CN1063218C - 蜡状倾点下降剂的分散体 - Google Patents
蜡状倾点下降剂的分散体 Download PDFInfo
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- CN1063218C CN1063218C CN96121729A CN96121729A CN1063218C CN 1063218 C CN1063218 C CN 1063218C CN 96121729 A CN96121729 A CN 96121729A CN 96121729 A CN96121729 A CN 96121729A CN 1063218 C CN1063218 C CN 1063218C
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
- C10M127/06—Alkylated aromatic hydrocarbons
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract
一种液态倾点下降剂组合物,包括:在室温是固态并且其数均分子量至少为500的倾点下降剂,和此倾点下降剂物料在室温下基本上不溶于其中的液体介质。这种倾点下降剂组分分散在液态介质中。
Description
本发明涉及蜡倾点下降剂的分散体。
各种类型的馏分燃料油如柴油、各种润滑粘度的油类、自动传动液、液压油、家庭炉用油、以及原油,为使其在较低温度自由流动而需要使用倾点下降剂添加剂。这些油通常含有煤油作为蜡,特别是馏分燃料油中存在的蜡的溶剂。但是近几年来,喷气式发动机燃料对煤油的需要使得馏出燃料油中煤油用量被减低。这样就轮到需要添加蜡晶体改良剂来弥补煤油的匮乏。而且,因为添加煤油被认为是不经济的,因此,对在原油中倾点下降剂添加剂的需求就更加重要。
许多倾点下降剂由于存在较长的烃基,其本身就是某种程度上的蜡固状材料。如果这些物质是液态的,即溶解在或分散在一些介质中,就可以在常温下得到更好的处理。
House的US专利4435309,1984年3月6日,公开了一种液化物质的方法,这种物质在环境温度或者是蜡状固体,或者是这些蜡物质及其种溶剂的固体或半固体的混合物。这种蜡物质在溶剂中于提高的温度下形成溶液,将溶液冷却产生半固体到固体,接着将混合物剪切。这些蜡物质是季铵化合物和聚氧乙烯烷基酚;溶剂是异丙基胺和水的混合物,或己二醇。
Martinek的US专利3061544,1962,10月30日,公开了一种制备胶态分散体的方法,通过剪切期间同时降低温度、压力和浓度来制备。胶体形成相通过采用足够的热溶于最小量的承载胶体相而形成溶液。将这种热的、浓缩的溶液在高压下通过喷射或喷咀进入低压和低温区,在此区域喷射物或喷雾碰到和撞击液相平面,也可在高压下注入。
Lockhart等的1968,7月16日的US专利3393078公开了一种汽车抛光剂,通过搅拌和加热配制剂直至蜡组份分散并乳化成细微的熔融(或接近熔融)微粒为止,并将所得的乳液组合物冷却至室温而制成。将此乳液快速搅拌,同时将其冷却至低于这种蜡熔点的温度;接着缓慢搅拌乳液,同时使其从(混合的)容器壁上的出口流入用于将其出售的容器中。
Davis等在1927年8月2日的US专利1637475中公开了用胶体物质作乳化剂的蜡乳液,胶体物质是硬和软皂的混合物。物料的加热和强搅拌是连续进行的,直至蜡被分散为止。进行分散时,为使物料快速变冷,通过容器的套管循环冷却或冷冻介质,同时继续搅拌。当物料温度达到约65℃时,用粗布进行粗滤并使其逐渐冷却至室温。
Martella等在1991年8月13日的US专利5039437,(和1992年1月21日的US专利5082470,上述一案的分案)公开了用于改进烃油低温流动性的烷基酚-甲醛缩合物添加剂。这种聚合的组合物的数均分子量至少是约3000,且分子量分布至少是1.5;在烷基化酚反应物中,烷基基本上是直链的,碳原子数在6和50之间,并且碳原子平均数在约12和26之间;在烷基化酚上的不超过约10%(摩尔)烷基部分碳原子数少于12,并且在烷基化酚上的不超过约10%(摩尔)烷基部分碳原子数多于26。
Dorer,Jr.,等在1986年1约14日的US4564460(1985年12月17日的US4559155,1986年1月21日的US4565550,1986年3月11日的US4575526和1986年9月23日的US4613342等分案),公开了为改进烃燃料组合物的冷流动性的添加剂。这种组合物包括倾点下降剂,它可以是烃基取代的酚,通式为(R*)a-Ar-(OH)b,其中R*选自碳原子数为8到39的烃基和碳原子数至少30的聚合物的烃基,Ar是芳烃部分,包括连接的多环芳烃部分,通式为ar-(-Lng-ar-)-w(Q)mw,其中w是1到约20的整数。每一个Lng是包括亚烷基键合型的(如其中有-CH2-)桥键。
本发明提供一种均化的液态倾点下降剂组合物,包括:
(ⅰ)在室温是固体并且数均分子量至少500的倾点下降剂,和
(ⅱ)液态基质,其中的物质(ⅰ)在室温基本上是不溶的;
其中组份(ⅰ)是分散在组份(ⅱ)中的。
本发明进一步提供一种均化以下混合物的方法:
(ⅰ)在室温是固态并且其数均分子量至少500的物料,和
(ⅱ)物料(ⅰ)基本上在室温不溶于其中的液体;
包括步骤:
(a)加热组份(ⅰ)和(ⅱ)到(ⅰ)在(ⅱ)中能溶解或熔融的温度;
(b)将加热的组份混合;和
(c)将加热的混合物冷却到(ⅰ)基本上不溶解的温度。
本发明是一个蜡倾点下降剂在一种物料中的分散体,这种物料对倾点下降剂是不溶的。该分散体通常是均化的,至少在宏观范围是均化的。这种蜡倾点下降剂是这样的物料,其数均分子量为至少500,优选至少700,更优选至少1000,优选高达500000,更优选高达50000,最优选5000。这种物料在10℃,优选在室温,也就是说至少高达约20℃,并优选高达30或40℃或更高是固态的(在没有加入溶剂时)。这种物料进一步是:当混合在含蜡烃液中时,通过ASTM D-97测定,起倾点下降剂的作用。合适的物料通常是低聚物,通常包括至少一个每分子含至少12个碳原子的烃基。
