CN1015642B - Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof - Google Patents

Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof

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Publication number
CN1015642B
CN1015642B CN87108239A CN87108239A CN1015642B CN 1015642 B CN1015642 B CN 1015642B CN 87108239 A CN87108239 A CN 87108239A CN 87108239 A CN87108239 A CN 87108239A CN 1015642 B CN1015642 B CN 1015642B
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lubricating oil
concentrate
additive concentrate
component
weight
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CN87108239A
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CN87108239A (en
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查理斯·肯
约翰·克拉福德
希恩·帕特里克·奥康诺尔
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Bp化学有限公司
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Abstract

一种适于掺进成品润滑油组合物的添加剂浓缩物,该添加剂浓缩物包括:(a)润滑油;(b)可溶于润滑油的硫化或非硫化碱土金属烃基酚盐,该酚盐通过掺进大于2%小于4%(基于组合物重量)的下列物质之一而得到改进:(i)至少一种具有结构式(I)的羧酸,其中R是C(ii)含有36~100个碳原子的二元或多元羧酸或其酐、酰氯或酯,该组合物的TBN值大于300。 Additive concentrate suitable for incorporation into one kind of finished lubricating oil composition, the additive concentrate comprising: (a) lubricating oil; (b) a lubricating oil soluble sulfurized or sulfurized alkaline earth metal hydrocarbyl phenate, the phenate (based on the weight of the composition) of one of the following materials braced improved by more than 2% less than 4%: (i) at least one carboxylic acid of formula (I) have, where R is a C (ii) comprising 36 to 100 two yuan carbon atoms or polycarboxylic acid or an anhydride, acid chloride or ester, TBN of the composition is greater than the value of 300.

Description

本发明一般涉及碱土金属烃基酚盐及其硫化衍生物,它们的制备和作为润滑油添加剂的应用。 The present invention relates generally to alkaline earth metal hydrocarbyl phenate, and sulfurized derivatives, their preparation and use as lubricating oil additives. 本发明特别涉及具有高总碱值(TBN)和令人满意的粘度的碱土金属烃基酚盐及其硫化衍生物的浓缩添加剂组合物,它们的制备和作为润滑油添加剂的使用。 The present invention particularly relates to an alkaline earth metal hydrocarbyl phenate, and the additive concentrate composition has a viscosity high total base number (TBN of) and satisfactory vulcanization derivatives, their preparation and use as lubricating oil additives.

在内燃机引擎中,来自燃烧室的付产物常从活塞边漏出并与润滑油混合。 In the internal combustion engine, by-products from the combustion chamber often leaks from the sides of the piston and mixing with the lubricating oil. 许多付产物在润滑油内会形成酸性物质。 Many by-products in the oil will form an acidic substance. 有种情况特别显著,即在靠高含硫量的低级燃料运行的柴油机中,可由燃烧产生腐蚀性酸。 Particularly remarkable kind, i.e., in a diesel engine operating on low-grade fuels of high sulfur content, the combustion can be corrosive acid. 因此,润滑油中结合的酸包括:硫氧化产生的含硫酸,燃料中铅卤净化剂衍生出的氢卤酸和燃烧室内空气中氮的氧化产生的含氮酸。 Thus, the lubricating oil in combination acids include: nitrogen acids produced by oxidation of sulfur-containing sulfuric acid, a halogen lead scavengers in the fuel derived from the hydrohalic acids combustion chamber and the air oxidation of nitrogen. 这些酸会造成淤渣沉积和轴承及发动机另部件的腐蚀,导致发动机的迅速磨损和早期损坏。 These acids cause deposition of sludge and corrosion of the bearings and other parts of the engine, leading to rapid wear and early engine failure.

在通常用来中和润滑油内酸性物以及分散淤渣的化合物中,有一类属于金属烷基酚盐及硫化的金属烷基酚盐,其中的金属是碱土金属,诸如钙、镁或钡。 Commonly used in lubricating oil and the acidic compounds and the sludge dispersion, belongs to a class of metal salts of alkylphenols and sulfurized metal alkyl phenates, wherein the metal is an alkaline earth metal, such as calcium, magnesium or barium. “标准的”和“高碱性的”碱土金属烷基酚盐都可采用。 "Normal" and "overbased" alkaline earth metal salts of alkyl phenols may be employed. 术语“高碱性的”一惯描述这样的碱土金属烷基酚盐:其中的碱土金属部分的当量数与酚部分的当量数之比大于1,通常大于1.2,还可高到4.5或更高。 The term "overbased" used to describe such an alkaline earth metal salt of alkylphenol: wherein the number of equivalents of the number of equivalents of alkaline earth metal moiety to phenol moiety is greater than 1, typically greater than 1.2, may be as high as 4.5 or higher . 相比之下,在“标准的”碱土金属烷基酚盐中,这个当量比是1。 In contrast, the "normal" alkaline earth metal alkyl phenates, this equivalent ratio is 1. 因此,“高碱性的”材料就含有比相应“标准的”材料多20%以上的碱土金属。 Thus, the "overbased" material can contain appropriate "standard" 20% or more materials plurality alkaline earth metal ratio. 由于这个原因,“高碱性的”碱土金属烷基酚盐比相应“标准的”碱土金属烷基酚盐具有更高的中和酸性物质的能力。 For this reason "overbased" alkaline earth metal alkyl phenates corresponding "normal" alkaline earth metal alkyl phenates have the ability to neutralize acidic substance higher than.

现有技术介绍了许多制备“标准的”和“高碱性的”金属烷基酚盐的方法。 Prior art describes a metal alkylphenol and "overbased" Many preparing "standard." 一种通常叫作“单次石灰添加”工艺制备“高碱性的”烷基酚盐的方法包括:将烷基酚,在有或没有硫存在的条件下,和润滑油、羟基化合物、过量的碱土金属氢氧化物(超过中和烷基酚所需要的化学计量比)进行反应,生成一个中间产物,随后进行羧化,蒸馏掉头馏分(heading distillation)(以便除去未反应的羟基化合物)然后过滤。 A common called "single lime addition" process for preparing "overbased" alkyl phenates method include: alkyl phenol, under conditions of presence or absence of sulfur, lubricating oil, a hydroxy compound, an excess of the alkaline earth metal hydroxide (above the stoichiometric ratio required and alkylphenol) is reacted to produce an intermediate product, followed by carboxylation, turn distillation fraction (heading distillation) (to remove unreacted hydroxy compound) and filter. 中间产物的生成伴随着粘度的显著增加,而随之的羧化将粘度减小到一相应低的水平。 Produce an intermediate product is accompanied by a significant increase in viscosity, and subsequent carboxylation reduce the viscosity to an appropriate low level. 伴随中间产物的生成而出现的粘度增加是不希望有的,因它使反应混合物变得难于搅拌以至妨害后续反应。 Accompanied by an increase in viscosity occurs produce an intermediate product is undesirable because it becomes difficult to stir the reaction mixture even hinder subsequent reactions. 通过反应中加入少量的碱土金属氢氧化物而将粘度的增加控制在一个可以接受的水平上,这种“高碱性的”烷基酚盐产物必定具有一个降低的中和能力。 By adding a small amount in the reaction of alkaline earth metal hydroxide and the viscosity increase control in an acceptable level, the products of such alkyl phenates "overbased" must have a reduced neutralization capacity. 为了获得一种高中和能力的产物同时把中间产物的粘度控制在适宜的范围内,可把碱土金属氢氧化物以两个反应步骤(一般叫作“双次添加石灰”工艺)或三步分别加入,随后进行羧化。 In order to obtain a high neutralizing capacity of the product while the viscosity of the intermediate product is controlled within a suitable range, the alkaline earth metal hydroxide in two reaction steps (commonly known as "double lime addition" process) or three, respectively, was added, followed by carboxylation. 因此这种方法具有相对较长的加料时间。 Therefore, this method has a relatively long charging time. 另一个替代方法是在中间产物生成过程中使用粘度抑制剂,诸如十三醇,2-乙基己醇或类似沸程的羟基溶剂;但这么一来会大大增加该工艺的原材料成本。 Another alternative is to use an intermediate product in the process of generating the viscosity inhibitors, such as tridecanol, 2-ethylhexanol, or similar boiling range hydroxylic solvent; but that way greatly increases the raw material cost of the process. 虽然以前技术的TBN值一般在200~300范围内,但通过一般现有技术可以获得的最高总碱值(TBN),用毫克KOH/克表示,大约为300;这个值与具有的令人满意的粘度相符合。 While the prior art is generally a TBN in the range of 200 to 300, but the prior art can be obtained by generally the highest total base number (TBN), in mg KOH / g indicated that about 300; with the value of having a satisfactory the viscosity of the match. 很清楚,我们所要求达到的目标是制备一种具有高TBN值的碱土金属烷基酚盐或其硫化衍生物构成的添加剂浓缩物,其TBN值应大于300,最好大于350。 Clearly, we achieve the desired goal is to prepare a concentrate of the additive having an alkaline earth metal salt of alkylphenol derivative or a sulfurized high TBN value constituted that a TBN greater than 300, preferably greater than 350. 至今尚未发现获得这种高TBN产品的可能性,因较高浓度的碱土金属碱的使用会导至高粘性产物,即便在随后羧化处理中用过量的二氧化碳“冲稀”该产物但仍会使它变成不溶性的东西。 This possibility has not yet been found that a high TBN product is obtained, because the use of higher concentrations of alkaline earth metal base will lead to high viscous product, even in the subsequent carboxylation treatment with excess of carbon dioxide "dilute" the product but will still it becomes something insoluble. 通过在反应混合物中掺进有限量的每个分子中至少具有10个碳原子的某些羧酸或其衍生物,我们便达到了这个目的并由此获得了其TBN值超过300,某些情况下可大于350的产品,该产品持有合适的粘度又避免了不溶性。 By braced in the reaction mixture has a limited amount of each molecule having at least some of the carboxylic acid or derivative thereof to 10 carbon atoms, we achieved this object and thus obtain a TBN of more than 300 which, in some cases 350 may be greater than the product, the product holding an appropriate viscosity and avoiding insolubility. 这个粘度在100℃时小于1000cSt(厘沲)。 The viscosity of less than 1000 cSt (centistokes) at 100 ℃.

