝4000的聚合物，其中R1代表正-戊基。
实施例E
重复实施例A中第一部份的步骤，用19.3克甲氧基钠和90克正-丁醇皂化100克含29%（重）的醋酸乙烯酯，数均分子量为3300，支链度为4CH3/100CH2的乙烯-醋酸乙烯共聚物。产量74克，数均分子量3000，93%水解。
20克得到的皂化聚合物室温下溶于由150毫升甲苯及6毫升吡啶构成的无水溶剂中，滴加10毫升己酰氯/100毫升甲苯，并在室温下将反应混合物搅拌5小时。产物按实施例C的方法干燥。得到20克类似的聚合物。
实施例F
重复实施例C的步骤，但用正-庚酰氯再酯化其皂化产物。
实施例G
重复实施例C的步骤，但皂化产物用正-辛酰氯再酯化。
实施例H
向3升搅拌在热釜中投入636克环己烷、148.5克丁酸乙烯酯和足够的乙烯，使其在124℃时压力达97巴（9.7MPa）。将18克过辛酸叔丁酯溶于85毫升环己烷中量入压热釜，并再加入351克丁酸乙烯酯和乙烯以在上述压力下保持75分钟。在浸湿10分钟后，将反应容器用二甲苯冲洗。溶剂蒸发后回收992克乙烯-丁酸乙烯酯共聚物，其丁酸乙烯含量为36%，Mn＝2400。
实施例J
含醋酸乙烯酯、异丁烯、乙烯和500ppm过辛酸叔丁酯的混合物在压热釜中于1200巴、220℃聚合。得到乙烯/醋酸乙烯/异丁烯三元共聚物，其醋酸乙烯含量为13.5%（重），异丁烯含量为7.8%（重），9.3CH3/100CH2（NMR法），Mn＝5450。
实施例K
将100克含36%（重）醋酸乙烯数均分子量为3300支链度为4CH3/100CH2的乙烯-醋酸乙烯共聚物加入装有搅拌器、与加热控制器相连的热电偶、氮气入口和蒸馏用冷凝管的烧瓶中并加热到60℃加入66.46克（摩尔当量）的辛酸甲酯和2.268克甲氧基钠（0.1摩尔当量，作为催化剂），将混合物加热到80℃，15分钟后再加热到120℃并保持在该温度，在蒸馏瓶中能收集到清亮的馏出物。每一定时间间隔取一次聚合物样，通过对比红外谱图中1240cm-1峰（醋酸酯峰）及1170cm-1峰（辛酸酯峰）的高度来跟踪转移酯化的进程。三个半小时后置换了79%的醋酸酯并得到11克馏出物。反应在120℃再继续5小时，此时已有92%的醋酸酯发生了转移酯化，在120℃又反应4小时后，总馏出物18.2克，得到产物122克，转移酯化率94%，数均分子量4250。
下列燃料被用于以下实施例中记述的试验。
Figure 93107715X_IMG3
实施例1
实施例E的产物（以下称为“产物”）用于上表列出的头10种燃料油的每一种，其用量适合于每种燃料。将加有产物的每种燃料的冷滤点与加有同样剂量的在以上实施例中用作起始物质的乙烯-醋酸乙烯酯共聚物（以下叫作EVA）后燃料的冷滤点进行对比。
燃料 蜡含量％ 添加剂ppm 冷滤点，℃
产物 EVA
12345678910 2.43.43.13.12.92.32.32.03.13.0 30030010020020010050100100400 -13-11-16-12-18-18-20-15-16-15 -15-11-14-6-17-11-24-15-12-12
可以看出，对低蜡燃料（1＃、6＃、7＃和8＃）本发明的共聚物，其中R1代表正-戊基，一般说不比相应的作为市售低温流动性改进剂的乙烯-醋酸乙烯共聚物更有效;相反地在多数高蜡含量的燃料中，本发明的共聚物则显示出比市售品的明显的优势，而且没有比其低效的情况发生。
实施例2
实施例C的产物（以下以产物代表）用于燃料11＃和12＃，添加量为250ppm，将燃料的冷滤点与在同样燃料中加有250ppm在实施例C中用作起始物质的乙烯-醋酸乙烯共聚物（以下以EVA代表）之结果进行对比。
Figure 93107715X_IMG4
实施例3
将类似于实施例C但用辛酸再酯化的产物（以下代之以产物）以300ppm的剂量用于燃料2＃试验。将加剂燃料的冷滤点与加有同样剂量的起始共聚物（以下称为EVA）的同一燃料之冷滤点进行对比。
燃料  蜡含量,%  冷滤点,℃
产物  EVA
2  3.4  -17  -12
实施例4
将类似于实施例C但用庚酸再酯化的产物（以下称为产物）加入燃料13中，将其冷滤点与含有初始共聚物（EVA）的同一燃料的冷滤点进行对比，二者的添加剂量均为100ppm。
燃料  蜡含量,%  冷滤点,℃
产物  EVA
13  3.5  -11  -4
实施例5
在此实施例中，将含有约5%（摩尔）己酸酯单元的实施例D的产物与含有约15%（摩尔）己酸酯单元的实施例C的产物相混合，其中实施例C的产物占混合物的14%，其余是实施例D的产物。以下将此混合物叫作产物。将含有适当浓度的混合聚合物的各种高蜡燃料的冷滤点与含同样浓度同样比率的初始乙烯-醋酸乙烯共聚物的混合物的燃油冷滤点进行对比，对比的混合物称之为EVAs。
Figure 93107715X_IMG5

