CN1012074B - Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereof - Google Patents

Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereof

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Publication number
CN1012074B
CN1012074B CN87108344A CN87108344A CN1012074B CN 1012074 B CN1012074 B CN 1012074B CN 87108344 A CN87108344 A CN 87108344A CN 87108344 A CN87108344 A CN 87108344A CN 1012074 B CN1012074 B CN 1012074B
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method according
weight
concentrate
alkaline earth
earth metal
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CN87108344A (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

一种适于掺入成品润滑油组合物中的添加剂浓缩物,该浓缩物包括:(a)润滑油;(b)能溶于润滑油经掺入大于2%至35%(以组合物的重量为基准)的(i)或(ii)而改性的硫化烃基酚碱的金属盐。 Suitable for incorporation in a finished lubricating oil composition an additive concentrate, the concentrate comprising: (a) lubricating oil; (b) can be dissolved in the lubricating oil by the incorporation of greater than 2 to 35% (in the composition weight basis) of (i) or (ii) modified by alkali metal salts of sulfurized hydrocarbyl phenol. (i)为至少一种具有分子式(I)的羧酸。 (I) is at least of formula (I) having a carboxylic acid. 式中R是C Wherein R is a C

Description

本发明通常涉及硫化烃基酚碱土金属盐,以及该盐的制备方法和它们作为润滑油添加剂的应用。 The present invention relates generally to sulfurized alkaline earth metal hydrocarbyl phenol, and methods for preparing the salts and their use as lubricating oil additives. 本发明特别涉及具有高总碱值(TBN)和适用粘度的含有硫化烃基酚碱土金属盐的组合物,以及以低总碱值(TBN)的硫化烃基酚碱土金属制备这种组合物的方法。 The present invention particularly relates to a method for preparing a high total base number (TBN of) the viscosity of the composition and application of sulfurized hydrocarbyl phenol containing alkaline earth metal salt, and a low total base number (TBN of) an alkaline earth metal sulfurized hydrocarbyl phenol such compositions.

在内燃机中,常常有副产物从燃料室与活塞的缝隙中漏出并与润滑油掺和。 In an internal combustion engine, there is often a byproduct of the fuel leaking from the gap in the piston chamber and blended with the lubricating oil. 许多这种副产物在润滑油中形成酸性物质。 Many such formation of acid by-products in the lubricating oil. 特别是在烧高硫含量的低级燃料的柴油机中,由于燃烧而产生了腐蚀性酸,这种与润滑油掺和的酸可能有由硫氧化而得到的硫酸,由燃料中卤铅清除剂所衍生的氢卤酸和由燃烧室内大气氮的氧化所产生的含氮酸。 Particularly in diesel engines burning high-sulfur fuels in the lower, the combustion is generated corrosive acids, which acids may be blended with the lubricating oil has a sulfur acid obtained by oxidizing, by a halogen lead scavengers in the fuel is hydrohalic acids derived from the acid and nitrogen oxide NOx combustion in the chamber atmosphere produced. 这些酸导致了淤渣的沉积、轴承的腐蚀,并使得发动机零部件快速磨损从而导致发动机的早期破裂。 These acids cause deposition of sludge and corrosion of the bearings and engine parts that wear quickly resulting in early breakage of the engine.

通常用于中和这些酸性物质并用于分散润滑油中淤渣的一类化合物是硫化烷基酚金属盐,其中的金属是一种碱土金属,例如钙、镁或钡。 One class of compounds commonly used to neutralize these acidic substances and for dispersing the sludge in the lubricating oil is sulfurized alkylphenol metal salts wherein the metal is an alkaline earth metal such as calcium, magnesium or barium. 目前不但“一般”的硫化烷基酚碱土金属盐被使用,而且“高碱性”硫化烷基酚碱土金属盐也被使用,术语“高碱性”通常用于描述下列的硫化烷基酚碱土金属盐,即该盐中碱土金属部分的当量值与酚部分的当量值之比大于1,通常大于1.2,也可以等于4.5或更高。 Currently only "normal" alkaline earth metal sulfurized alkylphenol is used, and "high overbased" alkaline earth metal sulfurized alkylphenol is also used, the term "overbased" is generally used to describe the following alkaline sulfurized alkylphenols salts, i.e., when the value when the value of the ratio of the alkaline earth metal salt of the phenol moiety of the portion is greater than 1, typically greater than 1.2, can also be equal to 4.5 or higher. 相反,在“一般”的烷基酚碱土金属盐中,碱土金属部分与酚部分的当量比是1。 In contrast, in the "general" alkylphenol alkaline earth metal salts, the alkaline earth metal moiety to phenol portion is an equivalent ratio. 因此,“高碱性”物质含有比相应的“一般”物质高20%以上的过量碱土金属。 Thus, the "overbased" material contains more than 20% higher than the corresponding "normal" alkaline earth metal excess material. 因此,“高碱性”硫化烷基酚碱土金属盐比相应的“一般”烷基酚碱土金属盐具有更高中和酸性物质的能力。 Thus, the "overbased" alkaline earth metal sulfurized alkylphenol and an acidic substance having a higher capacity than the corresponding "normal" alkaline earth metal alkyl phenols.