本发明包括多种类型的倾点下降剂。在这些倾点下降剂中,包括(a)和(b)的反应产物,(a)在室温是固态或半固态,通常是“蜡”物料并且是烃基取代基上有足够碳原子数的烃基取代酚,和(b)是碳原子数为1到12,优选为1到4的醛或其来源。
烃基取代酚是公知物质,其制备方法也是已知的。本文所用术语“酚”应理解为此术语通常不将酚的芳基限定为苯(除非文中如此作了说明,如在实施例中),不过苯可以是优选的芳族基团。反之,此术语可在更宽的意义上理解为通常包括羟基的芳族化合物,例如,取代的酚,羟基萘等等。这样,“酚”的芳基可以是单环和多环的,取代的,还可以包括其他类型的芳基。
羟基芳香化合物的芳基可以是一个单一芳香核,如苯核、吡啶核、噻吩核、1,2,3,4-四氢萘核等等,或多核芳香部分。这种多核部分可以是稠合型的;就是说,其中构成芳基的芳核对有两点共用,如在萘、蒽、氮杂萘等等中存在的。多核芳环部分也可以是连接型的,其中至少两个核(单核或多核)是相互通过桥键键合彼此连接的。这种桥键键合可以是芳环之间的碳-碳单键、醚键、酮键、硫醚键、含2到6个硫原子的多硫醚键、亚硫酰键、磺酰键、亚甲键、亚烷键、二-(低级烷基)亚甲键、低级亚烷基醚键、亚烷基酮键、低级亚烷基硫键、含2到6个碳原子的低级亚烷基多硫醚键、氨键、聚氨键和这种两个价的桥键键合的混合物。在一些例子中,在芳核之间的芳基上可以存在多于一个的桥键键合。例如芴核有两个通过亚甲键和共价键相连的苯核。可以认为这种核具有3个核,但是其中只有两个是芳核。芳基通常只在芳核本身含有碳原子,尽管也可存在其他非芳香取代基,如特别是短链的烷基取代基。这样,例如在芳基上可以存在甲基、乙基、丙基和叔丁基,尽管这些基团在此处所列的结构中未明确表示出。
单环芳香部分的特殊实例如下:等等,其中Me是甲基,Et适当地是乙基或亚乙基,Pr是正丙基。
当芳香部分是键合的多核芳香部分时,它可以用下面的通式表示
ar(-L-ar-)w其中w是1到约20的整数,每个ar是碳原子数为4到约12的单环和稠环芳核,每个L单独选自ar核之间的碳-碳单键、醚键(如-O-)、酮键(如-CO-)、硫醚键(如-S-)、含2到6个硫原子的聚硫醚键(如-S-2-6)、亚磺酰键(如-S(O)-)、磺酰键(如-S(O)2-)、低级的亚烷基键(如-CH2-,-CH2-CH2-,-CH2-CHR0-)、单(低级烷基)-亚甲基键(-CHR0-)、二(低级烷基)-亚甲基键(如-CR0 2-)、低级亚烷基醚键(如-CH2O-、-CH2O-CH2-、-CH2-CH2O-、-CH2CH2OCH2CH2-、-CH2CR0HOCH2CR0H-、-CH2CR0HOCR0HCH2-等等)、低级亚烷基硫醚键(如其中在低级亚烷基醚键上的一个或多个-O-被S原子取代)、低级亚烷基聚硫醚键(如其中一个或多个-O-被-S2-6-基团取代)、氨键(如-NH-、-NR0-、-CH2N-、-CH2NCH2-、-alk-N-,其中alk是低级亚烷基等等)、聚氨键(如-N(alkN)1-10,其中未饱和的自由N键被H原子或R0取代)、由氧桥-或酮-羧酸衍生的键其中每一个R1、R2和R3分别是烃基、优选是烷基或链烯基、更优选是低级烷基、或H,R6是H或烷基,X是从0到约8的整数,以及这些桥键键合的混合物(每一个R0都是低级烷基)。
连接部分的特殊实例是:等等。
所有这些ar基团通常都没有取代基,除了那些被特别提到的以外。出于成本、可获得的容易程度、性能等原因,芳基部分通常是苯核、低级亚烷基桥键的苯核、或萘核。最优选的芳基部分是苯核。
这种第一个反应物是羟基芳香化合物,即,一种至少一个羟基直接加到芳环的化合物。每个芳基的羟基数可从1变至这个基团的最大数,以便使烃基取代的芳香部分在保留至少一个,优选至少两个位置的同时,与其适应,至少其中一些优选与羟基相邻(邻位),这样的基团适于进一步与醛的缩合反应(下文详述)。因此,大多数这样的反应物分子就有至少两个未取代的位置。那么,适用的物质包括烃基取代的邻苯二酚、间苯二酚、对苯二酚,以及甚至1,2,3-苯三酚和间苯三酚。但是,最常见的是每一个芳核上有一个羟基,并且在优选情况下,当采用烃基取代的酚时,这种物质含有一个苯核和一个羟基。当然,芳香反应物分子的一小部分可以不含羟基取代基。例如,最小量的无羟基物质可以作为杂质存在。但是,这并不背离本发明精神,只要原料物质有官能团,并在每个分子上通常含有至少一个羟基即可。
羟基芳香反应物类似的特征在于,它是烃基取代的。术语“烃基取代基”或“烃基”用在此处是指本领域技术人员公知的通常所指的意义。特别是,它涉及的基团具有直接加到分子剩余部分的碳原子并具有占优势的烃性质。烃基的实例包括:
(1)烃取代基,即脂族(如烷基或链烯基)、脂环族(如环烷基、环烯基)取代基,和芳族、脂族和脂环族取代的芳香取代基,以及其中环由分子的另一部分成环构成(如两个取代基一起形成一个脂环基)的环取代基;
(2)取代的烃取代基,即取代基含有,在本发明内容中,不变更占优势的烃基取代基(如卤(特别是氯和氟)、羟基、烷氧基、巯基、烷巯基、硝基、亚硝基和亚砜)的非烃基团;
(3)杂取代基,即取代基是在具有占优势的烃性质的同时,在本发明内容中,在由碳原子构成的环或链上,还含有非碳原子。杂原子包括硫、氧、氮以及包括如下的取代基,如吡啶基、呋喃基、噻吩基和咪唑基。在烃基的每十个碳原子上一般存在不超过两个,优选不超过一个非烃取代基;通常在烃基上没有非烃取代基。
