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CN1085226C - 燃料油组合物 - Google Patents

燃料油组合物 Download PDF

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Publication number
CN1085226C
CN1085226C CN93107717A CN93107717A CN1085226C CN 1085226 C CN1085226 C CN 1085226C CN 93107717 A CN93107717 A CN 93107717A CN 93107717 A CN93107717 A CN 93107717A CN 1085226 C CN1085226 C CN 1085226C
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China
Prior art keywords
composition
multipolymer
oil
alkyl
ester
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Expired - Lifetime
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CN93107717A
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English (en)
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CN1081694A (zh
Inventor
R·J·布罗德
B·W·戴维斯
T·伊布拉海姆
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Abstract

包括(a)一种乙烯一混合不饱和酯共聚物或(b)两种或多种例如在其酯链上不同的，乙烯一不饱和酯共聚物的组合物，用来改进燃料油的低温性能。

Description

燃料油组合物
本发明涉及油的组合物，首先涉及燃料油组合物，尤其涉及在低温下易于成蜡的燃料油组合物，以及涉及用于此类燃料油组合物的添加剂组合物。
燃料油和其它馏出石油燃料，例如柴油，包含烷烃类，该烷烃在低温下趋向于沉淀形成蜡状大结晶，这样就形成凝胶结构，从而使燃料失去流动能力。燃料仍然能够流动的最低温度，公知是倾点。
当燃料的温度降低并接近于倾点时，通过管道和泵输送燃料出现团难。此外，蜡状结晶在略高于倾点的温度易堵塞燃料管道、筛网和过滤器。这些问题在现有技术中已被充分认识到，并推荐了各种添加剂(许多已在商业上使用)用于降低燃料油的倾点。同样地，已推荐了其它添加剂(在商业上已使用)用于减小所形成的蜡状结晶的尺寸和改变蜡状结晶的形状。较小尺寸的结晶是希望有的，因为它们不太可能阻塞过滤器。某些添加剂阻止蜡状物结晶成片晶，而是使它采取针状晶形，所得到的针晶比片晶更有可能通过过滤器。添加剂也可具有保持所形成的结晶在燃料中为悬浮状态的作用，结果是减少沉降，还有助于防止胆滞现象。
有效的蜡状结晶改性(由CFPP和其它可操作的试验，以及模拟的和现场进行的操作测定)可通过基于乙烯-乙酸乙烯酯或丙酸乙烯酯共聚物(EVAC或EVPC)的流动促进剂而实现。
在EP-A-45342中描述了一种冷流动添加剂，它是基于一种通过与2-乙基己酸、丙烯酸和苯二甲酸进行酯化反应而改性的EVAC。
在“Wissenschaft und Technik”42(6)，238(1989)，M.Ratsch & M.Gebauer中描述了包括一种特别是被正己酸酯化的EVAC的冷流动添加剂。
在美国专利No.3961，916中，描述了柴油流动促进剂，它包括一种蜡增长抑止剂和一种成核剂，前者优选一种具有较高酯含量的较低分子量乙烯-乙烯基酯共聚物，后者优选一种具有较低酯含量的较高分子量共聚物，这些酯类优选，但不是必需的，都是乙酸乙烯酯。