Claims (31)

1、使用一种油溶性除乙烯衍生的单元外还含有下式单元的乙烯共聚物来改进浊点以下10℃时蜡含量不低于2.5%(重)的油的低温性质，
-CH2CROOCR1-或-CH2CRCOOR1-Ⅰ
其中R代表H或CH3，R1代表至少有两个碳原子的烃基。
2、按照权利要求1中的应用，其中R1代表烷基。
3、按照权利要求2中的应用，其中烷基是线性的。
4、按照权利要求1-3中任何一项的应用，其中R1含3-9个碳原子。
5、按照权利要求1-4中任何一项的应用，其中R代表H。
6、按照权利要求1-5中任何一项的应用，其中聚合物的数均分子量Mn最多是14000，式I的单元最多聚合物的35%（摩尔）。
7、按照权利要求6中的应用，其中数均分子量在2000-5500范围内。
8、按照权利要求6或7的应用，其中式Ⅰ单元占共聚物的11-16%（摩尔）。
9、按照权利要求1-5中的任何一项的应用，其中聚合物的数均分子量最多是20000，式Ⅰ的单元最多为聚合物的10%（摩尔）。
10、按照权利要求9的应用，其中Mn在3000-10000范围内。
11、按照权利要求9或10的应用，其中式Ⅰ单元占聚合物的1.0-7.5%（摩尔）。
12、按照权利要求1-11中的任何一项的应用，其中聚合物是由乙烯-乙烯酯共聚物经皂化和再酯化制备的。
13、按照权利要求1-11中的任何一项的应用，其中聚合物是由乙烯-醋酸乙烯酯共聚物经皂化和再酯化制备的。
14、按照权利要求1-13中的任何一项的应用，其中油是中间馏份燃料油。
15、按照权利要求1-14中的任何一项的应用，其中油的蜡含量不低于2.9%。
16、按照权利要求1-15中的任何一项的应用，其中也用一种梳状聚合物。
17、按照权利要求16的应用，其中梳状聚合物有如下的通式：
其中：D＝R、COOR11、OCOR、R12COOR11或OR11，
E＝H、CH3、D或R12，
G＝H或D，
J＝H、R12、R12COOR11或芳基或杂环基，
K＝H、COOR2、OCOR12、OR12或COOH，
L＝H、R2、COOR2、OCOR2、COOH或芳基，
R11≥C10烃基，
R12≥C1烃基，
m.n.代表摩尔比，n为1.0-0.4，n为0-0.6。
18、按照权利要求16或17的应用，其中梳状聚合物是醋酸乙烯酯与富马酸酯的共聚物。
19、按照权利要求18的应用，其中富马酸酯的酯基是12-20个碳原子的烷基。
20、按照权利要求19的应用，其中酯基是由14碳醇或14/16碳醇的混合物衍生的。
21、按照权利要求1-15中的任何一项的应用，其中使用了两种或多种不同梳状聚合物的混合物。
22、按照权利要求16的应用，其中混合物由（ⅰ）C14的富马酸酯-醋酸乙烯酯的共聚物和（ⅱ）C14/C16的富马酸酯-醋酸乙烯酯的共聚物组成。
23、按照权利要求1-22中的任何一项的应用，其中也使用了极性含氮化合物。
24、按照权利要求1中的应用，其中实质上系在任何编号的实施例中所记述的。
25、一种由在浊点以下10℃测得的蜡含量不低于2.5%的油及少量除乙烯衍生的单元外还含有权利要求1中所确定的式Ⅰ单元的乙烯共聚物构成的组合物。
26、按照权利要求25中的组合物，其中它含有总量为油重0.005-1%的添加剂组合物。
27、按照权利要求25中的组合物，其中它含有总量为油重0.001-0.1%的添加剂。
28、按照权利婪25中的组合物，其中它含有总量为油重0.004-0.06%的添加剂。
29、按照权利要求25-28中的任何一项的组合物，其中它含有权利要求2-23中的任何一项所确定的添加剂。
30、按照权利要求25中的组合物，其中它实质上是在任何一个编号的实施例中所记述的组合物。
31、本文所记述的任何新特性，或本文所记述的任何特性的新的组合。
CN93107715A 1992-06-30 1993-06-29 油品添加剂的用途及其组合物 Expired - Lifetime CN1092217C (zh)

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EP0649456A1 (en) 1995-04-26
AU4561293A (en) 1994-01-24
CA2137229C (en) 2004-06-08
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