既可在碱土金属烷基酚盐及其硫化衍生物的制备过程中也可在与润滑油组合物的掺进过程中使用羧酸,对此已有先例,参阅US-A-3,372,116,GB-A-1,440,261,US-A-4,049,560和EP-A-0,094,814。 Can also be used in the preparation of alkaline earth metal alkylphenols and sulfurized derivatives during the course of the lubricating oil mixed into the composition in acid, there is precedent for this, see US-A-3,372, 116, GB-A-1,440,261, US-A-4,049,560 and EP-A-0,094,814.

US-A-3,372,116公开了一种制备碱金属酚盐的改进方法,该方法包括:在25℃到分馏温度之间将(A),(B)和(C)进行反应;(A)是至少含有6个碳原子的烃基取代酚,所说的酚与至多一个当量的至少含有6个碳原子烃基取代琥珀酸或其酸酐的混合物,或基本是中性的碱金属或碱土金属盐,以上所述物品中任何一个;(B)是大约1~10当量的钙或锶碱,对应于每个当量的(A);(C)是二氧化碳。 US-A-3,372,116 discloses an improved process for preparing an alkali metal phenate, the method comprising: (A), (B) and (C) to carry out the reaction at reflux temperature between 25 ℃; ( a) is a hydrocarbon group containing at least 6 carbon atoms, a substituted phenol, a mixture of 6 carbon atoms, hydrocarbyl-substituted succinic acid or anhydride of said phenol with up to contain at least one equivalent of, or a substantially neutral alkali metal or alkaline earth metal salts of any of these items; (B) about 1 to 10 equivalents of calcium or strontium base, corresponding to each equivalent of (a); (C) carbon dioxide. 该方法改进之处在于:对应于每个当量的钙或锶碱,反应进行时存在大约0.002~0.2当量的至多含有100个碳原子的羧酸或其碱金属、碱土金属、锌或铅的盐。 The improvement which that: corresponding to each equivalent of calcium or strontium base, the presence of about 0.002 to 0.2 equivalents of a salt of a carboxylic acid containing up to 100 carbon atoms or an alkali metal, alkaline earth metal, zinc or lead as the reaction proceeds . 优选的羧酸是那些至多含有10个碳原子,最好是至多含有10个碳原子的一元羧酸及其碱土金属盐。 Preferred carboxylic acids are those monocarboxylic acids and alkaline earth metal salts containing up to 10 carbon atoms, preferably containing up to 10 carbon atoms. 在许多实施例中都采用水和羧酸盐。 In many embodiments, the water and carboxylic acid salts are used. 我们不仅要求避免水的存在,而且还发现因羧酸盐在该体系中固有的不溶性,它们是不能用于本发明所述工艺的。 Not only do we need to avoid the presence of water, but also found that carboxylates due to the inherent insolubility in the system, they can not be used in the process of the invention. US-A-3,372,116所述工艺并未使用足以产生具有超过300TBN值的酚盐所需要的酚对碱土金属碱的比值。 US-A-3,372,116 said process does not use a phenol having a ratio exceeding 300TBN phenate value required to generate sufficient alkaline earth metal base.

GB-A-1,440,261公开了一种润滑油组合物。 GB-A-1,440,261 discloses a lubricating oil composition. 包括润滑油、去垢剂或分散剂添加物和一种至少由两种羧酸构成的混合物,其中一种羧酸的熔点至少为20℃并且它的每个分子中有不多于30个的碳原子,另种羧酸的熔点低于20℃,低熔点羧酸对高熔点羧酸之重量比在1.5∶5~8∶1之间。 Comprising oil, detergent or dispersant additive mixtures, and one consisting of two carboxylic acids of at least a melting point of at least one acid and it is 20 ℃ per molecule of not more than 30 carbon atoms, the melting point of the other carboxylic acids is less than 20 ℃, low melting point acid to high melting point acid weight ratio between 1.5:5 ~ 8:1. 去垢剂可是高碱性酚盐,它具有适宜的TBN值为50~100之间。 But overbased detergent phenate having 50 to 100 TBN is suitable. 该润滑油组合物中,酸的混和物存在量为0.05~2.0Wt%。 The lubricating oil composition, the acid mixture is present in an amount of 0.05 ~ 2.0Wt%. (Wt指重量比)US-A-4,049,560描述了一种高碱性镁去垢剂的制备,采用的工艺为将二氧化碳引入反应混和物中,包括:(a)15~40Wt%的含有一个或多个烃基取代的硫化酚或苯硫酚,或含有一个或多个烃基取代的酚或苯硫酚,或带有硫的所说的含有一个或多个烃基取代酚或苯硫酚,(b)5~15Wt%的有机磺酸,有机磺酸酯(盐)或有机硫酸酯(盐); (Wt refer to weight ratio) US-A-4,049,560 describes the preparation of a magnesium overbased detergents, the process uses carbon dioxide is introduced into the reaction mixture, including: (a) 15 ~ 40Wt% containing one or more hydrocarbyl substituted phenols or sulfurized thiophenol containing one or more hydrocarbyl or substituted phenol or thiophenol or with said sulfur containing one or more hydrocarbyl substituted phenols or thiophenols phenol, (b) 5 ~ 15Wt% organic sulfonic acid, organic sulfonate (salt) or an organic acid ester (salt);

(c)5~15Wt%的甘醇,C1-C5的一元醇或C2-C4的烷氧基醇,(d)2~15Wt%的氢氧化镁或活性氧化镁,(e)至少0.1Wt%的C1-C18的羧酸,其酐,或其铵,胺盐,所说的C1-C18羧酸的第Ⅰ族或第Ⅱ族金属盐及,(f)至少10Wt%的稀释油(包括存在于组分(a)和(b)中的)。 (C) 5 ~ 15Wt% glycols, C1-C5 monohydric C2-C4 alcohols or alkoxy alcohols, (d) 2 ~ 15Wt% of magnesium hydroxide or active magnesium oxide, (e) at least 0.1Wt% the C1-C18 carboxylic acids, their anhydrides, or ammonium, amine salt of said C1-C18 group ⅰ ⅱ or metal salt of a carboxylic acid and, (f) at least 10 Wt% of diluent oil (including the presence of in component (a) and (b) in a).

羧酸的数量(组分(e)中的)最好在0.5~2.0Wt%内。 The number of the carboxylic acid (component (e) in a) is preferably in the 0.5 ~ 2.0Wt%. 通过这种方法制备的产品据说其TBN大约为200~250,例如225。 The product prepared by this method is said TBN of about 200 to 250, 225 for example.

EP-A-0,094,814公开了一种掺进润滑油组合物的添加剂浓缩物,该浓缩物包括润滑油,及10~90Wt%的高碱性碱土金属烃基硫化酚盐;该酚盐,在高碱处理期间或其后,用0.1~10Wt%最好是2~6Wt%(基于添加剂浓缩物重量)的羧酸进行处理,所说的羧酸具有下述结构式: EP-A-0,094,814 discloses a lubricating oil composition braced additive concentrate, the concentrate comprising a lubricating oil and 10 ~ 90Wt% of the overbased alkaline earth metal sulfurized hydrocarbyl phenate; the phenate , during or after the high alkali treatment with 0.1 ~ 10Wt% preferably 2 ~ 6Wt% of the treated carboxylic acid (based on weight of additive concentrate), said carboxylic acid having the following structural formula: (这里的R是C10-C24无侧链烷基或链烯基,R1是H,C1-C4的烷基或-CH2-COOH);或这个酸的酐或盐来代替该羧酸。 (R here is no side-chain C10-C24 alkyl or alkenyl group, R1 is H, C1-C4 alkyl or -CH2-COOH); or the salt of the acid anhydride or the carboxylic acid in place. EP-A-0,094814的发明目的是解决许多用含有高碱性添加剂的添加剂浓缩物所遇到的问题,即缺乏稳定性所引起沉淀增多及发泡的问题。 EP-A-0,094814 object of the invention is to solve the problem with many additive concentrates containing overbased additives encountered, i.e., the lack of stability caused by increased precipitation and foaming. EP-A-0,094,814的问题并不是制备具有高于300TBN值的酚盐添加剂浓缩物的问题,事实上用该发明的工艺制备的酚盐添加剂浓缩物时,尽管证实克服了稳定性和发泡的问题但其TBN值是小于300的。 EP-A-0,094,814 the problem of not having the problems above prepared 300TBN value phenate additive concentrate, in fact, when using an additive concentrate phenate prepared by the process of the invention, although overcoming the stability demonstrated and foaming problem but a TBN of less than 300.

由此可得出结论:凡采用羧酸的现有技术并没有提出由具有大于300TBN值和合适粘度的高碱性碱土金属烃基酚盐构成的添加剂浓缩物的制备问题。 It can be concluded: all of the prior art using a carboxylic acid and having no questions prepared by a greater than additive concentrate and a suitable viscosity value 300TBN overbased alkaline earth metal hydrocarbyl phenate constituted.

据此,一方面本发明提供了一种适宜掺进成品润滑油组合物的添加剂浓缩物,该添加剂浓缩物包括:(a)润滑油(b)可溶于润滑油的改进的硫化或非硫化碱土金属烃基酚盐,改进之处是通过掺进大于2%小于40%的下列组合物之一的方式,基于组合物总重量,(ⅰ)至少一种具有下述结构式的羧酸: Accordingly, in one aspect the present invention provides a finished lubricating oil composition suitably braced with the additive concentrate, the additive concentrate comprising: (a) lubricants (b) improved lubricating oil soluble sulfurized or sulfurized one of the following compositions alkaline earth metal hydrocarbyl phenate embodiment, the improvement is braced by more than 2% less than 40%, based on the total weight of the composition, (i) at least one carboxylic acid having the following structural formula: 其中R是C10-C24的烷基或链烯基而R1是H或C1-C4的烷基或-CH-COOH,或者是该羧酸的酐、酰氯或酯;(ⅱ)含有36~100个碳原子的二元或多元羧酸或其酐、酰氯或其酯,该组合物具有大于300的TBN值。 Wherein R is a C10-C24 alkyl or alkenyl group and R1 is H or C1-C4 alkyl group or a -CH-COOH, or an anhydride, acid chloride or ester of the carboxylic acid; (ii) containing from 36 to 100 two yuan carbon atoms or polycarboxylic acid or an anhydride, acid chloride or ester thereof, the composition has a TBN greater than 300.