在DE——AS——2407158中，描述了柴油流动促进剂，它包括一种低分子量乙烯-乙烯基酯和乙烯-丙烯酸酯共聚物的混合物，两者都包含至少40％(摩尔)酯组分。
本发明涉及提供一种油(尤其一种燃料油)的添加剂，它能有效地促进这种油的低温流动，本发明基于这样的观察：一种包括至少两种不同的乙烯与不饱和酯的共聚物的组合物，或一种包括乙烯与至少两种不同类型酯的可衍生单元的共聚物的组合物，是一种有效的冷流动促进剂，它比以前推荐的组合物更优越。
首先，本发明提供一种组合物，它包括：
(a)一种油可溶的乙烯共聚物具有，除了由乙烯衍生的单元之外，结构单元
    -CH2-CRR1-                      I和结构单元
       -CH2-CRR2-                II结构单元I和II在共聚物中的总摩尔比率不高于10％，其中每一个R独立地表示H或CH3，和每一个R1和R2各自独立地表示结构式COOR3或OOCR3的一个基团，其中每一个R3独立地表示一个烃基，只是结构单元I与结构单元II不同，或者
(b)包括
(i)一种油可溶的乙烯共聚物具有，除了由乙烯衍生的单元之外，不超过10％(摩尔)的结构单元
    -CH2-CRR1-                      I和(ii)一种油可溶的乙烯共聚物具有，除了由乙烯衍生的单元之外，不超过10％(摩尔)的结构单元
    -CH2-CRR2-                      II其中R，R1和R2具有以上所给定的意义，只是共聚物(i)与共聚物(ii)不同。较好地，R表示H。
在本说明书中使用的术语“烃基”指具有一个直接连接于分子骨架上的碳原子和具有一种烃的或主要是烃的特征的基团。在这些当中，还可以提到的烃类基团包括脂肪族(如，烷基或链烯基)，脂环族(如，环烷基或环链烯基)，芳香族，脂基和脂环基取代的芳香族，和芳基取代的脂肪族和脂环族基团。脂肪族基团较好是饱和的。这些基团还要包含非烃类取代基，只要它们的存在不改变这些基团主要的烃的特征。这些例子包括酮基、卤、羟基、硝基、氰基、烷氧基和酰基。如果烃基是被取代的，优选单取代基。取代的烃基的例子包括2-羟基乙基，3-羟基丙基，4-羟基丁基，2-酮丙基，乙氧基乙基，和丙氧基丙基。这些基团除了由碳原子组成之外，也可以或交替地在链或环上包含除碳以外的原子。合适的杂原子包括，例如，氮，硫，和优选氧。理想地，烃基包含不超过30个，优选不超过15个，更优选不超过10个和最优选不超过8个碳原子。
理想地，R3表示一种链烯基或如上所指的，优选一种烷基，较好是直链烷基，优选是具有至少4个碳原子的直链烷基。如果烷基或链烯基是支链的，例如，在2-乙基己基中，α-碳原子较好是亚甲基部分。理想地，烷基或链烯基包含至多30个碳原子，优选1(对于链烯基是2)-14个碳原子，和更优4-10个碳原子。可以列举的烷基或链烯基例子有丙基，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、十环烷基、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，优选直链异构体，及它们相应的链烯基(较好是链-ω-烯基)。当R1和/或R2为结构式OOCR3时，R3最优选表示丙基，丁基，或戊基，和如上所指的较好是直链异构体。
在本发明的一种优选实施方案中，本发明组合物为组合物(b)，其中R1和R2每一个表示结构式OOCR3的一个基团，其中R3表示具有5-13个碳原子的一种烷基。
可以列举的环烷基、烷芳基和芳基，例如环己基、苄基和苯基。
这种共聚物或这类共聚物也可包含不同于前面所列举的结构单元，例如结构单元
            -CH2-CRR4-              III其中R4表示-OH；或结构式
            -CCH3(CH2R5)-CHR6-      IV其中R5和R6各自独立地表示H或具有至多4个碳原子的烷基，单元IV较好由异丁烯，2-甲基-2-丁烯或2-甲基-2-戊烯衍生而来。