烃基优选烷基。烷基优选含有至少12个,更优选至少20个,最优选至少30个碳原子,或者如果这个烷基是烷基的混合物,这种混合物优选平均含有至少30个碳原子,通常含有31到400个碳原子,优选31到60,更优选32到50或45个碳原子,尽管这不是必须的。在优选实施方案中,在组合物中的烷基是烷基的混合物,它在链的长度上可以从一个特定的烷基变成另一个。当这种分子的部分含有一个少于30个碳原子的烷基时,组合物作为整体一般具有长度上至少30个碳原子烷基取代基的特征。对于本发明的特定实施方案来说,烷基可以更短,含有少于30个碳原子,如主要是24到28个碳原子或20-24个碳原子。在任何情况下,烷基既可以由直链又可以由支链烯烃反应物衍生;尽管链长较长的物质趋于增加支链部分,有时仍优选直链。一定程度的支化同样似乎是在烷基化过程中通过重排机理引入的。
在一个优选实施方案中,所用烃基包括一个烷基长度主要为30到36个碳原子,数均碳数大约34.4,并且重均碳数大约35.4的烷基混合物。这种物质的特点是具有大约如下的链长分布:
C26 0.3% C40 3.8
C28 11.9 C42 2.9
C30 16.7 C44 2.3
C32 11.3 C46 1.8
C34 8.6 C48 1.5
C36 6.6 C50 1.4
C38 5.0 C52 1.3因此这种烃基取代基含有的数均数大于30个碳原子。这种取代基优选是烷基,其中在烷基链上的碳原子数均数是31-40,更优选是32-38。
烃基可由相应的烯烃衍生;例如一个C26烷基是由C26烯烃,优选是1-烯烃衍生的,一个C34烷基是由C34烯烃衍生的,并且混合的链长基团是由相应的烯烃混合物衍生的。但是,当烃基具有至少30个碳原子时,它通常是,含有2到10个碳原子的一烯烃或二烯烃,如乙烯、丙烯、1-丁烯、异丁烯、丁二烯、异戊二烯、1-己烯、1-辛烯等等的均聚物或互聚物(如共聚物或三聚物)制得的脂族基(或这种基团的混合物)。为了适于用作倾点下降剂,至少烷基的一部分优选直链,就是说基本上是链状的。应当相信,为了使得链更有利与成蜡烃的链状结构相互作用,优选这种特征。可以认为在许多情况下,甚至在采用α-烯烃时,在烷基链加到芳环的连接点上有甲基支链。可以认为这是在直链或链状烷基的范围之内。另外,也许由于烷基化反应期间活性位置的转移,在一些情况下,烷基部分可以在连接点(或α-位置)上含有低级烷基支链。所用烯烃通常是1位一烯烃,如乙烯的均聚物。这些脂族烃基也可由这种均聚物或互聚物的卤代(如氯代的或溴代的)类似物衍生的。但是,这些基团可以由其他来源衍生,如高分子量烯烃单体(如1-四十碳烯)和它们的氯代类似物和氢氯化的类似物,脂族石油馏份,特别是石蜡和裂解的和氯化的类似物及其氢氯化的类似物,轻油,合成烯烃如通过齐格勒-纳塔方法制备的物质(如聚(乙烯)油)和本领域技术人员已知的其他来源。在烃基中的任何不饱和度都可以按照本领域已知的氢化反应来还原或消除。制备途径或采用基本无氯或其他卤素的原料有时基于环境原因来进行优选。
在一个实施方案中,烃基部分由聚丁烯衍生。在另一实施方案中,烃基部分由聚丙烯衍生。在优选实施方案中,如上所述,烃基由链长主要是30-36个碳原子的基本上无支链的烯烃混合物衍生。
这样的烃基可以存在不止一个,但对于每一个芳基芳核通常不超过2或3个。更普遍的是每个芳香部分只有一个烃基,特别是烃基取代的酚是基于一个苯环时。
将烃基连接在本发明第一个反应物的芳香部分上可以通过本领域技术人员已知的众多技术完成。一个特别适用的技术是佛瑞德-克来福特反应,其中烯烃(如含烯键的聚合物)、或其卤代或氢卤代的类似物在存在路易斯酸催化剂的情况下与酚进行反应。进行这种反应的方法和条件对本领域技术人员是已知的。例如参见在由John Wiley和Company,N.Y.的Interscience Publishers出版,第3版,第2卷,第65-66页的在“Kirk-Othmer Encyclopedia of Chemical Technology”中的题为“酚的烷基化”文章中所讨论的。其他将烃基基团连接到芳香部分的等效和便利的技术对本领域技术人员是容易得到的。
反应形成如上所述倾点下降剂的第二组份是碳原子数为1到12的醛,或其来源物。适用醛的通式是RC(O)H,其中R如上所述优选是氢或烃基,不过,R可以包括不影响醛与羟基芳香化合物缩合反应(下面描述)的其他官能团。这种醛优选含1到12个碳原子,更优选1到4个碳原子,最优选1或2个碳原子。这种醛包括甲醛、乙醛、丙醛、丁醛、异丁醛、戊醛、己醛、苯甲醛和更高级醛。优选单醛。最优选的醛是甲醛,它可用作溶液,但通常采用其多聚型,如多聚甲醛。多聚甲醛可以被认为是醛的反应等效物或其源物。其他反应等效物还包括醛的水合物或环状三聚物。
烃基酚和醛以相对量的范围在从约等摩尔到醛过量约30%(摩尔)(基于醛单体计算)来反应的。优选醛的量比烃基酚多5到20,更优选8到15%(以摩尔计)。这种组份是在导致低聚物或聚合物形成反应的条件下进行反应。产物的分子重量根据包括反应物的当量比、反应的温度和时间、以及存在的杂质等特征而定。这种产物可以在其链上含有2到50个重复的芳香单元,优选3到30个这样的单元,更优选4到14个单元。当烃基酚特别是在烷基链上有24-28个碳原子的烷基酚时,并且当醛是甲醛时,优选物质的数均分子量是1000到24000,更优选2000到18000,最优选300到6000。基于链长为约34个碳原子的烃基取代基的物质分子量相应的可以更高。
这种烃基酚和醛是通过将烷基酚和醛在适量的稀释油或视需要而存在的其他溶剂,例如芳香溶剂如二甲苯中,存在酸如硫酸、磺酸如烷基苯基磺酸、对甲苯磺酸或甲磺酸、有机酸如二羟乙酸,或AmberlystTM催化剂,即一种来自Rohm和Haas的固体、大孔的、轻度交联的磺化的聚苯乙烯-二乙烯基苯树脂催化剂的情况下混合反应。将混合物加热,通常是90到160℃,优选是100到150或到120℃,经适当的时间如30分钟到6小时,优选1到4小时,去除缩合反应的水。时间和温度要相符,因此在低温下进行反应就需要较长的时间等等。确定精确的条件是本领域技术人员能够做到的。如果需要,反应混合物可以被加热到更高的温度,如140-180℃,优选145-155℃,进一步去除挥发物,使反应进行完全。根据需要,这种产物可以用碱如NaOH处理,来中和强酸催化剂,并制备这种产物的钠盐,根据需要,此后还可借助适当的常规技术如过滤进行分离。