组合物的(a)组分是润滑油。 Component (a) is a lubricating oil composition. 适宜的润滑油是动物油,植物油和矿物油。 Suitable lubricants are animal oils, vegetable oils and mineral oils. 适宜的润滑油可以是石油衍生的润滑油,如环烷基、链烷烃基或混和基油。 Suitable lubricating oil may be a petroleum-derived lubricating oil, such as a cycloalkyl group, or a group paraffinic base oil blend. 有溶解力的中性油特别适用。 There neutral oil solubility are particularly suitable. 作为替代,润滑油可为合成的润滑油。 Alternatively, the lubricating oil may be a synthetic lubricating oil. 合适的合成润滑油包括合成酯润滑油,它包括二酯如己二酸二辛酯、癸二酸二辛酯和己二酸十三烷基二酯,或聚合烃润滑油如液态聚异丁烯和聚d链烯。 Suitable synthetic lubricating oils include synthetic ester lubricating oils, which include diesters such as dioctyl adipate, dioctyl sebacate and tridecyl diesters of adipic acid, or polymeric hydrocarbon lubricating oils such as liquid polyisobutylene and d alkenes. 润滑油的合适量为组合物重量的10~90%,最好是10~70%。 Suitable amount of the lubricant is 10 to 90% by weight of the composition, preferably 10 to 70%.

组分(b)是可溶于润滑油的改进的硫化或非硫化的,最好是硫化的碱土金属烃基酚盐,该酚盐通过掺进,以大于2%小于40Wt%,基于组合物的量,(ⅰ)或(ⅱ)中的一个而改进。 Component (b) is a lubricating oil soluble sulfurized improved or cured, preferably sulfurized alkaline earth metal hydrocarbyl phenate, braced by the phenate, more than 2% to less than 40 wt%, based on the composition amount, a (i) or (ii) is improved. 合适的碱土金属可以是锶、钙、镁和钡,其中钙、镁和钡较佳,最佳是钙。 Suitable alkaline earth metal may be strontium, calcium, magnesium and barium, with calcium, magnesium and barium preferred, most preferably calcium. 碱土金属烃基酚盐中烃基酚部分最好由至少一种烷基酚衍生得来。 Alkaline earth metal hydrocarbyl phenate is preferably derived in part hydrocarbyl phenols come from at least one alkyl phenol. 烷基酚中的烷基可以是有支链或无支链的。 Alkylphenols the alkyl group may be branched or unbranched. 合适的烷基含有4~50,最好是9~28个碳原子。 Suitable alkyl groups contain from 4 to 50, preferably 9 to 28 carbon atoms. 一种特别适合的烷基酚是通过丙烯的四聚物使酚烷基化而得的C12-烷基酚。 A particularly suitable alkyl phenol is a phenol by alkylation of propylene tetramer obtained C12- alkyl phenols.

碱土金属烃基酚盐通过掺进组合物(ⅰ)或(ⅱ)而得到改进。 Alkaline earth metal hydrocarbyl phenate compositions braced by (i) or (ii) be improved. 至于(ⅰ),它至少是一种具有结构式(Ⅰ)的羧酸或其酐、酰氯或其酯。 As regards (i), which is at least one carboxylic acid having the structural formula (Ⅰ), or anhydride, acid chloride or ester thereof. 在结构式(Ⅰ)中,R优先选用无侧链的烷基或链烯基。 In formula (Ⅰ), R preferred no side chain alkyl or alkenyl group. 优选的结构式(Ⅰ)的酸是那些R为C10-C24、最好是C18-C24的直链烷基且R1是H的酸。 Preferred acids of formula (Ⅰ) are those wherein R is C10-C24, preferably C18-C24 straight chain alkyl and R1 is H acid. 结构式(Ⅰ)的合适的饱和羧酸举例包括癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、山萮酸和二十四酸。 Suitable saturated carboxylic acids of formula (Ⅰ) examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. 结构式(Ⅰ)的合适的不饱和羧酸举例包括月桂烯酸、肉豆蔻脑酸、棕榈油酸、油酸、顺9-二十碳烯酸、芥酸、蓖麻油酸、亚油酸和亚麻酸。 Suitable unsaturated carboxylic acids of formula (Ⅰ) examples include lauric acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid and linen acid. 也可采用酸的混合物,如油菜头脂肪酸。 Mixtures of acids may be employed, such as rapeseed fatty acids head. 特别适用的酸的混合物是一系列商品级酸,包括饱和的和非饱和酸。 Particularly suitable mixtures of acids are a series of commercial grade acids include saturated and unsaturated acids. 这些混合物可由合成的方法也可由中性产物衍生获得,例如棉油、花生油、椰子油、亚麻子油、棕榈仁油、橄榄油、玉米油、棕榈油、蓖麻油、豆油、葵花油、鲱鱼油、沙丁油和动物脂。 Mixtures of these may also be synthesized derives neutral product, e.g. cottonseed oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, soybean oil, sunflower oil, herring oil , sardine oil and tallow. 也可采用硫化的酸和酸的混合物。 Acids and acid mixtures may also be sulfurized. 除了羧酸,还可用其酐、酰氯或其酯的衍生物,最好用酸酐。 In addition to the carboxylic acid, anhydride derivative thereof can also be used, acid chloride or ester thereof, preferably with an acid anhydride. 无论如何,优先考虑的是用羧酸或混和羧酸。 In any case, priority is given to a mixture with a carboxylic acid or carboxylic acid. 一个结构式(Ⅰ)的优选羧酸是硬脂酸。 Preferably a carboxylic acid of formula (Ⅰ) is stearic acid.

除了(ⅰ),或代替(ⅰ)来改进碱土金属烃基酚盐的是掺进(ⅱ),(ⅱ)是含有36~100个碳原子的二元或多元羧酸或其酐、酰氯或酯的衍生物,最好是其酸的酐。 In addition to (i), or in lieu of (i) to improve the alkaline earth metal hydrocarbyl phenate is braced (ii), (ii) is 36 to 100 containing a binary carbon atoms or polycarboxylic acid or an anhydride, acid chloride or ester derivative, preferably the acid anhydride. 优选的(ⅱ)是聚异丁烯琥珀酸或聚异丁烯琥珀酐。 Preferred (ii) is a polyisobutene succinic acid or a polyisobutene succinic anhydride.

优选的具有结构式(Ⅰ)的羧酸、二元或多元羧酸、其酐、酰氯或其酯掺在组合物中所占的重量为大于10%到35%,最好是12~20%,例如大约为16%。 Preferred carboxylic acids, di- or polycarboxylic acids having the structure of formula (Ⅰ), the anhydride, acid chloride or ester incorporated in the composition in the proportion by weight greater than 10% to 35%, preferably 12 to 20% for example about 16%. 羧酸或其衍生物的掺进量大于10Wt%的优点在于有一个相对较低的浓缩粘度。 Carboxylic acid or its derivative braced advantage greater than 10Wt% is to have a relatively lower concentrate viscosity.

存在于组合物中碱土金属合适的量为基于组合物重量的10~20Wt%。 Is present in the composition in an amount of alkaline earth metal is suitably 10 ~ 20Wt% based on the weight of the composition.

碱土金属烃基酚盐可被硫化或不硫化,最好是硫化。 Alkaline earth metal hydrocarbyl phenate may be sulfurized or sulfurized, preferably vulcanized.

适当的硫可存在于组合物中,其量为,基于组合物的重量,1~6%,最好是1.5~3%。 Suitable sulfur may be present in the composition in an amount, based on the weight of the composition, 1 to 6%, preferably 1.5 to 3%.

组合物中还可存在适当的二氧化碳,其量为基于组合物重量的5~20%,最好是9~15%。 Suitable carbon dioxide may also be present in the composition, based on an amount of 5 to 20% by weight of the composition, preferably 9 to 15%.

组合物优选的TBN值是大于350,最好大于400。 Preferred compositions is a TBN greater than 350, preferably greater than 400.

合适的组合物具有的粘度为100℃时小于1000CSt,较佳为小于750cSt,最佳为小于500cSt(厘沲)。 Suitable compositions have a viscosity of less than 1000CSt when 100 ℃, preferably less than 750cSt, and most preferably less than 500 cSt (centistokes).

另一方面,本发明提供了一种适宜掺进成品润滑油的添加剂浓缩物,它的获得是通过在提高了的温度下将(A)、(B)、(C)、(D)、(E)和(F)进行反应;(A)是(ⅰ)烃基酚或(ⅱ)烃基酚和硫,二者取一;(B)是碱土金属碱。 Another aspect, the present invention provides a finished lubricating oil is mixed into a suitable additive concentrate, which is obtained by at elevated temperature to (A), (B), (C), (D), ( E) and (F) reacting; (a) is (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulfur, whichever one; (B) an alkaline earth metal base. 在反应中间分一次或多次在多个中介点加入均可;(C)是下列物质之一,具有2~4个碳原子的多元醇、二或三(乙到丁)二醇、亚烷基二醇烷基醚或聚亚烷基二醇烷基醚;(D)是润滑油;(E)是二氧化碳,在组分(B)的每次投入之后加进;(F)基于组合物重量的从大于2%到小于40%的充分提供的(ⅰ)或(ⅱ)二者之一,(ⅰ)是具有结构式(Ⅰ)的羧酸、或其酐、酰氯或其酯,(ⅱ)是含有36~100个碳原子的二元或多元羧酸或其酐、酰氯或其酯;组分(A)~(F)的重量比调至一定程度使得制成的浓缩物具有大于300的TBN值。 In one or more intermediate reaction was added to a plurality of intermediate points available; (C) is one of the following materials, polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri- (B to D) glycols, alkylene glycol alkyl ether or polyalkylene glycol alkyl ether; (D) a lubricating oil; (E) is carbon dioxide, added after component (B) per input; (F.) based on the composition from greater than 2% to less than 40% by weight sufficient to provide (i) or (ii) either, (i) is a carboxylic acid having the structural formula (ⅰ), or an anhydride, acid chloride or ester thereof, (ii ) is 36 to 100 containing a binary carbon atoms or polycarboxylic acid or an anhydride, acid chloride or ester thereof; weight of component (a) ~ (F) ratio is adjusted to such an extent that the concentrate is made greater than 300 the TBN value.