结构单元I或II可以是链端单元，但较好是中间单元，理想地，结构单元-CRR1-CH2-和-CRR2-CH2-占有聚合物不超过7.5％(摩尔)，优选在0.3-7.5％，和最优选在3.5-7.0％。
共聚物(a)和每一种共聚物b(i)和(ii)较好地具有数均分子量(由凝胶渗透色谱法测定)为不超过20,000，较好不超过15,000，更好在1,200-10,000的范围，优选3,000-10,000，更优选3,000-6,000，和最优选在5,000左右。优选的数均分子量在某种程度上取决于在R3中的碳原子数，碳原子数越高，优选的分子量在上述范围中越高。较好地，聚合物b(i)和b(ii)的数均分子量相差最多不超过2000，尤其不超过1000。
R1或R2表示OOCR3的聚合物是优选的，更优选的是RR1和R2均表示OOCR3。
在同一种添加剂组合物中同时使用聚合物(a)和使用聚合物(b)的混合物，是在本发明的范围内。采用具有两种以上不同类型I和II单元的聚合物(a)或采用两种或多种聚合物(a)的混合物，也是在本发明的范围内，当采用聚合物(b)的混合物时，在聚合物(b)i中的单元I较好地与聚合物(b)ii中的单元II不同，但是，采用共聚物的混合物，在这些共聚物中单元I和II相同，只是这些聚合物在至少一个方面不相同，例如，在聚合物中单元I和II的比例，聚合物的分子量或分子量分布，聚合物的直线度，或在聚合物中其它单元的存在，也是在本发明的范围内。
在一优选实施方案中，本发明组合物为一种组合物(b)，其中共聚物(i)是一种乙烯-乙酸乙烯酯共聚物和/或一种其中R1表示OOCR3，其中R3是一具有2-7个碳原子的直链烷基的共聚物，共聚物(ii)是一种其中R2表示OOCR3，其中R3代表一具有2-7个碳原子的直链烷基的共聚物。
本发明还提供一种包含该添加剂组合物的油，和一种包括该添加剂组合物与一种油或一种与这种油可混溶的溶剂的添加剂浓缩物。本发明进一步提供这种添加剂组合物的改进油的低温性能的用途。这种油可以是原油，即直接由钻井得到的和炼制前的油，本发明的组合物适于用作流动促进剂。
这种油还可以是润滑油，它可以是动物油、植物油或矿物油，例如，从石脑油或锭子油到SAE(美国汽车工程师学会)30，40或50润滑油级的石油馏分，蓖麻油，鱼油或氧化矿物油。此类油可以包含由其预定用途而定的添加剂；这些例子是粘度指数促进剂(比如乙烯-丙烯共聚物)。基于琥珀酸的分散剂，含金属的分散剂添加剂和二烷基二硫代磷酸锌抗磨剂添加剂。本发明的组合物可以合适地用于润滑油作为流动促进剂，倾点降低剂或脱蜡助剂。
这种油可以是一种燃料油，尤其一种中间馏出燃料油。此类馏出燃料油一般在110℃至500℃，例如在150℃至400℃的范围内沸腾。该燃料油可以包括常压馏出油或真空馏出油，或裂化瓦斯油或直馏馏分与热和/或催化裂化馏出液以任何比例的混合液。最普通的石油馏出燃料是煤油，喷气式发动机燃料，柴油，燃料油和重质燃料油。燃料油可以是常压直馏馏出油，或它可以包含少量(例如至多35wt％)的真空瓦斯油或裂化瓦斯油或它们两者。上述低温流动问题对于柴油和燃料油是经常遇到的。本发明也适用于基于植物的燃料油，例如菜籽油。
这种添加剂或这类添加剂于环境温度下在这种油中的溶解程度优选应至少在1000ppm％(重量/油重)。然而，至少一些添加剂在油的浊点附近从溶液中游离并能有效地改变所形成的蜡状结晶。
而根据本发明的组合物(b)中，聚合物(i)较好是一种乙烯-乙酸乙烯酯或丙酸乙烯酯共聚物。较好地，由每100个亚甲基单元甲基数目表示的该聚合物直线度为1-15，它是通过质子NMR测得的。
这些共聚物，尤其是乙烯-乙酸乙烯酯或丙酸乙烯酯共聚物可以通过在现有技术中任何已知方法制得，例如，通过由自由基引发的溶液聚合反应，或通过在高压釜或管状反应器中方便地进行的高压聚合反应。
另一方面，共聚物可以通过乙烯-不饱和酯共聚物如乙烯-乙酸乙烯酯或丙酸乙烯酯共聚物，或乙烯-(甲基)丙烯酸甲酯或乙酯共聚物的皂化和再酯化而制得。
还有一种制备共聚物的方法是通过酯基交换作用，只要进入的酸或醇与所要除去的酸和醇相比具有较低的挥发性。