其他类型的蜡倾点下降剂也适用于本发明内容。一个示范的种类是用脂肪醇酯化的α烯烃/酰化剂共聚物。这种在共聚物中是共聚单体的烯烃是一个或多个c-烯烃(有时是指单-1-烯烃)或异构的α-烯烃。α-烯烃的实例通常包括乙烯、丙烯、丁烯、1-辛烯、1-壬烯、1-癸烯、1-十二碳烯、1-十三碳烯、1-十四碳烯、1-十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1-十九碳烯、1-二十碳烯、1-二十一碳烯、1-二十二碳烯、1-二十四碳烯等等。市售的适用-烯烃部分包括C15-18α-烯烃、C12-16α-烯烃、C14-16α-烯烃、C14-18α-烯烃、C16-18α-烯烃、C6-20α-烯烃、C22-28α-烯烃等等。在一个实施方案中,烯烃是C16和C16-18α-烯烃。另外,可以采用商标Gulftene的C30+α-烯烃部分,Gulf Oil Company有售。在优选实施方案中,α烯烃是在C16至C30和更高范围内。
用于制备烯烃的方法对本领域技术人员是公知的,并且在题为“烯烃”的文中作了详细的描述,此文摘自Encyclopedia of ChemicalTechnology,第二版,Kirk和Othmer增版,第632,657页,Jonh Wiley和Son的Interscience Publishers出版,1971。
这种共聚物的其他组份是可共聚的酰化剂。一种酰化剂是一种可与醇反应生成酯的原料;通常是一种酸、一种酯、或优选是反应性更强的等效物,如酰基卤或酐。包括单羧基和多羧基的酰化剂。特别优选的是二羧基酰化剂,如丁二酸酰化剂。它们还包括丁二酸、卤化物、酯和酸酐,优选酸、酯或酸酐,更优选酸酐。
这种共聚物用一种或多种脂肪醇酯化。脂肪醇就是烷基羟基化合物,特别是直链的烷基羟基化合物,并且更特别是含至少6,优选至少12或18个碳原子的。优选的脂肪醇含有16到30个碳原子。脂肪醇的实例包括辛酰基醇、壬酰基醇、月桂醇、十四烷酰基醇、十六烷酰基醇、十七烷酰基醇、十八烷酰基醇、二十醇、二十二醇、二十六醇,市售的和如含8-12个碳原子、16-20个碳原子等等醇的混合物。
上述类型的一个有代表性的倾点下降剂是C20-24α-烯烃和马来酐(摩尔比1∶1)的共聚物的二十二醇二酯。
适用于本发明的其他类型蜡倾点下降剂包括含酯的聚合物和低聚物,包括亚乙基/乙烯基乙酸酯共聚物,特别是那些熔体指数小于100(ASTM1238条件E)并且也包括含有丙烯酸酯或甲基丙烯酸酯单体的聚合物;由脂肪醇制备的脂肪醇的酯聚合物,如乙烯基羧酸酯/二烷基反丁烯二酸酯的共聚物,尤其是乙烯基丙烯酸酯/C16-30烷基反丁烯二酸酯;聚(丙烯酸甲酯)或聚(甲基丙烯酸甲酯),与含16到30个碳原子的脂肪醇进行酯转移反应形成长链酯;通过用C16-30醇酯化丙烯酸并且接着进行聚合而制得的类似的聚合物;以及苯乙烯/马来酐共聚物,由C16-30脂肪醇酯化而来。一些特定的聚α烯烃也可用作倾点下降剂。还包括烷基化萘,包括那些由氯化石蜡和α烯烃与萘反应生成的物质。这些或其他类型的蜡倾点下降剂对本领域技术人员是已知的,并且通常是商品。
本发明的倾点下降剂是作为在液态介质中的分散剂提供的,其在液体中于10℃一般是不可溶的,优选在室温,即约20℃,甚至30℃或40℃同样是不可溶的。这就是说,首先这种介质在室温(约20℃)是液态的,并且优选凝固点是10℃或更低。一些优选介质,尤其是混合物的凝固点低至0℃、-20℃、-30℃、-40℃或更低。而且,这种介质在这些温度下,优选室温下不能大量溶解这种倾点下降剂。更具体的说,介质优选在室温或适度升温下,能够溶解低于4%,优选低于2%或甚至1%(重)的倾点下降剂。(在一些情况下溶解性低的部分可能包括杂质和未反应的物质,因此实际上倾点下降剂溶解的量成比例的减小,如小于0.5%重量。)优选的介质直至30℃或优选40℃或50℃或更高仍保持不溶。
为了使蜡倾点下降剂不溶于液态介质,介质通常应该具有一定程度的极性。极性可以通过不同的方法测定和表示。因此在一个实施方案中,在溶剂的分子中优选有10到80%重量,更优选20到70%重量,进一步优选25到60%重量的杂原子,如氧或氮。可选择的是介质的介电常数是至少3,优选至少10。上述参数通常是指介质作为整体的参数,如果是混合物,包括混合的所有组份。
合适的液态介质包括乙酸酯(如乙酸2-乙氧基乙酯,也叫做CellosolveTM乙酸酯),酮类(如丙酮、丁酮、戊酮、己酮),或者含水1,2-乙二醇混合物(如乙二醇和水的混合物)。在这些原料中可以单独或与水结合使用的是乙二醇及其衍生物,如一甲基醚(MethylCellosolveTM),一乙基醚(CellosolveTM),一丙基醚,一丁基醚,和一己基醚;二乙二醇及其衍生物,如一甲基醚(Methyl CarbitolTM),一乙基醚(CarbitolTM),一丙基醚,一丁基醚,和一己基醚;丙二醇及其衍生物,包括一甲基醚(Methyl PropasolTM),一丙基醚和一丁基醚;和二丙二醇及其衍生物,如一甲基醚(Methyl DipropasolTM),一丙基醚和一丁基醚。
其他适用类型的原料是内酯类,如丁内酯,和醇类,如丁醇,二丙酮醇(4-羟基-4-甲基-2-戊酮),2,6-二甲基-4-庚醇(Diisobutyl CarbinolTM)己醇、异丙醇、2-乙基己醇和1-戊醇。
液态原料可以是任何前述原料的混合物,包括与水的混合物,尽管蜡倾点下降剂在这些混合物中是近似不溶的。如果这些液态原料是二元醇和水的混合物,原料的相对用量就是:水组份在低温,如0--40℃不凝固。对这些含水混合物来说,重量比优选是约1∶1,通常是1∶2到2∶1,优选1∶1.5到1.5∶1是令人满意的。