还有一方面,本发明提供了制备成品润滑油所用的添加剂浓缩物的工艺,该工艺包括在提高了的温度下将(A)~(F)组分进行反应,组分(A)~(F)的重量比要适于具有大于300TBN浓缩物的制备。 In yet another aspect, the present invention provides a process for preparing the additive concentrate used in the finished lubricating oil which process comprises (A) - (F.) Reacting component, component (A) at elevated temperatures - ( preparation of the concentrate is greater than 300TBN F) having a weight ratio to be adapted.

反应混合物中组分(A)是(ⅰ)烃基酚或(ⅱ)烃基酚和硫,二者之一。 The reaction mixture of component (A) is (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulfur, either. 使用组分(A)(ⅰ)时产物是碱土金属烃基酚盐,使用组分(A)(ⅱ)时产物是硫化的碱土金属烃基酚盐。 When using the component (A) (i) the product is an alkaline earth metal hydrocarbyl phenate, when using the component (A) (ii) the product is sulfurized alkaline earth metal hydrocarbyl phenate. 采用的烃基酚是前面所说过从烷基酚中衍生出所需要的烃基酚部分。 Hydrocarbyl phenol employed is that alkyl phenol collected from the aforesaid hydrocarbyl phenol moiety derived required.

碱土金属碱(组分B)适宜的是碱土金属氧化物或氢氧化物,最好是氢氧化物。 Alkaline earth metal base (component B) is suitably an alkaline earth metal oxide or hydroxide, preferably the hydroxide. 可以加入氢氧化钙,例如以熟石灰的形式。 Calcium hydroxide may be added, for example in the form of slaked lime. 优选的碱土金属是钙、镁和钡,最好是钙。 Preferred alkaline earth metals are calcium, magnesium and barium, preferably calcium. 碱土金属碱的加入量与组分(A)有关,以足够产生具有大于300,最好大于350TBN值为准。 An amount of alkaline earth metal base is added to the component (A) is related sufficient to produce greater than 300, preferably greater than 350TBN whichever. 这个量取决于储多因素,包括硫化烷基酚的性质,它高于现有技术一般的使用量。 This amount depends on a multi-reservoir factors including the nature of the sulfurized alkylphenols, which is higher than the prior art in general usage. 组分(B)对组分(A)的重量比,典型的是适于在0.2~50,最好是在0.4~10之间。 Component (B) to the weight of component (A) ratio, typically 0.2 to 50 adapted, preferably between 0.4 and 10. 碱土金属碱(B)可整体加到初始反应物中,或部分加到初始反应物中,剩余的随后以一次或多次在工艺中加入。 Alkaline earth metal base (B) may be integrally added to the initial reactants, or in part added to the initial reactants, the remaining one or more added subsequently in the process. 为了制备一种具有大于350TBN和100℃时具有小于1000cSt粘度的添加剂浓缩物,特别希望将组分(B)至少分两次,最好是多次加入,并且将组分(F)以大于,以添加剂浓缩物产品重量为准,10%的数量加入。 To prepare a 350TBN greater than 100 deg.] C and having a viscosity of less than 1000cSt additive concentrates, particularly desirable to at least twice the component (B), is preferably added several times, and the component (F) greater than, product additive concentrate weight basis, 10% of the amount added.

组分(C)是C2-C4的多元醇、二或三(乙到丁)二醇烷基醚,其中之一。 Component (C) is a C2-C4 polyhydric alcohol, di- or tri- (B to D) glycol alkyl ethers, one. 适宜的多元醇是一种二羟基醇,例如乙二醇或丙二醇,或三羟基醇,例如丙三醇。 Suitable polyhydric alcohol is a dihydric alcohol such as ethylene glycol or propylene glycol, or a trihydric alcohol, such as glycerol. 二或三(乙到丁)二醇适宜是一缩二乙二醇或二缩三乙二醇。 Di- or tri- (B to D) is suitably a diol or diethylene glycol triethylene glycol. 亚烷基二醇烷基醚或聚亚烷基二醇烷基醚适宜具有下述结构式:R(OR1)XOR2(Ⅱ)其中R是C1-C6的烷基,R1是亚烷基,R2是H或C1-C6的烷基,X是1-6的整数。 Alkylene glycol alkyl ether or polyalkylene glycol alkyl ether having the following structural formula suitable: R (OR1) XOR2 (Ⅱ) wherein R is C1-C6 alkyl group, R1 is alkylene, R2 is H or C1-C6 alkyl group, X is an integer from 1-6. 优选的具有结构式(Ⅱ)的优选溶剂包括乙二醇独甲醚或乙二醇二甲醚,一缩二乙二醇、二缩三乙二醇或三缩四乙二醇的独甲或二甲醚。 Preferred solvents preferably have a structure of formula (Ⅱ) include ethylene glycol monomethyl ether or ethylene glycol dimethyl ether, diethylene glycol, triethylene glycol or tetraethylene glycol alone or two methyl ether. 一种特别合适的溶剂是一缩二乙二醇独甲醚(CH3OCH2CH2OCH2CH2OH)。 A particularly suitable solvent is diethylene glycol monomethyl ether (CH3OCH2CH2OCH2CH2OH). 也可采用甘醇和具有结构式(Ⅱ)的二醇醚的混合物。 It may also be a mixture of glycol and glycol ethers having the structure of formula (Ⅱ) a. 在使用甘醇或结构式(Ⅱ)的二醇醚作溶剂时,优先考虑的是将无机卤化物如氯化铵和一种低级-即C1到C4的羧酸如乙酸结合使用。 When using a glycol or structural formula (Ⅱ) glycol ether as solvent, priority is given to an inorganic halide such as ammonium chloride and one lower - i.e. C1 to C4 carboxylic acid such as acetic acid in combination. 优先考虑的组分(C)是乙二醇或一缩二乙二醇独甲醚,后者与氯化铵和乙酸结合使用。 Component (C) is ethylene glycol or priority diethylene glycol monomethyl ether, the latter in combination with ammonium chloride and acetic acid.

组分(D)是润滑油,参照前面所述的添加剂浓缩物。 Component (D) is a lubricating oil additive concentrate with reference to previously described.

组分(E)是二氧化碳,它可以气态或固态,最好以气态形式加入。 Component (E) is carbon dioxide, it may be gaseous or solid, is preferably added in gaseous form. 气态形式中,适于从反应混合物中吹过。 In gaseous form, adapted blowing from the reaction mixture. 我们发现在一般情况下掺进二氧化碳的量随组分(F)的浓度的增高而增大。 We found that the amount of carbon dioxide is braced in general with increasing concentrations of component (F) is increased. 为了制备具有大于350TBN值的浓缩物,二氧化碳最好是随着每次(B)组分加入后而加入,分两次或最好是多次加入。 For the preparation of a value greater than 350TBN concentrate, carbon dioxide, preferably with each (B) is added after the addition of the component, in two or preferably more additions.

组分(F)是结构式(Ⅰ)的羧酸,含有36~100个碳原子的二或多元羧酸,或它们的酸酐、酰氯或其酯,其中的任一个,参照前述的添加剂浓缩组合物。 Component (F) is a carboxylic acid of formula (Ⅰ) containing di- or polycarboxylic acids 36 to 100 carbon atoms, or their anhydrides, acid chloride or ester thereof, any of which, with reference to the additive concentrate composition . 前述所要求提供的基于浓缩物重量的大于2%小于40%的量将是浓缩物所要求的初步概算量。 The request based on the weight of the concentrate is greater than 2% of the amount will be less than 40% of the initial estimates of the required amount of concentrate. 计算这个量时,例如,余额应考虑来自羧酸的水损耗。 When calculating this amount, for example, consider the balance of water loss from the carboxylic acid.

反应可以在稀释剂存在的条件下进行。 The reaction may be performed in the presence of a diluent. 合适的稀释剂是具有满足工序运行的挥发性液体,亦即具有的挥发性可使得在反应结束时能迅速地从反应混和物中除去。 Suitable diluents are liquids having a volatility satisfying step operation, i.e. having a volatility such that can be quickly removed from the reaction mixture at the end of the reaction. 适宜稀释剂的例子包括2-乙基乙醇、异辛醇、异庚醇和三癸醇。 Examples of suitable diluents include 2-ethyl alcohol, iso-octanol, iso-heptanol and tridecanol.

反应最好在附加组分-反应的催化剂存在的条件下进行。 The reaction is preferably additional components - the presence of a catalyst for the reaction. 无机卤化物可用作催化剂,适宜的卤化物是卤化氢。 Inorganic halides used as catalysts, the appropriate halide is hydrogen halide. 卤化铵或金属卤化物。 An ammonium halide or a metal halide. 金属卤化物的金属部分优选的是锌、铝或碱土金属,最好是钙。 Preferably the metal portion of the metal halide is zinc, aluminum or an alkaline earth metal, preferably calcium. 卤化物的卤部分最好是氯。 Halide halide moiety is preferably chloro. 优选的催化剂是氯化氢,氯化钙,氯化铵,氯化铝和氯化锌,最好是氯化钙。 Preferred catalysts are hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride. 催化剂的用量最好不大于2.0%Wt/Wt。 The amount of catalyst is preferably not more than 2.0% Wt / Wt.

组分(A)~(F)的反应及羧化反应适于在120~200℃,最好在130~165℃的高温下进行,然而,如果需要,(A)~(F)的反应的实际温度和羧化的实际温度可有所不同。 Reaction components (A) ~ (F) and the carboxylation reaction is suitably 120 ~ 200 ℃, preferably at a high temperature of 130 ~ 165 ℃, however, if desired, (A) ~ (F) reaction the actual temperature and the actual temperature may vary carboxylated. 压力可以是大气压,低于大气压或高于大气压。 The pressure may be atmospheric, subatmospheric or superatmospheric.

可用常规方法回收浓缩物,例如通过组分(C)和稀释剂(假如有)的蒸馏分离来回收。 Concentrate recovered by conventional methods, for example, be recovered by the component (C) and diluent (if any) of the distillation.