如果需要，所有的(或基本上所有的)现存酯基团可以被水解和完全被所需要的链上取代基取代。此外，只水解一部分，以使得所得到的聚合物包含，例如，乙酸基侧基和较长的链。
在制备共聚物(a)时，以合适的比例使用酯类单体(由它直接制备聚合物)的或酸或醇反应物(它们能使再酯化反应或酯基交换作用得以进行)的混合物，并考虑这些原料的反应活性的差异。
在本发明的实施方案(a)中，单元I和单元II存在的摩尔比优选在2∶98-98∶2，较好在5∶95-95∶5，尤其在1∶10-10∶1的范围。在实施方案(b)的聚合物中包含的单元I和单元II，它们存在的重量比率较好在10∶1-1∶10优选在3∶1-1∶3 ，和更优选在约1∶1 。
这种添加剂组合物和这种油的组合物可以包含用于改进低温和/或其它性能的其它添加剂，它们中的许多已经在现有技术中使用或在文献中是已知的。
例如，该组合物也可包含另外一种乙烯—乙烯基酯共聚物。如上所提到的，参考美国专利No.3961916，流动促进剂组合物可以包括一种蜡增长抑止剂和一种成核剂。不希望受任何理论的约束，本申请人相信，本发明的添加剂组合物首先起抑止剂的作用并受益于成核剂的加入，例如，一种乙烯—乙烯基酯(尤其乙酸酯)，它具有数均分子量在最高不超过14,000的范围，和乙烯基酯含量在7.5-35％(摩尔)，理想地酯含量较高，以及与如上所定义添加剂组合物中任何酯的含量相比，酯含量优选高至少2％(摩尔)，更优选高至少3％(摩尔)。
这种添加剂组合物也可包括一种梳状聚合物。此类聚合物在“梳状聚合物。结构与性能”，N.A.Plat和V.P.Shibaev，J.Poly.Sci.MacromolecularRevs.，8，P117-253(1974)中讨论过。
较好地，该梳状聚合物是一种均聚物或者一种共聚物，该均聚物或者该共聚物的至少25％(摩尔)和优选至少40％(摩尔)，更优选至少50％(摩尔)的单元，含有至少6个和优选至少10个原子的侧链。
那些可列举的优选的梳状聚合物例子具有通式
Figure C9310771700141
其中D＝R11，COOR11，OCOR11，
   R12COOR11，或OR11，
E＝H，CH3，D，或R12 ，
G＝H或D，
J＝H，R12，R12COOR11，或一种芳基或杂
   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。
而m和n表示摩尔比，m在1.0-0.4的范围，n在0-0.6的范围。R11较好地表示一种具有10-30个碳原子的烃基，而R12较好地表示一种具有1-30个碳原子的烃基。
如果需要或被要求的话，这种梳状聚合物可以包含由其它单体衍生来的单元。包括两种或多种不同梳状共聚物的情况，是在本发明的范围内。
这些梳状聚合物可以是马来酸酐或富马酸和另一种烯属不饱和单体的共聚物，例如，一种α-烯烃或一种不饱和酯(如乙酸乙烯酯)。尽管在2-1和1-2的范围的摩尔比是合适的，使用等摩尔量的共聚用单体是优选的但不是必需的。可以与例如马来酸酐共聚合的烯烃的例子包括1-癸烯，1-十二碳烯，1-十四碳烯，1-十六碳烯，和1-十八碳烯。
可以通过任何合适的技术将共聚物酯化，马来酸酐或富马酸至少50％被酯化尽管是优选的，但不是必需的。可以使用的醇类的例子包括正癸醇-1，正十二烷醇-1，正十四烷醇-1，正十六烷醇-1，和正十八烷醇-1。这些醇类也可以在每一个链上包括至多一个甲基支链，例如，1-甲基十五烷醇-1，2-甲基十三烷醇-1。这种醇可以是正常的醇和单个甲基支化的醇的混合物。优选使用纯的醇类，而不使用商业上可购的醇混合物，但是，如果使用混合物，则R12指在烷基中碳原子的平均数；如果使用在1或2位包含一个支链的醇类，则R12指这种醇的直链骨架部分。
这些梳状聚合物尤其是富马酸酯的或衣康酸酯的聚合物或共聚物，例如那些在欧洲专利申请153176；153177，和225688，和WO91/16407中所描述的。