许多蜡倾点下降剂通常采用浓缩的形式,包括各种比例的芳香溶剂,如二甲苯或沸点约为179℃的市售混和芳香溶剂。存在适量的这些溶剂(如以倾点下降剂/溶剂混合物的重量来计,是10-50%,如25%)已被证明有时有助于将倾点下降剂分散在介质中,尽管其存在是不要求的。如果存在这些芳香溶剂,可以把它当作是液体介质的一个组份,并且构成介质的总量一部分,同时有利于介质中溶剂的性质(极性)的形成。
分散组合物也优选包括一种有助于形成并保持分散体的分散剂。分散剂,又叫做表面活性剂,可分为阴离子的、阳离子的、两性离子的或非离子的。阴离子表面活性剂包括含有在另一端键合水溶性(亲水性)基团的亲油长尾链的物质,其中亲水基含有阴离子部分,如羧酸、磺酸或被阳离子,如碱金属或铵中和的酚基团。这种亲油尾链优选是烷基,通常的是含8到21个碳原子的烷基。
通常的阴离子表面活性剂包括羧酸盐,如具有通式R1COOR2的脂肪酸盐,其中R1是直链的、饱和或不饱和的、含约8到21个碳原子的烃基,R2是碱形成基,如Li、Na、K或NH4的基团,其可以使洗涤剂类的表面活性剂能溶于水或提高这种表面活性剂对水的亲和性。可选择性的是R2可以是二价或多价金属,其中,通常存在适当数量的酸基是为了提供中性盐。多价金属离子包括Mg、Ca、Sr、Ba、Cr、Mn、Fe、Co、Ni、Cu、Zn、Sn、Pb等等。通常的脂肪酸盐包括硬脂酸钠、软脂酸钠、油酸铵、软脂酸三乙醇胺盐。另外的可用作阴离子表面活性剂的羧酸盐包括椰子油脂肪酸和妥尔油酸的盐,特别是钠和钾盐,以及其他羧酸盐化合物,包括胺盐,如三乙醇胺盐、酰化多肽和N-月桂基肌氨酸的盐,如N-十二酰基-N-甲基甘氨酸钠盐。
其他的阴离子表面活性剂包括芳基和烷基芳基磺酸盐,如烷基苯磺酸盐、链状烷基苯磺酸盐、四亚丙基苯磺酸钠、十二烷基苯磺酸钠、苯-、甲苯-、二甲苯、和枯烯磺酸盐、木素磺酸盐、石油磺酸盐、石蜡磺酸盐、仲正构烷基磺酸盐、α-烯烃磺酸盐、烷基萘磺酸盐、正构酰基正构烷基牛磺酸盐、磺基丁二酸酯、异硫代硫酸盐、烷基硫酸盐,通式为R1OSO3R2,其中R1和R2如上限定,如十二烷基硫酸锂、十二烷基硫酸钠、十二烷基硫酸钾、十四烷基硫酸钠、烷基磺酸盐,其通式为R1SO3R2,其中R1和R2如上限定,如月桂基磺酸钠,硫酸化的和磺化的酰胺和胺,硫酸化的和磺化的酯如月桂酸单酸甘油酯硫酸钠、磺乙基油酸钠、月桂基磺基乙酸钠、硫酸酯盐如硫酸化链状伯醇、硫酸化聚氧亚乙基化直链醇和硫酸化甘油三酯油、磷酸和聚磷酸酯、全氟化羧酸、聚合的阴离子表面活性剂如藻酸。
还包括聚合的阴离子表面活性剂,如丙烯酸烷基酯和/或甲基丙烯酸烷基酯和丙烯酸和/或甲基丙烯酸的聚合物的盐,以及马来酐-苯乙烯共聚物的偏酯的盐。
其他可以被划归阴离子表面活性剂的物质是高碱性的或超高碱性的物质。它们是酸性有机化合物(羧酸、磺酸、膦酸、酚等等)的碱性金属盐,优选是碱金属或碱土金属盐。高碱性物质通常是一相的,以超出为了按照金属和特定与金属反应的酸性有机化合物的化学计量进行中和而存在的金属含量为特征的均相牛顿体系。这种高碱性物质是通过酸性物质(通常的是无机酸或低级羧酸,优选二氧化碳)与含酸性有机化合物的混合物反应制得的,反应介质包括至少一种对所说的酸性有机物质是惰性的有机溶剂(矿物油、石脑油、甲苯、二甲苯等等)、化学计量过量的金属碱和一种促进剂如苯酚或醇。这种酸性有机物质通常含有足够的碳原子数,能够以一定程度溶于油中,并且使产品具有表面活性剂活性。过量金属的量通常以金属比率表示。术语“金属比率”是金属的总当量与酸性有机化合物的当量比:中性金属盐的金属比率是1;一种具有中性盐中金属存在量的4.5倍的盐金属过量3.5当量,或金属比率4.5。
高碱性物质通常用作润滑添加剂,这是本领域公知的技术。它们还有其他的用途,其使用的范围不同于其他的表面活性剂。这就是说,它们在电场暴露之后,偶尔可以观察到被认为是碳酸钙的沉淀出现。不过,在这种情况不会引起麻烦的条件下,使用上述物质仍是可行的,并且仍然认为是在本发明的范围之内。描述了制备磺酸、羧酸和任何两种或多种该物质的混合物的碱性盐的技术的专利包括US2501731;2616905;2616911;2616925;2777874;3256186;3384585;3365396;3320162;3318809;3488284;和3629109。
阳离子表面活性剂与阴离子表面活性剂类似,不同的是分子的表面活性部分带正电。阳离子表面活性剂的实例是长链胺及其盐,如由动物和植物脂肪酸和妥尔油衍生的伯胺和合成的C12-18伯胺、仲胺或叔胺;二胺及其盐,季铵盐包括四烷基铵盐和由如脂或氢化脂衍生而来的咪唑啉盐,或者N-苄基-N-烷基二甲基铵的卤化物;聚氧亚乙基化的长链胺;季铵化的聚氧亚乙基化的长链胺;和胺氧化物如N-烷基二甲基胺氧化物(实际上是两性离子)如十六烷基二甲基胺氧化物或硬脂酰基二甲基胺氧化物。
两性离子表面活性剂包括氨基酸,如β-N-烷基氨基丙酸,N-烷基-β-亚氨基二丙酸,咪唑啉羧化物,N-烷基三甲铵乙内酯、磺基三甲铵乙内酯和sultaines。
本发明所优选的非离子表面活性剂是这样的类似物质,其中它的极性官能团不是由阴离子或阳离子基团提供的,而是由中性基团提供的,通常的如醇、胺、醚、酯、酮或酰胺官能团。通常的非离子表面活性剂包括聚氧亚乙基化烷基酚,如聚氧亚乙基化对壬基酚、对辛基酚或对十二烷基酚,由椰子油,牛脂,包括油基衍生物在内的合成物质衍生的聚氧亚乙基化直链醇;聚氧亚乙基化聚氧丙二醇(环氧乙烷与环氧丙烷的嵌段共聚物),通常的分子量是1000到30000;聚乙二醇;聚氧亚乙基化硫醇;长链羧酸酯,包括天然脂肪酸的甘油酯和聚甘油酯,丙二醇酯,山梨醇酯,聚氧亚乙基化的山梨醇酯,聚氧乙二醇酯,和聚氧亚乙基化脂肪酸;链烷醇胺“缩合物”如通过脂肪酸的甲酯或三酸甘油酯与等摩尔或两倍摩尔量的链烷醇胺反应制备的缩合物;叔炔二元醇;聚氧亚乙基化硅氧烷,通过可反应的硅氧烷中间体与封端的烯丙基聚亚烷基氧化物如氧化丙烯或混和的氧化乙烯/氧化丙烯共聚物反应而制得;N-烷基吡咯烷酮,和烷基聚苷(聚糖的长链缩醛)。这些中的多数及其他离子的或非离子的表面活性剂公开在Rosen的“Surfactants and Interfacial Phenomena”,John Wiley和Sons出版,pp.7-31,1989。