最后,优先考虑过滤所得的该浓缩物。 Finally, priority of the concentrate obtained was filtered. 一般说来,本发明的工艺将制备一种具有令人满意的粘度的浓缩物,即在100℃时粘度小于1000cSt,并能制备在100℃时粘度小于750cSt或500cSt的浓缩物。 Generally the concentrate, the process of the present invention is prepared having a satisfactory viscosity, i.e. a viscosity at 100 ℃ less than 1000cSt, and the concentrate can be prepared at 100 ℃ or 500cSt a viscosity of less than 750cSt. 此外,浓缩物一般可以具有所需要的粘度指数的特性。 In addition, it concentrates generally have desirable properties of viscosity index. 这种粘度特性有许多优点,因为它们便于浓缩物的工艺(包括过滤)。 Such viscosity characteristics have many advantages, as they are easy to process concentrate (including filtering). 因而制备100℃时粘度大于1000cSt,其TBN值一般是更高些,的浓缩物也是可能的。 Thus preparing a viscosity greater than 1000 cSt 100 deg.] C, a TBN which is generally higher, the concentrates are also possible. 过滤这样的浓缩物就带来了问题,这个问题可通过过滤前添加稀释剂和过滤后将稀释剂除去来解决。 This filtered concentrate on bringing the issue that by adding a diluent prior to filtration and filtration to remove the diluent will be resolved. 在维持TBN值大于300的情况下,高粘性浓缩物,例如在100℃时粘度大于1000cSt并且有高TBN值例如大于350的浓缩物,可进一步通过添加润滑油而被稀释,由此以利过滤。 While maintaining a TBN greater than 300, high viscosity concentrates, for example at 100 ℃ high viscosity of greater than 1000cSt and concentrate a TBN greater than 350, for example, may be further diluted by the addition of the lubricating oil, thereby to facilitate filtration .

在最后一个方面,本发明提供了一种成品润滑油组合物,它包括润滑油及足够量的前面所述的添加剂浓缩物以便提供一个0.5~120的TBN值。 In a final aspect, the present invention provides a finished lubricating oil composition, the additive concentrate comprising a lubricating oil and a sufficient amount of a previously described to provide a TBN value of from 0.5 to 120.

优先考虑的成品润滑油组合物是具有足量的添加剂浓缩物使得其TBN值为0.5~100。 Preferred compositions are finished lubricating oil additive concentrate having a TBN such that a sufficient amount is 0.5 to 100.

存在于成品润滑油中的添加剂浓缩物的量取决于最终使用它的实际情况。 It is present in the finished lubricating oil additive concentrate it depends on the end use of the actual situation. 因此,对于船用润滑油中存在的添加剂浓缩物的量来说,较合适的是足以提供的TBN值为9~100,而用于汽车发动机的润滑油来说,这个量要足以提供的TBN值为4~20。 Thus, for marine lubricating oils the amount of additive concentrate present, the more suitable is sufficient to provide a TBN of 9 to 100 and for automobile engine lubricating oil, this amount sufficient to provide a TBN 4 to 20.

成品润滑油也可以掺进有效量的一种或多种其他类型的常规润滑油添加剂,例如粘度指数改善剂,抗摩损剂,抗氧化剂,分散剂,防锈剂,倾点下降剂等这类物质;可以直接的形式或通过浓缩组合物中介物的形式掺进成品润滑油中。 Finished lubricating oil may also be braced effective amount of one or more other types of conventional lubricating oil additives, such as viscosity index improvers, anti-wear agents, antioxidants, dispersants, rust inhibitors, pour point depressants, and the like which substances; direct form or in the form of a concentrate composition interposer braced finished lubricating oil.

除了可以作为掺进润滑油组合物的添加剂使用之外,本发明的该添加剂浓缩物还可用作燃料添加剂。 In addition to use as an additive mixed into the lubricating oil compositions outside the additive concentrates of the invention are also useful as fuel additives.

本发明将通过参照下列实施例作进一步说明。 The present invention will be further illustrated by reference to the following examples.

所有实施例中都使用术语“TBN”。 All the embodiments use the term "TBN". TBN是总碱值,用ASTMD 2896的方法进行测定。 TBN is the TBN, measured by the ASTMD 2896 method. 以毫克KOH/克为单位。 In mg KOH / g units.

用ASTMD 445的方法测定粘度。 Methods of measuring the viscosity ASTMD 445.

所有实施例中,除明确说明的以外,采用的C12-烷基酚均为通过用丙烯四聚物将酚烷基化而获得的商用品。 All embodiments, except expressly stated, are used C12- alkyl phenol with propylene tetramer phenol obtained by alkylating commercially supplies through.

实施例1用料:C13-烷基酚:75克润滑油(100SN):131克石灰:82克硫:23克硬脂酸:70克氯化钙:4克2-乙基己醇:112克方法:(a)将料加热到145~165℃/700mmHg同时添加乙二醇36克,(b)混合物在165℃/700mmHg时保温一小时,(c)在165℃/1巴时加入二氧化碳40克,(d)将混和物冷却到125℃/700mmHg,(e)在125℃/700mmHg时加石灰35克,(f)将混和物加热到165℃/700mmHg并保温一小时,(g)在165℃/1巴时加二氧化碳20克,(h)在200℃/10mmHg时将产品与溶剂分离,并且,(i)将产品过滤,过滤速度要快。 Example 1 Ingredients: C13-alkyl phenol: 75 g Lubricating oil (100SN): 131 gm limestone: 82 g Sulfur: 23 g Stearic acid: 70 g Calcium chloride: 4 g 2-Ethyl hexanol: 112 g method: (a) the charge was heated to 145 ~ 165 ℃ / 700mmHg while adding 36 g of ethylene glycol, (b) the mixture was incubated at 165 ℃ / 700mmHg one hour, (c) adding carbon dioxide at 165 ℃ / 1 bar when 40 g, (d) the mixture was cooled to 125 ℃ / 700mmHg, (e) adding lime 35 g at 125 ℃ / 700mmHg, (f) the mixture was heated to 165 ℃ / 700mmHg and incubated one hour, (g) added at 165 ℃ / 1 bar, 20 g of carbon dioxide, (h) the product from the solvent at 200 ℃ / 10mmHg, and, (I) the product was filtered, the filter faster.

产品重量:粗产品:436克蒸馏物:169克过滤后的产品成分:钙:14.1%W/W硫:2.9%W/WCO2:12.4%W/WTBN:396 Weight: Crude Product: 436 g Distillate: 169 g Product composition after filtration: Calcium: 14.1% W / W Sulfur: 2.9% W / WCO2: 12.4% W / WTBN: 396

V100:308CStBPHV150:1硬脂酸:16.1%W/W本例说明:根据本发明,采用“两次加石灰”工艺可制备出具有高TBN值和合适粘度的添加剂浓缩物。 V100: 308CStBPHV150: 1 Stearic acid: 16.1% W / W of the present embodiment explained: According to the present invention, a "twice lime addition" process can be prepared having a high TBN additive concentrate and a suitable viscosity value.

实施例2用料:除了所用石灰的总量从82克增加到117克(符合于两次加料量总和)以外,其他均与实施例1相同。 Example 2 Ingredients: (conforming to twice the sum of feeding amount) than, are the same as in Example 1 except that the total amount of lime added to 117 g from 82 g other.

方法:除了步骤(c)中二氧化碳加入量从40克增到60克及省略步骤(d)、(e)、(f)和(g)之外,其余和实施例1相同。 Method: In addition to step (c) increasing the amount of carbon dioxide added from 40 g to 60 g and omitting step (d), other than (e), (f) and (g), the same as in Example 1 and the remaining embodiments. 过滤速度是慢的。 Filtration rate is slow.

产品重量:粗产品:514克过滤后的产品成分:钙:14.1%W/W硫:3.0%W/WCO2:12.3%W/WTBN:390V100:7600cSt硬脂酸:13.6%W/W本例说明:采用“一次加石灰”工艺可制备具有高TBN值的添加剂浓缩酚盐,但在本例条件下得到的产品粘度如不经润滑油稀释不能在商业应用。 Weight: Crude Product: 514 g of the filtered product ingredients: Calcium: 14.1% W / W Sulfur: 3.0% W / WCO2: 12.3% W / WTBN: 390V100: 7600cSt Stearic acid: 13.6% W / W of the present embodiment described : a "primary lime" process may be prepared having a high TBN additive concentrate phenate value, but in the present embodiment resulting conditions such as viscosity of the product can not be diluted without a lubricant in commercial applications.

实施例3用料:同实施例1。 Example 3 Charge: same as in Example 1.

方法:除了在步骤(g)中将二氧化碳从20克增到40克以及将下列步骤加在步骤(g)之后、步骤(h)和(i)之前以外,其他均同实施例1:(j)混合物被冷却到120℃,(k)在120℃时加石灰35克,(l)将混和物加热到165℃/700mmHg,以及(m)将二氧化碳50克加到混和物中。 Method: In addition to the outside before step (g) carbon dioxide will be increased from 20 g to 40 g and the following steps will be added after step (g), step (h) and (i), the other was the same as Example 1: (j ) mixture was cooled to 120 ℃, (k) 35 g of lime was added at 120 ℃, (l) the mixture was heated to 165 ℃ / 700mmHg, and (m) 50 g of carbon dioxide into the mixture.

产品重量:粗产品:484克蒸馏物:169克过滤后产品成分:钙:15.8%W/W硫:2.6%W/WCO2:15.0%W/WTBN:439V100:506cSt硬脂酸:14.5%W/W本例说明:通过本发明所述的“三次加石灰”工艺可制备具有高TBN值的添加剂浓缩物。 Weight: Crude Product: 484 g Distillate: 169 g After filtering Ingredients: Calcium: 15.8% W / W Sulfur: 2.6% W / WCO2: 15.0% W / WTBN: 439V100: 506cSt Stearic acid: 14.5% W / W this Example demonstrates: the "three lime addition" process according to the present invention is prepared having a high TBN additive concentrate can values.

实施例4用料:除了将润滑油的用量从131克增到158克及硬脂酸的用量从70克降到43克以外,其余均同实施例1。 Example 4 Ingredients: In addition to increasing the amount of lubricant used in an amount from 131 grams to 158 grams of stearic acid and from 70 g down to 43 g, the rest were the same as in Example 1.

方法:除了步骤(d)中将混和物的冷却温度从135℃变为125℃以外,其余均同实施例1。 Method: In addition to step (d) cooling the temperature in the mixture was changed from 135 ℃ 125 ℃, the rest were the same as in Example 1.