特别优选的富马酸酯梳状聚合物是富马酸烷基酯类和乙酸乙烯酯的共聚物，其中烷基具有12-20个碳原子，尤其是那些聚合物，其中烷基具有14个碳原子或其中烷基是C14/C16烷基的混合物，它们是通过，例如，等摩尔富马酸和乙酸乙烯酯的混合物的溶液共聚合反应和让所得到的共聚物与醇或醇类混合物反应而制得，其中这些醇优选是直链醇类。当使用混合物时，它较好是正常C14和C16醇类的1∶1(重量)混合物。此外，还可较好地使用C14酯与混合C14/C16酯的混合物。在此类混合物中，C14与C14/C16的重量之比较好在1∶1--4∶1的范围，优选在2∶1--7∶2，和最优选约3∶1 。
其它合适的梳状聚合物是α-烯烃的聚合物和共聚物，苯乙烯和马来酸酐的酯化共聚物，和苯乙烯和富马酸的酯化共聚物；根据本发明可以使用两种或多种梳状聚合物的混合物，而如上所表明的，这样使用也许是较好的。
添加剂组合物也可包括极性氮化合物，如那些在美国专利No.4211534中所描述的，尤其一种邻苯二甲酸酐与二摩尔比例的氢化牛脂胺的酰胺--胺盐，或邻--磺苯甲酸酐的相应的酰胺--胺盐。
本发明的添加剂组合物也可包括乙烯与至少一种α-烯烃的一种共聚物，该共聚物具有数均分子量至少为30,000。优选的α-烯烃具有最多不超过20个碳原子。此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。该共聚物也可包括少量，例如至多10％(重量)的其它可共聚合的单体，比如不同于α-烯烃的烯烃，和非共轭二烯。优选的共聚物是一种乙烯-丙烯共聚物。包括两种或多种这种类型的不同的乙烯-α-烯烃共聚物的情况，是在本发明的范围内。
如上所表明，这种乙烯-α-烯烃共聚物的数均分子量至少是30,000，它是相对于聚苯乙烯标准由凝胶渗透色谱法(GPC)测定的，较好是至少60,000和优选是至少80,000。就功能而言分子量没有上限，但是在分子量高于约150,000时增高的粘度使得混合困难，因此，优选的分子量在60,000和80,000到120,000的范围。
较好地，这种共聚物具有的乙烯摩尔含量在50％和85％之间。更好地，乙烯含量在57-80％的范围，和优选乙烯含量在58-73％，更优选在62-71％，和最优选在65-70％。
优选的乙烯-α-烯烃共聚物是乙烯摩尔含量在62-71％和数均分子量在60,000-120,000的范围的乙烯-丙烯共聚物，尤其优选的共聚物是乙烯含量在62-71％和分子量在80,000-100,000的乙烯-丙烯共聚物。
这些共聚物可以由在现有技术中已知的任何方法制备，例如使用一种齐格勒型催化剂。这些聚合物应该基本上是无定形的，因为高度结晶的聚合物于低温下在燃料油中是相对地不溶的。
这种添加剂组合物也可以包括另外一种乙烯-α-烯烃共聚物较好地具有数均分子量为最多不超过7,500，较好在1,000-6,000，和优选在2,000-5,000，它是由汽相渗透压测定法测定的。合适的α-烯烃是如上所给的，或苯乙烯，而丙烯再一次是优选的。较好地，乙烯含量在60-77％(摩尔)尽管对于乙烯-丙烯共聚物来说，采用至多86％(摩尔)的乙烯是比较好的。
这种组合物也可以包括聚(乙二醇)酯类，较好地，是在链上包含18-22个碳原子的脂肪酸的酯类，尤其当燃料被处理后不含作为蜡状结晶成核剂的较高级烷烃时。
另外，该添加剂组合物和燃料油组合物可以包含用于其它目的添加剂，例如，用于在贮存过程中减少颗粒析出或阻止变色和沉降物的形成。
本发明的燃料油组合物较好地包含本发明的添加剂，即上述组分(a)和(b)，基于燃料重量其比例在0.0005％至1％较好在0.001-0.1％，和优选在0.04-0.06％(重量)。
下列实施例用来说明本发明，在这些实施例中所有的份数和百分数均以重量计，及数均分子量都是由凝胶渗透色谱法测定。
实施例A--C--聚合物的制备
                    实施例A
将450g包含13.5％(重量)乙酸乙烯酯，Mn5,000，支化度6 CH3/100CH2的乙烯-乙酸乙烯酯共聚物加入到一装有冷凝器的烧瓶中。然后在氮气氛中加热到60℃，并搅拌。在50g正丁醇中的47.5g甲醇钠被小心加入到该聚合物中，随后，再加入200g正丁醇。该溶液由透明变至橙黄色，而温度降至46℃。然后将该混合物加热到90℃，颜色变为深红色，然后保持在该温度搅拌2小时。