一些通常以作为非离子表面活性剂为特征的物质与某些上述液态介质相似。对这些物质之间的区别需要作说明,如果这种物质具有非离子表面活性剂的性质而且在室温,优选甚至在30℃或40℃是固态的,它就可以归为本发明所说的非离子表面活性剂。在上述温度,特别是室温或者更低的温度是液态的物质倒不如可以归作液态介质的组份。
其他的非离子表面活性剂更具体的说包括乙氧基化可可酰胺、油酸、叔十二烷基硫醇、改性的聚酯分散剂,酯、酰胺、或基于异丁烯基丁二酐的混合的酯-酰胺分散剂、基于聚异丁基酚的分散剂、ABA型嵌段共聚非离子表面活性剂、丙烯酸接枝共聚物、辛基苯氧基聚乙氧基乙醇、壬基苯氧基聚乙氧基乙醇、烷基芳基醚、烷基芳基聚醚、胺聚二醇缩合物、改性的聚乙氧基加合物、改性的封端烷基芳基醚、改性的聚乙氧基化直链醇、封端乙氧基化的链状伯醇、高分子量的叔胺如1-羟基乙基-2-烷基咪唑啉、恶唑啉、全氟代烷基磺酸酯、脱水山梨醇脂肪酸酯、聚乙二醇酯、脂基或芳基磷酸酯。还包括烃基取代的琥珀酰化剂和胺的反应产物。这些反应产物和它们的制备方法在US4234435;4952328;4938881;和4957649作了记载。
其他的非离子表面活性剂包括官能化的聚硅氧烷。这些物质含有官能团如氨基、酰胺基、亚氨基、磺酰基、亚砜基(sulfoxyl)、氰基、羟氧基、烃氧基、巯基、羰基(包括醛和酮)、羧基、环氧、乙酰氧基、磷酸酯、膦酰基和卤代烷基。这些聚硅氧烷可以是链状的或支链的,并且其分子量通常是在800以上,即高达10000或20000。这种官能团还可被随机地分布在聚酯链或存在于嵌段之中。这种官能团可以是烷基或烷芳基,以及基团如-(C2H4O)a-(C3H6O)b-R,其中a和b分别是0到约100的数,而a或b中至少一个是至少1,R是氢、乙酸基、或烃基。其他适用的基团包括C3H6X,其中X是OH、SH、或NH2。这种物质的实例包括来自Union Carbide的SilwetTM表面活性剂和来自Goldschmidt ChemicalCorp.,Hopewell,VA的TegoprenTM硅氧烷表面活性剂。
非离子表面活性剂包括聚氧亚烷基烷基醇或酚,如乙氧基化壬基酚、多元醇的链烷酸酯(优选链烷酸偏酯)、如一油酸甘油酯、一月桂酸甘油酯、一油酸脱水山梨醇酯、一倍半油酸脱水山梨醇酯、一月桂酸脱水山梨醇酯和一倍半月桂酸脱水山梨醇酯,以及4,4-二羟基甲基-2-十七烷基-2-恶唑啉。优选的物质包括被二乙醇胺中和的妥尔油脂肪酸、TritonTM表面活性剂(来自Rohm和Haas),包括有1到70个环氧乙烷单元的辛基酚系列和有4到40个环氧乙烷单元的壬基酚系列、由2~13个环氧乙烷单元的NeodolTM表面活性剂乙氧基化物(来自Shell Chemical Co.)、含7到50个环氧乙烷单元的IgepalTM表面活性剂(来自Rhone-Poulenc)、含4到41个环氧乙烷单元的TergtitolTM表面活性剂(来自UnionCarbide)。这些前述的市售物质通常是链状伯醇的乙氧基化物或(在是Triton物质的情况下)支链的烷基酚乙氧基化物。
脂肪的倾点下降剂、液态介质和可选择的表面活性剂的相对量非常广泛地变化,但是优选以重量份计在(20-60)∶(40-80)∶(0-10)范围内,优选在(30-50)∶(50-70)∶(1-7)范围内,更优选(35-45)∶(55-65)∶(2-6)范围内,尤其是约38∶58∶4。
本发明的分散组合物按下列方式制备,首先将组分加热到这种蜡状物质能够以适当的方式分散到液态介质和视需要而存在的表面活性剂中的温度。如果在适当提高的温度下,这种蜡物质可溶解在液态介质中的活,这种条件是可以得到满足的。通常这种溶解性不仅是由蜡物质本身所固有的溶解性和介质的溶解性,并且还由液态介质的沸点决定的。优选的液态介质和蜡物质的组合如下:在此实施方案中,能够在介质的正常沸点或低于介质正常沸点情况下获得适量的溶解,如每100克介质溶解80克,不过,如果需要也可通过为提高介质的熔点将组份在高压下结合的方式提高溶解度。作为选择,可以通过将混合物加热到高于蜡物质沸点的温度来改进蜡物质的分散性,即使是蜡物质不溶于介质。一般说来,将混合物加热直至组合物成为液态。最后只要对分散体进行适当的机械处理,在一些情况下就能够获得具有适当分散性的在升温下既不溶解又不熔化的物质。被加热的组合物,特别是如果它们是液态的(熔化的或溶解的),就会混合而制成所需的分散体。这种混合可以在高剪切或空化条件下进行。“高剪切”通常是指剪切条件至少是每秒103,优选至少是每秒105,并且更优选至少是每秒106。空化条件也可认为是高剪切条件;空化通常包括在液体中形成细微的气泡,这些气泡在超声波能量的影响下膨胀,接着在剧烈的剪切作用下暴聚。能够产生足够的高剪切和空化条件的设备包括SonicatorTM,高强度超声波处理器,其中高频电压(如20kHz)被转换成机械振动能,通过探针直接作用于液体样品。还包括高剪切分散混合器(如DispersatorTM),其中高速转子以紧密间隙与固定的定子装配,当液体流入转子,并被以高速推动通过定子时,由于机械的和水的力量而产生相当高的剪切环境,或者用MicrofluidizerTM(来自Microfluidics Intl.Inc),其中两个高压流在设定的微通道以高速相互作用,因此剪切、撞击、空化力通常产生超微颗粒。组合物要被加热的温度取决于熔点、溶解度和所用物质的挥发性;通常加热到40到100℃,优选加热到50到90℃,更优选70到83℃。将被加热的混合物冷却至其中蜡物质实际上不溶解并且通常以固态或半固态存在的温度,同时保持混合条件。所得的混合物是稳定的分散体。