产品重量:粗产品:442克蒸馏物:155克过滤后产品成分:钙:14.1%W/W硫:2.9%W/WCO2:11.9%W/WTBN:393V100:3440cSt硬脂酸:9.8%W/W和实施例1相比较,本例说明:尽管在低于10%W/W的酸水平下仍可制备具有高TBN值的产品,但产品粘度也是高的。 Weight: Crude Product: 442 g Distillate: 155 g After filtering Ingredients: Calcium: 14.1% W / W Sulfur: 2.9% W / WCO2: 11.9% W / WTBN: 393V100: 3440cSt Stearic acid: 9.8% W / W 1 with Comparative Example, the present Example: Although the level of acid below 10% W / W of preparing a product still under high TBN values, but also high viscosity of the product.

实施例5用料:C12-烷基酚:35.3克润滑油(100SN):131克硫:14.7克氯化钙:4.0克硬脂酸:109.1克2-乙基己醇:224克方法:(a)将混和物加热到120℃,(b)在120℃/2″Hg真空时加石灰82克,(c)在145~165℃/2″Hg时加乙二醇36克,(d)将混和物在165℃/2″Hg保持一小时,(e)加二氧化碳40克,(f)将混和物冷却到130℃并且于130℃/2″Hg加石灰35克,(g)将混和物在165℃/2″Hg时保持一小时,(h)在165℃时加二氧化碳20克,(i)在200℃/30″Hg时将溶剂从产品中分离,以及(j)将产品过滤。 Example 5 Ingredients: C12-alkylphenol: 35.3 g lubricant (100SN): 131 g of sulfur: 14.7 g Calcium chloride: 4.0 g Stearic acid: 109.1 g 2-Ethyl hexanol: 224 g Method :( a) the mixture was heated to 120 ℃, (b) at 120 ℃ / 2 "Hg vacuum when lime 82 g, (c) at 145 ~ 165 ℃ / 2" Hg in 36 g of ethylene glycol was added, (d) the mixture was "Hg for one hour, (e) adding carbon dioxide 40 g, (f) the mixture was cooled to 130. deg.] C and at 130 ℃ / 2" at 165 ℃ / 2 35 g of Hg lime, (g) the mixture "holding Hg in one hour, (h) at 165 deg.] C was added carbon dioxide 20 g, (I) at 200 ℃ / 30" was 165 ℃ / 2 Hg when the solvent is separated from the product, and (j) the product was filtered .

产品重量:粗产品:397克蒸馏物:245克过滤后产品成分:钙:13.6%W/W硫:1.2%W/WCO2:13.9%W/WTBN:376V100:142cStV40:1881cStVI:180羧酸:27.5%W/W本例说明:加入27.5%W/W的硬脂酸,基于终产物重量,可获得具有合适粘度的高TBN值产品。 Weight: Crude Product: 397 g Distillate: 245 g Product Composition After Filtration: Calcium: 13.6% W / W Sulfur: 1.2% W / WCO2: 13.9% W / WTBN: 376V100: 142cStV40: 1881cStVI: 180 Carboxylic acid: 27.5 % W / W of the present embodiment described: addition of 27.5% W / W of stearic acid, based on the weight of the final product is obtained having a suitable viscosity value high TBN products.

实施例6用料:除了将C12-烷基酚的用量从35.3克降到15.6克及将硬脂酸用量从109.1克增到128.7克以外,其余均同实施例5。 Example 6 Ingredients: In addition to the amount of alkylphenol C12- down from 35.3 g to 15.6 g and the amount of stearic acid increased from 109.1 g to 128.7 g, the rest were the same as in Example 5.

方法:同实施例5。 Method: Example 5 the same embodiment.

产品重量:粗产品:416克蒸馏物:242克过滤后产品成分:钙:14.5%W/W硫:1.0%W/WCO2:13.6%W/WTBN(毫克KOH/克):395V100:255cStV40:3100cStVI:221硬脂酸:30.9%W/W本例说明:加入30.9%W/W的硬脂酸即能得到具有高TBN值的产品。 Weight: Crude Product: 416 g Distillate: 242 g Product Composition After Filtration: Calcium: 14.5% W / W Sulfur: 1.0% W / WCO2: 13.6% W / WTBN (mg KOH / g): 395V100: 255cStV40: 3100cStVI : 221 stearic acid: 30.9% W / W of the present embodiment described: addition of 30.9% W / W of stearic acid that can obtain a product having a high TBN value.

实施例7~13用料:如表所示。 Examples 7 to 13 Charge: As shown in Table.

方法: method:

(a)把烷基酚、润滑油、氯化钙、硬脂酸和2-乙基己醇构成的混和物加热到120℃/700mmHg,(b)在120℃/700mmHg时加石灰(c)在145℃~165℃/700mmHg时加乙二醇并将混和物在165℃/700mmHg保持一小时,(d)在165℃/1巴时加二氧化碳,(e)在200℃/10mmHg回收溶剂,及(f)将产物过滤。 (A) The alkylphenols, lubricating oil, a mixture of calcium chloride, stearic acid, and 2-ethylhexyl alcohol was heated to constituting 120 ℃ / 700mmHg, (b) at 120 ℃ / 700mmHg lime (c) ethylene glycol was added and the mixture was kept at 145 ℃ ~ 165 ℃ / 700mmHg at 165 ℃ / 700mmHg one hour, (d) CO2 is added at 165 ℃ / 1 when the bar, (e) at 200 ℃ / 10mmHg recovery of the solvent, and (f) the product was filtered.

产品重量:如表所示。 Product weight: As shown in Table.

过滤后产品成分:如表所示。 Product Composition After Filtration: As shown in Table.

本例说明:采用“一次加石灰”工艺对于硬脂酸含量占浓缩物总重量的2.6~29.7%的整个范围内均可制备具有高于300TBN值的添加剂浓缩物。 This example illustrates: a "primary lime addition" process for the content of stearic acid accounted for the entire range of 2.6 to 29.7% of the total weight of the concentrate may be prepared having a higher value 300TBN additive concentrate.

表实施例 7 8 9 10 11 12 13产品的硬脂酸含量(%W/W) 2.6 7.7 12.9 18.2 18.0 23.0 29.7用料量(克)润滑油 131 131 131 131 131 131 131C12-烷基酚135 115 95 75 75 55 36石灰 82 82 82 82 82 82 85硫 23 23 23 23 23 23 15硬脂酸 10 30 50 70 70 90 113二氯化钙 4 4 4 4 4 4 4 7 8 9 10 Content (% W / W) Example 11 12 13 Product Table embodiment stearate 2.6 7.7 12.9 18.2 18.0 23.0 29.7 amount of materials used (g) lubricating oil 131 131 131 131 131 131 131C12- alkylphenol 135115 9575755536 lime 82828282828285 sulfur 23232323232315 stearate 103,050,707,090,113 calcium dichloride 4,444,444

(b)加石灰70克,(c)将混合物从145℃加热到165℃/700mmHg并加乙二醇32克,(d)将混和物在165℃/700mmHg时保持5分钟,(e)在165℃/1巴时加二氧化碳44克,(f)将混和物冷却到120℃并加石灰60克,(g)将混和物在165℃/700mmHg时保持5分钟,(h)在165℃/1巴时加二氧化碳44克,(i)在200℃/10mmHg时通过分离回收溶剂,以及(j)将产品过滤。 (B) 70 g of lime was added, (c) heating the mixture from 145 deg.] C to 165 ℃ / 700mmHg and added 32 g of ethylene glycol, (d) The mixture was held at 165 ℃ / 700mmHg 5 minutes, (e) the 165 ℃ / 1 when the bar plus carbon dioxide 44 g, (f) the mixture was cooled to 120 deg.] C and lime 60 g, (g) the mixture was held at 165 ℃ / 700mmHg 5 minutes, (h) at 165 ℃ / 1 bar was added 44 grams of carbon dioxide, (I) at 200 ℃ / 10mmHg product recovered by separating the solvent by filtration, and (j).

产品重量:粗产品:408克蒸馏物:245克过滤后产品成分:钙:16.0%W/W硫:2.6%W/WCO2:14.6%W/WTBN:450V100:488cSt硬脂酸:14.5%W/W本例说明:用本发明的工艺可制备具有高达450TBN值及令人满意粘度的添加剂浓缩物。 Weight: Crude Product: 408 g Distillate: 245 g After filtering Ingredients: Calcium: 16.0% W / W Sulfur: 2.6% W / WCO2: 14.6% W / WTBN: 450V100: 488cSt Stearic acid: 14.5% W / W this example illustrates: the process of the present invention may be prepared having a satisfactory and high viscosity values ​​450TBN additive concentrate.

实施例15用料:C12-烷基酚:64克润滑油(100SN):111克硫:20克硬脂酸:59克乙酸:2克氯化铵:3克一缩二乙二醇独甲醚:40克方法:(a)将料加热到120℃/100mmHg,(b)加石灰70克,(c)将混和物从145℃加热到165℃/700mmHg,同时加入一缩二乙二醇独甲醚90克,(d)将混和物在165℃/700mmHg时保持一小时,(e)加二氧化碳34克,(f)将混和物冷却至120℃并加石灰30克,(g)将混和物在165℃/700mmHg时保持一小时,(h)加二氧化碳17克,(i)在200℃/10mmHg时通过分离回收溶剂,以及(j)将产品过滤。 Example 15 Ingredients: C12-alkyl phenol: 64 g Lubricating oil (SN 100): 111 g of sulfur: 20 g Stearic acid: 59 g of acetic acid: 2 g of ammonium chloride: 3 g of diethylene glycol alone A ether: 40 g method: (a) the charge was heated to 120 ℃ / 100mmHg, (b) 70 g of lime was added, (c) the mixture was heated from 145 deg.] C to 165 ℃ / 700mmHg, while adding a diethylene glycol monomethyl ether 90 g, (d) the mixture was held at 165 ℃ / 700mmHg one hour, (e) was added 34 grams of carbon dioxide, (f) the mixture was cooled to 120 deg.] C and 30 grams of lime was added, (g) the the mixture was kept at 165 ℃ / 700mmHg one hour, (h) was added 17 grams of carbon dioxide, (I) at 200 ℃ / 10mmHg separated and recovered by the solvent, and (j) the product was filtered.