将50g所得到的聚合物(Mn 5600)溶于包括300ml甲苯和8.25g吡啶的无水溶剂混合物中。滴加在250ml甲苯中的14ml己酰氯，然后将得到的混合物在室温下搅拌5小时。固体物被过滤出来，洗涤并除去溶剂，得到38g粘性聚合物(Mn 6000)，在该聚合物中R1表示-OOCR3，R3表示正戊基。
                实施例B
以同样的方法，使用丁酰氯制得一种聚合物，Mn 5000在该聚合物中R3表示正丙基。
                实施例C
一种包含乙酸乙烯酯、异丁烯和乙烯，及500ppm过辛酸叔丁酯的混合物在一高压釜中于1200巴、200℃下进行聚合反应。
回收到一种乙烯/乙酸乙烯酯/异丁烯三元共聚物，它含有13.5％(重量)乙酸乙烯酯和7.8％(重量)异丁烯，由NMR测得支化度为9.3CH3/100CH2，Mn5450。
下列燃料在后面编号的实施例中使用：燃料                      1                 2倾点，℃                  -3                -3CFPP，℃                  -4                -5IBP，℃                   162               168FBP，℃                   375               37190-20，℃                 126               127FBP-90，℃                43                41％蜡状物                  1.4               1.5(低于倾点10℃)
CFPP是根据如在“Journal of theInstitute of Petroleum”，52(1966)，173中的描述而测定的。
                    实施例1和2
在这些实施例中，按在以上实施例A和B中的描述所制备的共聚物及由它们衍生而来的聚合物(包含13.5％乙酸乙烯酯，以下标明为聚合物1)在燃料1中用作添加剂，其总处理量为50ppm。其中使用了两种添加剂的混合物，在混合物中两者等比例存在。
实施例            添加剂                CFPP，℃
(对比)            聚合物1               -11
1                 1/A                   -14
2                 1/B                   -12
                实施例3和4
在这些实施例中，按在实施例A、B和C中的描述所制备的共聚物，在燃料2中用作添加剂，其总处理量为50ppm；其中使用了两种添加剂的混合物，在混合物中两者等比例存在。
实施例            添加剂                CFPP，℃
(对比)            聚合物C               -9
3                 C/A                   -11
4                 C/B                   -12
编号的实施例的结果表明，使用两种成核剂的混合物，使CFPP得到改良。

Claims (25)

1.一种燃料油组合物，它包括一种燃料油和一种添加剂组分，添加剂组分包含：
(a)一种油可溶的乙烯共聚物，除了由乙烯衍生物的单元之处，具有结构单元I：
  -CH2-CRR1-               I和结构单元II：
  -CH2-CRR2                II结构单元I和II在共聚物中的总摩尔比率不高于10％，其中每个R独立地代表H或CH3，和每一个R1和R2各自独立地表示式COOR3或OOCR3的一个基团，其中每一个R3独立地表示一个含最多8个碳原子的烃基，只是结构单元I与结构单元II不同，或者
(b)包括
(i)一种油可溶的乙烯共聚物，除了由乙烯衍生的单元之外具有不高于10％(摩尔)的结构单元I