在一个实施方案中,将倾点下降剂熔融,往此熔融体中加入适量的表面活性剂,同时搅拌。加入适量的同样经过加热的液态介质(如水/1,2-乙二醇),并将组分混合。将混合物在热的时候以及在冷却过程中,或者选择性的在混合物冷却之后,进行高剪切混合或声处理。
通过任何前述方法制备的物料还可以被描述成均相物料。这就是说它们是这样的物料,即由于前述的处理方法,悬浮物料的粒度相对的减小并优选比较均一,并且悬浮的颗粒相对均匀地分布在介质中,并在工业上合理的时间内保持分散状态。
本发明的分散体可以浓缩形式用作含蜡(石蜡)烃物质如原油或原油馏分如残油、真空瓦斯油或真空残油(Bunker C原油),也就是说天然的或部分精炼的油,包括部分加工的石油派生油的倾点下降剂。用在含石蜡液体中的倾点下降剂的量为适合将倾点降低到可测量数值即至少0.6℃(1°F),优选至少2℃(3或4°F),更优选3℃(5°F),甚至更优选6℃(10°F)的量。这种倾点的减低可以很容易的由本领域专业人员通过采用ASTM D-97的方法测定。倾点下降剂的典型用量,除其分散于其中的液体介质之外,基于加入其中的流体重量,占百万分之50到10000份(ppm),优选100到5000ppm,更优选200到2000ppm。浓缩物的总量基于倾点下降剂在其中的浓度可以按比例升高。
实施例1
乙二醇571.5g,和蒸馏水571.5g通过搅拌混合,并加热到约50℃(120°F)。分别加入1143.0g甲醛和烷基酚的缩合物,烷基取代基的链长主要为C30-36个碳原子,如上所述(在50%的稀释矿物油中含50%活性成分),再加入114.3g含75.6%重量妥尔油脂肪酸和24.4%重量二乙醇胺的分散剂组合物,加热,直至发生熔融(约82℃,180°F)为止,并且以充分剪切的形式混合约10分钟以上,制成均相混合物。将加热的乙二醇/水混合物加入其他混合物中,充分剪切20分钟以上。
将制成的混合物冷却,再两次通过MicronizerTM,其装有“3669”相互作用室(产生75微米的粒子)和3839背压模量(200微米),压力设定为170MPa(25000psi)。收集被完全处理的物质。
实施例2
往一个小不锈钢杯中加入(a)70.57g用2.2摩尔的二十二醇酯化的苯乙烯/马来酐共聚物(摩尔比为1∶1,比浓粘度约0.42)的倾点下降剂,和(b)105.86g的2-乙氧乙基乙酸酯(CellosolveTM乙酸酯)。用顶部装有均化器的实验DispersatorTM混合这些化学物质。同时继续剪切,将混合物加热到77℃(170°F),在此温度下,混合物变的透明。继续加热到82℃(180°F)。终止加热,继续剪切将混合物冷却至室温。
实施例3
往50毫升未改进倾点为-18℃(0°F)的原油样品中加入0.05g的实施例2的倾点下降剂组合物。制得的混合物的倾点是-46℃(-50°F)。
实施例4
往在加热板上的PyrexTM烧杯中加入28.0重量份在实施例2制备的倾点下降剂(a)和(b)65.0重量份的丙二醇叔丁基醚(来自Arco的ArcosolveTMPTB)。将这些化学物质加热,并用实验室搅拌器混合,同时将混合物加热直至倾点下降剂完全溶解为止。终止加热,继续搅拌将混合物冷却至室温。
通过将混合物放入油脂轧机(包括钢管和装入其中的圆柱形棒,以及混合物)中,并且将混合物捏炼1小时,将在混合物中的倾点下降剂的粒度进一步减小。
实施例5
重复实施例4,不同的是混合物含有120g的实施例1的倾点下降剂(a)和(b)含60g的丙二醇一丁基醚、60g的CellosolveTM乙酸酯和60g丙二醇的介质。开始加热直至倾点下降剂熔化为止。
实施例6
往PvrexTM烧杯中加入(a)15重量份的含甲醛和烷基酚缩合物的倾点下降剂,其中烷基取代基链长主要为C30-36个碳原子,如上所述(在50%的稀释矿物油中含50%活性成分),和(b)1.5重量份的含75.6%重量妥尔油脂肪酸和24.4%重量二乙醇胺的分散剂组合物。将混合物加热到82℃(180°F),搅拌,置于加热板上,并向混合物缓慢加入已被预热到50-70℃(120-160°F)的(c)7.5重量份乙二醇和7.5重量份水的混合物。添加完之后,将混合物通过MicrofluidizerTM并将其冷却至室温。实施例7
重复实施例6,不同的是用组份(a)15重量份的实施例1的倾点下降剂来代替烷基酚缩合物。
实施例8
往PvrexTM烧杯中加入(a)15重量份的含乙烯乙酸乙烯酯共聚物(来自Du Pont的ElvaxTM150,含33%的乙酸乙烯酯,熔体指数43(ASTM D1238-E))的倾点下降剂,和(b)1.5份重量的含75.6%重量妥尔油脂肪酸和24.4%重量二乙醇胺的分散剂。将混合物加热到82℃(180°F),搅拌,置于加热板上,并往这种混合物中加入7.5重量份的乙二醇(已加热到82℃),接着加入7.5重量份的水(已加热到71℃)。添加完之后,将混合物通过MicrofluidizerTM并将其冷却至室温。
实施例9
重复实施例2,不同的是用2.2摩尔二十二醇酯化的C18α烯烃/马来酐共聚物(摩尔比为1∶1)来代替苯乙烯-马来酐聚合物。
上述的每一个文件都可供结合参考。除了在实施例中,或者除非有另外的明确指示,在这些描述物料的具体量、反应条件、分子量、碳原子数等等所有的数值量都可理解为是“大约”的。除非有其他说明,此处所指的每一个化学物质或组合物都是指市售等级的物质,即它们可以含有异构体、副产物衍生物及其他通常认为在市售产品中存在的物质。但是,出现的每一种化学组份的量不包括任何通常在市售产品中存在的溶剂或稀释油,除非有特别的指示。此处所采用的“主要含有”表示方式是允许包括不会实质上影响该组合物基本的和新的性质的物质。