产品重量:粗产品:361克蒸馏物:146克 Weight: Crude Product: 361 g Distillate: 146 g

2-乙基已醇 112 112 112 112 112 112 112乙二醇 36 36 36 36 36 36 36CO228 28 28 28 40 40 40产品重量(克) 389 391 386 385 389 391 382蒸馏物(克) 158 159过滤后产品成分钙(%) 11.2 11.0 11.1 11.2 11.0 11.1 11.1硫(%) 3.7 3.6 3.4 3.0 3.0 2.7 1.6CO2(%) 6.5 6.9 7.1 6.5 8.2 10.8 10.2TBN 314 310 311 310 308 312 302V100(cSt) 286 190 163 160 109 128 84实施例14用料:C12-烷基酚:64克润滑油(100SN):111克硫:20克硬脂酸:59克氯化钙:4克2-乙基己醇:190克方法:(a)将料加热到120℃/700mmHg, After ethyl 112 112 glycol 112,112,112,112,112 36 36 36 36 36 36 36CO228 28 28 28 40 40 40 Weight (g) 389 391 386,385,389,391,382 distillate (g) was filtered alcohol 158159 calcium product composition (%) 11.2 11.0 11.1 11.2 11.0 11.1 11.1 sulfur (%) 3.7 3.6 3.4 3.0 3.0 2.7 1.6CO2 (%) 6.5 6.9 7.1 6.5 8.2 10.8 10.2TBN 314 310 311 310 308 312 302V100 (cSt) 286 190 163 160 10912884 Example 14 Ingredients: C12-alkyl phenol: 64 g lubricating oil (SN 100): 111 g of sulfur: 20 g stearic acid: 59 g calcium chloride: 4 g 2-ethyl hexanol: 190 g method: (a) the charge was heated to 120 ℃ / 700mmHg,

过滤后产品成分:钙:14.1%W/W硫:2.7%W/WCO2:12.4%W/WTBN:394V100:164cSt硬脂酸:16.3%W/W本例说明:本发明工艺中,一缩二乙二醇独甲醚可用作组分(c)以及氯化铵用作催化剂。 Product Composition After Filtration: Calcium: 14.1% W / W Sulfur: 2.7% W / WCO2: 12.4% W / WTBN: 394V100: 164cSt Stearic acid: 16.3% W / W This Example demonstrates: the process of the present invention, dipropylene ethylene glycol monomethyl ether used as component (c) and ammonium chloride as catalyst.

实施例16用料:C12-烷基酚:64克润滑油(100SN):73克C13-直链α烯:38克硫:23克硬脂酸:59克氯化钙:3克2-乙基己醇:190克方法:除了在步骤(c)中用乙二醇(31克)代替一缩二乙醇独甲醚(90克)以及步骤(d)和(g)中混和物在165℃/700mmHg时保持的时间由一小时变为10分钟以外,其他均同实施例15。 Example 16 Ingredients: C12-alkyl phenol: 64 g Lubricating oil (100SN): 73 g of linear α C13- alkenyl: 38 g Sulfur: 23 g Stearic acid: 59 g Calcium chloride: 3 g of 2-B hexanol: 190 g method: ethanol except that dipropylene monomethyl ether (90 g) and the step (d) and (g) in step (c) with ethylene glycol (31 g) and the mixture was 165 ℃ the holding time was changed from one hour / 700mmHg 10 minutes, other embodiments are the same in Example 15.

产品重量: product weight:

粗产品:373克蒸馏物:239克过滤后产品成分:钙:14.4%W/W硫:2.3%W/WCO2:13.3%W/WTBN:405V100:460CSt硬脂酸:15.8%W/W本例说明:长碳链α烯烃可在反应中被结合。 The crude product: 373 g Distillate: 239 g Product Composition After Filtration: Calcium: 14.4% W / W Sulfur: 2.3% W / WCO2: 13.3% W / WTBN: 405V100: 460CSt Stearic acid: 15.8% W / W of the present embodiment Description: long carbon-chain α-olefin may be incorporated in the reaction.

实施例17用料:除了采用具有500的Mn的聚异丁烯(38克)代替C18-α烯(38克)以外,其余均同实施例16。 Example 17 Ingredients: except that polyisobutylene (38 g) having Mn 500 in place of C18-α-ene (38 g), the rest were the same as Example 16.

方法:同实施例16。 Method: same as in Example 16.

产品重量:粗产物:363克蒸馏物:246克过滤后产物成分:钙:14.3%W/W硫:2.8%W/WCO2:13.8%W/WTBN:406V100:697cStV40:26,600cSt Weight: Crude product: 363 g Distillate: 246 g product composition after filtration: Calcium: 14.3% W / W Sulfur: 2.8% W / WCO2: 13.8% W / WTBN: 406V100: 697cStV40: 26,600cSt

VI:175硬脂酸:16.3%W/W本例说明聚异丁烯可被反应结合。 VI: 175 Stearic acid: 16.3% W / W of the present embodiment can be explained polyisobutylene binding reaction.

实施例18用料:C12-烷基酚:55.2克润滑油(100SN):131克硫:23克氯化钙:4克动物脂肪酸:89.8克2-乙基己醇:112克方法:除省略步骤(f)、(g)和(h)以外,即采用“一次性加石灰”工艺,其余均同实施例5。 Example 18 Ingredients: C12-alkylphenol: 55.2 g lubricant (100SN): 131 g of sulfur: 23 g Calcium chloride: 4 g Tallow Fatty Acid: 89.8 g of 2-ethyl hexanol: 112 g Method: In addition to omit except step (f), (g) and (H), i.e., a "disposable lime" process, Example 5 the rest were the same embodiment.

产品重量:粗产品:396克蒸馏物:151克过滤后产品成分:钙:10.8%W/W硫:3.1%W/WCO2:11.3%W/WTBN:305V100:388cStV40:20,000cSt Weight: Crude Product: 396 g Distillate: 151 g Product Composition After Filtration: Calcium: 10.8% W / W Sulfur: 3.1% W / WCO2: 11.3% W / WTBN: 305V100: 388cStV40: 20,000cSt

VI:101羧酸:22.7%W/W本例说明可采用动物脂肪酸来获得高TBN值的浓缩添加剂。 VI: 101-carboxylic acid: 22.7% W / W of the present embodiment described tallow fatty acid may be employed to obtain high TBN additive concentrates value.

对比实验用料:C12-烷基酚:75克润滑油(100SN):131克硫:23克氯化钙:4克乙酸:15克2-乙基己醇:112克方法:步骤(a)~(d)同实施例5。 Comparative Experiment materials: C12-alkyl phenol: 75 g Lubricating oil (100SN): 131 g of sulfur: 23 g Calcium chloride: 4 g of acetic acid: 15 g 2-Ethyl hexanol: 112 g Method: step (a) ~ (d) in Example 5. 此后混和物成为粘稠的不均匀物质。 Thereafter the mixture became a viscous substance unevenness. 搅拌无效,随着冷却混和物变成凝胶状。 Invalid stirring, the mixture was cooled with become gelatinous. 反应中止。 The reaction was quenched.

这个实验说明不能把乙酸作为本发明工艺所用的羧酸。 This experiment can be described as the acid used in the process of the invention the carboxylic acid.

实施例19用料:C12-烷基酚:135克润滑油(100SN):131克石灰:82克硫:23克硬脂酸:10克氯化钙:4克方法: Example 19 Ingredients: C12-alkyl phenol: 135 g lubricant (100SN): 131 gm limestone: 82 g Sulfur: 23 g Stearic acid: 10 g Calcium chloride: 4 g Method:

(a)将料加热到145℃/700mmHg并加入异辛醇112克,(b)将混和物从145℃加热到165℃/700mmHg并加乙二醇36克,(c)将混和物于165℃/700mmHg保持一小时,(d)在165℃/1巴加二氧化碳28克,(e)在210℃/1巴时通过分离回收溶剂,以及(f)将产品过滤。 (A) The charge was heated to 145 ℃ / 700mmHg was added 112 grams of isooctanol, (b) The mixture was heated from 145 deg.] C to 165 ℃ / 700mmHg and added 36 g of ethylene glycol, (c) the mixture was at 165 ℃ / 700mmHg for one hour, (d) at 165 ℃ / 1 Baga 28 grams of carbon dioxide, (e) at 210 ℃ / 1 bar through the separation and recovery of the solvent, and (f) the product was filtered.

产品重量:粗产品:380克蒸馏物:144克过滤后产品成分:钙:10.8%W/W硫:3.6%W/WCO2:6.0%W/WTBN:301V100:216cSt硬脂酸:2.6%W/W Weight: Crude Product: 380 g Distillate: 144 g After filtering Ingredients: Calcium: 10.8% W / W Sulfur: 3.6% W / WCO2: 6.0% W / WTBN: 301V100: 216cSt Stearic acid: 2.6% W / W

Claims (30)