-CH2-CRR1-           I和(ii)一种油可溶的乙烯共聚物，除了由乙烯衍生的单元之外具有不高于10％(摩尔)的结构单元II：
-CH2-CRR2            II其中R，R1和R2具有以上所给的定义，只是COOR3中的R3代表含至多30个碳原子的链烯基或烷基，并且共聚物(i)与共聚物(ii)不同，
其中共聚物组分(a)和(b)基于燃料重量的总比例为0.0005％至1％(重量)。
2.根据权利要求1的组合物，其中R3表示具有至少4个碳原子的直链烷基。
3.根据权利要求1的组合物，其中R1和R2各自表示-OOCR3。
4.根据权利要求1的组合物，其中R表示H。
5.根据权利要求1的组合物，采用添加剂组分(b)，并且其中R1和R2每一个表示结构式OOCR3的一个基团，其中R3表示具有5-13个碳原子的一种烷基。
6.根据权利要求5的组合物，其中聚合物组分(b)(i)和(ii)每一个的数均分子量为最高不超过20,000。
7.根据权利要求6的组合物，其中数均分子量是在3,000-6,000的范围内。
8.根据权利要求6或7的组合物，其中(b)(i)的数均分子量和(b)(ii)的数均分子量相差不超过2000。
9.根据权利要求6的组合物，其中聚合物组分(b)(i)和(ii)每一个包含0.3-7.5％(摩尔)的结构单元I或II。
10.根据权利要求1的组合物，其中组分(a)或组分(b)(i)和(ii)的至少一种是通过一种乙烯-不饱和酯共聚物的皂化和再酯化而制备的。
11.根据权利要求1的组合物，其中R1和R2同时表示-OOCR3，并且这种聚合物是通过一种乙烯-乙酸乙烯酯共聚物的皂化和再酯化而制备的。
12.根据权利要求1的组合物，采用添加剂组分(b)，并且其中共聚物(i)是一种乙烯-乙酸乙烯酯共聚物和/或一种其中R1表示OOCR3，其中R3是一具有2-7个碳原子的直链烷基的共聚物，共聚物(ii)是一种其中R2表示OOCR3，其中R3代表一具有2-7个碳原子的直链烷基的共聚物。
13.根据权利要求1的组合物，它也包括一种蜡结晶抑止剂。
14.根据权利要求13的组合物，其中抑止剂是一种乙烯-乙烯基酯共聚物，其酯含量比聚合物(a)的最高至少2％(摩尔)，或比聚合物b(i)和(ii)中酯含量较高者高至少2％(摩尔)。
15.根据权利要求1的组合物，它还包括一种梳状聚合物。
16.根据权利要求15的组合物，其中梳状聚合物具有通式：
Figure C9310771700041
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，OR12，或COOH，
L＝H，R12，COOR12，OCOR12，COOH，或芳基，
R11≥C10烃基，
R12≥C1烃基，而m和n表示摩尔比率，m在1.0-0.4的范围，n在0-0.6的范围。
17.根据权利要求15或16的组合物，其中梳状聚合物是乙酸乙烯酯和富马酸酯的共聚物。
18.根据权利要求17的组合物，其中酯基是具有12-20个碳原子的烷基。
19.根据权利要求18的组合物，其中酯基是由具有14个碳原子的醇，或由具有14和16个碳原子的醇的混合物衍生而来。
20.根据权利要求1的组合物，它包括两种或多种不同梳状聚合物的混合物。
21.根据要求20的组合物，其中混合物包括：
(i)一种C14富马酸酯-乙酸乙烯酯共聚物，和
(ii)一种C14/C16富马酸酯-乙酸乙烯酯共聚物。
22.根据权利要求1的组合物，它还包括一种极性氮化合物。
23.根据权利要求22的组合物，它包含总比率为以燃料重计0.001-0.1％的聚合物(a)和(b)。
24.根据权利要求1的组合物，它包含总比率为以燃料重计0.04-0.06％的共聚物(a)和(b)。
25.根据权利要求1的添加剂组合物的用途，是改进燃料油的低温性能。
CN93107717A 1992-06-30 1993-06-29 燃料油组合物 Expired - Lifetime CN1085226C (zh)

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