Claims (14)
1.一种均化液态倾点下降剂组合物,其中包括:
(ⅰ)以该组合物总重为100重量份为基准计20~60重量份在10℃是固态并且其数均分子量至少为500的选自下列物质的倾点下降剂:烃基取代的酚与C1-12醛或其来源形成的反应产物、α-烯烃的酯/酰化剂共聚物和乙烯/乙酸乙烯酯共聚物;和
(ⅱ)物料(ⅰ)基本上在10℃不溶于其中的40~80重量份选自下列物质的液体介质:水、链烷二醇、乙酸烷氧基乙酯、链烷二醇烷基醚及其混合物;
其中组份(ⅰ)分散在组份(ⅱ)中。
2.权利要求1的组合物,其中倾点下降剂包括(a)烃基取代酚和(b)C1-12醛或其来源的反应产物。
3.权利要求2的组合物,其中醛是甲醛或其来源。
4.权利要求1的组合物,其中倾点下降剂包括一种被脂肪醇酯化的α烯烃/酰化剂共聚物、含酯的聚合物或低聚物、羧酸乙烯酯/二烷基富马酸酯共聚物、烷基化萘、或者聚α烯烃。
5.权利要求1的组合物,其中液态介质的凝固点等于或低于10℃。
6.权利要求1的组合物,其中液态介质含有10~80%重量杂原子。
7.权利要求1的组合物,其中液态介质的介电常数至少为3。
8.权利要求1的组合物,其中液态介质选自乙酸酯、酮、醇、和含水二醇混合物。
9.权利要求1的组合物,其中还包括(ⅲ)分散剂,其量应有助于形成并保持组份(ⅰ)在组分(ⅱ)中的分散体。
10.权利要求1~10中任一项的均化液态倾点下降剂组合物的制备方法,其中包括下列步骤:
(a)加热组份(ⅰ)和(ⅱ)到(ⅰ)在(ⅱ)中能溶解或熔融的温度;
(b)将加热的组份混合;和
(c)将加热的混合物冷却到(ⅰ)在(ⅱ)的液体中基本上不溶解的温度。
11.权利要求10的方法,其中组份(ⅰ)和(ⅱ)被加热到40~100℃。
12.权利要求10的方法,其中被加热的组份在高剪切或空化条件下混合。
13.权利要求10的方法,其中冷却步骤(c)在混合条件下进行。
14.权利要求1~10中任一项的均化液态倾点下降剂组合物在降低含石蜡液体的倾点方面的用途。
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US5451630A (en) * | 1994-08-02 | 1995-09-19 | Dsm Copolymer, Inc. | Solid sheared polymer blends and process for their preparation |
AU701875B2 (en) * | 1995-09-08 | 1999-02-11 | Lubrizol Corporation, The | Pour point depressants and their use |
-
1996
- 1996-11-20 CN CN96121729A patent/CN1063218C/zh not_active Expired - Fee Related
- 1996-11-22 CA CA002191036A patent/CA2191036C/en not_active Expired - Lifetime
- 1996-11-26 AU AU74004/96A patent/AU713217B2/en not_active Ceased
- 1996-11-28 NO NO19965075A patent/NO318427B1/no unknown
- 1996-11-28 RU RU96122562/04A patent/RU2171272C2/ru not_active IP Right Cessation
- 1996-11-28 GB GB9624768A patent/GB2308129B/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4564460A (en) * | 1982-08-09 | 1986-01-14 | The Lubrizol Corporation | Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same |
EP0311452B1 (en) * | 1987-10-08 | 1993-03-24 | Exxon Chemical Patents Inc. | Alkyl phenol-formaldehyde condensates as fuel and lubricating oil additives |
CN1102855A (zh) * | 1993-09-11 | 1995-05-24 | 王至善 | 金属防锈脂 |
Also Published As
Publication number | Publication date |
---|---|
CN1158887A (zh) | 1997-09-10 |
GB2308129A (en) | 1997-06-18 |
GB2308129B (en) | 1999-11-10 |
GB9624768D0 (en) | 1997-01-15 |
AU713217B2 (en) | 1999-11-25 |
AU7400496A (en) | 1997-06-05 |
CA2191036A1 (en) | 1997-05-30 |
RU2171272C2 (ru) | 2001-07-27 |
CA2191036C (en) | 2006-01-10 |
NO965075L (no) | 1997-05-30 |
NO318427B1 (no) | 2005-04-18 |
NO965075D0 (no) | 1996-11-28 |
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