1.一种适于掺进成品润滑油组合物的添加剂浓缩物,该添加剂浓缩物包括:(a)润滑油,(b)一种可溶于润滑油的硫化或非硫化的钙、镁和钡的烃基酚盐,该酚盐是通过反应掺进2%以上,40%以下(基于浓缩物总重量)的下列物质之一而得到改进的:(i)至少一种具有结构式(Ⅰ)的羧酸, An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: (a) lubricating oil, (b) A lubricating oil soluble sulfurized or sulfurized calcium and magnesium, and barium hydrocarbyl phenate, by reacting the phenate is braced 2% or more than 40% (based on total weight of concentrate) of one of the following materials and improved: (i) at least one having the structure of formula (ⅰ) of carboxylic acid, 其中R是C10-C24的烷基或链烯基且R1是H或C1-C4的烷基或-CH2-COOH,或者是该酸的酐或酯,(ii)含有36~100个碳原子的二元或多元酸或其酐或酯,该浓缩物的TBN值大于300,在100℃下的粘度小于1000cSt。 Wherein R is a C10-C24 alkyl or alkenyl group and R1 is H or C1-C4 alkyl or -CH2-COOH, or an anhydride or ester of the acid, (ii) contains 36 to 100 carbon atoms, di- or polycarboxylic acid, anhydride or ester thereof, TBN of the concentrate is greater than a value of 300, a viscosity at 100 deg.] C is less than 1000cSt.
2.根据权利要求1的添加剂浓缩物,其中润滑油的量占组合物重量的10~90%。 2. The additive concentrate according to claim 1, wherein the lubricating oil 10 to 90% by weight of the total composition.
3.根据权利要求1或2的添加剂浓缩物,其中的烃基酚盐为钙烃基酚盐。 3. The additive concentrate as claimed in claim 1 or 2, wherein the hydrocarbyl phenate is a calcium hydrocarbyl phenate.
4.根据上述任一项权利要求的添加剂浓缩物,其中的烃基酚盐是硫化的烃基酚盐。 According to any preceding claim additive concentrate, wherein the hydrocarbyl phenate is a sulfurized hydrocarbyl phenate.
5.根据上述任一项权利要求的添加剂浓缩物,其中可溶于油的烃基酚盐中的烃基酚部分由至少一种烷基酚衍生,烷基酚的烷基含有9~28个碳原子。 According to any preceding claim additive concentrate, wherein the hydrocarbyl portion of the oil-soluble phenolic hydrocarbyl phenate is derived from at least one alkyl phenol, alkylphenol alkyl group contains 9 to 28 carbon atoms .
6.根据权利要求5的添加剂浓缩物,其中烃基酚部分是由丙烯四聚物使酚烷基化所得C12-烷基酚衍生的。 6. The additive concentrate according to claim 5, wherein the moiety is a hydrocarbyl phenol propylene tetramer phenol alkylation of the resulting C12- alkyl phenols derived.
7.根据权利要求6的添加剂浓缩物,其中在结构式(Ⅰ)的羧酸中R是C10-C24的直链烷基且R1是H。 7. The additive concentrate according to claim 6, wherein the carboxylic acid of formula (Ⅰ) in which R is a linear C10-C24 alkyl and R1 is H.
8.根据权利要求1~6中任何一项的添加剂浓缩物,其中掺进具有结构式(Ⅰ)的羧酸的混合物,该混合物是一系列商业级酸,包括饱和及非饱和酸。 According to claim 1 to 6 additive concentrate according to any one of claims, wherein there is incorporated a mixture of carboxylic acids having the structural formula (Ⅰ), which mixture is a series of commercial grade acids, including saturated and unsaturated acids.
9.根据权利要求1~6中任一项的添加剂浓缩物,其中掺进硬脂酸。 9. The additive concentrate of any one of claims 1 to 6, wherein there is incorporated stearic acid.
10.根据权利要求1~6中任一项的添加剂浓缩物,其中掺进具有36~100个碳原子的二元或多元羧酸或其酐。 10. The additive concentrate of any one of claims 1 to 6, wherein there is incorporated with 36 to 100 carbon atoms, dicarboxylic or polycarboxylic acids or anhydrides.
11.根据权利要求10的添加剂浓缩物,其中掺有聚异丁烯琥珀酸或聚异丁烯琥珀酸酐。 11. The additive concentrate of claim 10, wherein the doped polyisobutylene succinic acid or polyisobutylene succinic anhydride.
12.根据上述任一项权利要求的添加剂浓缩物,其中掺进组分(b)的(ⅰ)或(ⅱ)的量为浓缩物重量的大于10%~35%(重量)。 According to any preceding claim additive concentrate, wherein the amount of (i) or (ii) is braced component (b) is more than 10% by weight of concentrate to 35% (by weight).
13.根据权利要求12的添加剂浓缩物,其中掺进组分(b)的(ⅰ)或(ⅱ)的量为浓缩物重量的12~20%(重量)。 13. The additive concentrate according to claim 12, wherein the amount of (i) or (ii) is braced component (b) is (by weight) 12 to 20% by weight of the concentrate.
14.根据上述任一项权利要求的添加剂浓缩物,其中浓缩物的TBN值大于350。 According to any preceding claim additive concentrate, wherein the concentrate is a TBN greater than 350.
15.根据权利要求13的添加剂浓缩物,其中浓缩物的TBN值大于400。 15. The additive concentrate according to claim 13, wherein a TBN greater than 400 concentrate.
16.根据上述任一项权利要求的添加剂浓缩物,其中在100℃下粘度小于500cSt。 16. any preceding claim additive concentrate, wherein the viscosity at 100 deg.] C less than 500cSt.
17.一种适于掺进成品润滑油的添加剂浓缩物,该浓缩物可以在高温下于催化剂存在下将下列物质进行反应而得到:(A)(ⅰ)烃基酚或(ⅱ)烃基酚和硫,(B)钙、镁或钡碱,在反应中既可一次全加入到初始反应剂中又可部分地加到初始反应剂中,而将剩余部分一次或多次在后续阶段中加入。 17. A method suitable for incorporation into a finished lubricating oil additive concentrates, the concentrate may be in the presence of a catalyst of the following substances in the reaction at elevated temperature: (A) (ⅰ) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulfur, (B) a calcium, magnesium or barium base, either all at once in the reaction is added to the initial reactants turn partly added to the initial reactants, and the remaining portion is added in one or more subsequent stages. (C)C2-C4的多元醇,二或三(C2-C4)二醇,亚烷基二醇烷基醚或聚亚烷基二醇烷基醚,(D)润滑油,(E)二氧化碳,随(B)组分的每次加入后添加,和(F)其量足以达到浓缩物重量2%以上,40%以下的(ⅰ)具有结构式(Ⅰ)的羧酸或其酐或酯,或(ⅱ)含有36~100个碳原子的二元或多元羧酸或其酐或酯组分(A)对(F)的重量比要使浓缩物的TBN值大于300。 (C) C2-C4 polyhydric alcohols, di- or tri (C2-C4) glycol, an alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) the lubricating oil, (E) carbon dioxide , with (B) is added after each addition of component, and (F) in an amount sufficient to reach more than 2% by weight was concentrated to 40% of (i) having the structural formula (ⅰ) carboxylic acid or anhydride or ester, or (ii) containing a dicarboxylic or polycarboxylic acids or their anhydrides or ester component is 36 to 100 carbon atoms (a) by weight of (F) than a TBN greater than 300 make the concentrate.
18.根据权利要求1~16中任一项的添加剂浓缩物的制备方法,该方法包括在高温下将下列物质进行反应:(A)(ⅰ)烃基酚或(ⅱ)烃基酚和硫,(B)钙、镁或钡碱,在反应中既可一次全加入到初始反应剂中又可部分地加到初始反应剂中,而将剩余部分一次或多次在后续阶段中加入,(C)C2-C4的多元醇,二或三(C2-C4)二醇,亚烷基二醇烷基醚或聚亚烷基二醇烷基醚,(D)润滑油(E)二氧化碳,随(B)组分的每次加入后添加,和(F)其量足以达到浓缩物重量2%以上,40%以下的(ⅰ)具有结构方(Ⅰ)的羧酸或其酐或酯,或(ⅱ)含有36~100个碳原子的二元或多元羧酸或其酐或酯组分(A)对(F)的重量比要使浓缩物的TNB值大于300。 18. A method for preparing an additive concentrate according to any one of claims 1 to 16, which comprises the following substances at elevated temperature: (A) (ⅰ) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulfur, ( B) a calcium, magnesium or barium base, either all at once in the reaction is added to the initial reactants turn partly added to the initial reactants, and the remaining portion is added in one or more subsequent stages, (C) C2-C4 polyhydric alcohols, di- or tri (C2-C4) glycol, an alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) the lubricating oil (E) carbon dioxide, with (B ) is added after each addition of component, and (F) in an amount sufficient to reach more than 2% by weight of the concentrate, of 40% or less of (i) the structure side (ⅰ) carboxylic acid or anhydride or ester, or (ii ) containing a dicarboxylic or polycarboxylic acids or their anhydrides or ester component (a) 36 ~ 100 weight of carbon atoms (F) is greater than 300 than the value so TNB concentrate.
19.根据权利要求18的方法,其中组分(B)是石灰。 19. The method according to claim 18, wherein the component (B) is lime.
20.根据权利要求18或19的方法,其中组分(B)对组分(A)的重量比为0.4~10。 20. The method according to claim 18 or claim 19, wherein the component (B) to the weight of component (A) is 0.4 to 10.
21.根据权利要求18~20中任一项的方法,其中组分(C)是乙二醇。 21. The method of any one of 18 to 20 claims, wherein the component (C) is ethylene glycol.
22.根据权利要求18~20中任一项的方法,其中组分(C)是一缩二乙二醇独甲醚。 22. The method of any one of 18 to 20 claims, wherein the component (C) is dipropylene glycol monomethyl ether.
23.根据权利要求18~22中任一项的方法,其中二氧化碳(组分(E))随两次或多次加组分(B)的每次添加之后而加入。 22 23. A method according to any one of claims 18 to, wherein after the carbon dioxide (component (E)) plus twice or more with the component (B) is added each time to join.
24.根据权利要求18~23任一项的方法,其中存在稀释剂。 24. The method according to any one of claims 18 to 23, wherein the presence of a diluent.
25.根据权利要求18~24中任一项的方法,其中催化剂为无机卤化物。 25. The method of any one of 18 to 24 claim, wherein the catalyst is an inorganic halide.
26.根据权利要求25的方法,其中所说的无机卤化物催化剂的卤化部分为氯。 26. The method according to claim 25, wherein the halide portion of said inorganic halide catalyst is chloride.
27.根据权利要求18-26中任一项的方法,其中催化剂是氯化钙。 27. The method according to any one of claims 18-26, wherein the catalyst is calcium chloride.
28.成品润滑油组合物,其中包括润滑油和其量足以使TBN达到0.5~120的权利要求1-16所述添加剂浓缩物。 28. A finished lubricating oil composition which comprises lubricating oil and an amount sufficient to achieve TBN claimed in claim 0.5-120 1-16 additive concentrate.
29.根据权利要求28的成品润滑油组合物,其中润滑油为船用润滑油并有其量足以使TBN达到9~100的添加剂浓缩物存在。 29. A finished lubricating oil composition according to claim 28, wherein the lubricating oil is a marine lubricating oil and an amount sufficient to have a TBN additive concentrate reached 100 ~ 9 is present.
30.根据权利要求28的成品润滑油组合物,其中润滑油为汽车发动机用润滑油并有其量足以使TBN达到4~20的添加剂浓缩物存在。 30. A finished lubricating oil composition according to claim 28, wherein the lubricant is an automobile engine lubricating oil and an amount sufficient to have a TBN additive concentrate reached 4 to 20 is present.
CN87108239A 1986-11-29 1987-11-29 Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof CN1015642B (en)

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