现有工艺讲授了许多制备“一般”或“高碱性”硫化烷基酚金属盐的方法。 Prior art teaches many methods for preparing "general" or "overbased" sulfurized alkylphenol metal salts. 其中有一种制备“高碱性”硫化烷基酚盐的方法通常称之为“一步石灰加入法”工艺,该工艺包括烷基酚在润滑油、硫磺、羟基化合物和过量碱土金属氢氧化物(为中和烷基酚所需的上述化学计量比)的存在下反应,生成一种中间产物,然后碳酸化,拔头蒸馏(以除去未反应的羟基化合物)并过滤。 Wherein there is a method of preparing "overbased" sulfurized alkylphenol process commonly referred to as "lime-step addition method", the lubricating oil in the process include alkylphenol, sulfur, a hydroxy compound and an excess of alkaline earth metal hydroxides ( reaction in the presence of the above-described alkyl phenol and the desired stoichiometric ratio) to generate an intermediate product, and then carbonated, topped by distillation (to remove unreacted hydroxy compound) and filtered. 中间产物的生成伴随着粘度的明显增加,而后续碳酸化则将粘度降低到一个较低值,伴随中间产物生成而出现的粘度增加是不希望有的,因为这将使反应混合物变得难以搅拌而对后续反应不利。 Produce an intermediate product is accompanied by a marked increase in viscosity while the subsequent carbonation will reduce the viscosity to a low value, the intermediate product generated concomitant increase viscosity occurs it is undesirable, as it will become difficult to stir the reaction mixture was The adverse subsequent reaction. 然而这种粘度的增加通过在反应中掺入少量碱土金属氢氧化物可以控制到一个适宜值,高碱性烷基酚盐产物必然要具有已降低的中和能力。 However, this increase in viscosity by incorporating a small amount of alkaline earth metal hydroxide can be controlled to a suitable value, overbased phenate product necessarily have to have a reduced ability to neutralize the reaction. 为了获得高中和能力的产物并且同时控制中间产物的粘度在可接受值范围内,碱土金属氢氧化物可以分两步,(通常称之为“两步石灰加入法”工艺)或三个单独的反应步骤,接续在其后的为碳酸化步骤。 In order to obtain a product of high neutralizing capacity and simultaneously controlling the viscosity of the intermediate product within an acceptable range of values, an alkaline earth metal hydroxide may be in two steps, (commonly referred to as process "two-stage Addition of lime") or three separate reaction step, subsequent to the subsequent carbonation step. 然而,这种方法包含了相当长的间歇时间。 However, this approach involves considerable interval of time. 另外一种方法是在中间产物的制备中使用粘度抑制剂,例如十三烷醇、2-乙基己醇,或类似沸程的羟基溶剂,但这样一种办法增加了工艺中的原材料成本。 Another method is to use an intermediate product in the preparation of inhibitors of viscosity, for example tridecanol, 2-ethylhexanol or similar boiling range hydroxylic solvent, but such an approach increases the cost of raw materials in the process. 尽管一般现有工艺的总碱值范围为200-300,但通常可由现有工艺方法获得与适用粘度相一致的最高总碱值(TBN)(用mgKOH/g作计量单位,是300,很清楚理想的目标是生产具有高总碱值(TBN)的硫化烷基酚碱土金属盐组合物,所说的高总碱值(TBN)是TBN大于300,最好大于350。还有一个理想的目标是从具有较低总碱值(TBN)的硫化烷基酚碱土金属盐来制备上述组合物。到目前为止,还未发现有人能获得这样高总碱值的产物。这是因为使用的碱土金属碱浓度太高,导致了产物的高粘度,使这种高粘度产物变成不溶物,而且这种高粘度产物试图用过量二氧化碳进行接续碳酸化也不“变稀”。但我们已达到了这些目的,并获得了总碱值(TBN)超过300(有时超过350)的组合物,同时又保持了合意的粘度,一个小于1000厘沲(cst)的粘度,通过将分子中有至少10个碳 While the prior art generally TBN range of 200-300, but usually by the conventional process for obtaining a viscosity suitable for consistent highest TBN (TBN of) (with mgKOH / g measurements are made, is 300, it is clear the desirable goal is to produce alkaline earth metal sulfurized alkylphenol composition having a high total base number (TBN), said high total base number (TBN) is a TBN greater than 300, preferably greater than 350. there is also a desirable goal the composition is prepared from the above-described sulfurized alkylphenols having a lower TBN alkaline earth metal salts (TBN of) the so far, one can obtain a product has not been found such a high total base number. this is because the use of an alkaline earth metal the alkali concentration is too high, resulting in high viscosity of the product, the product becomes so high viscosity insolubles, and this high viscosity of the product with excess carbon dioxide attempted connection is not carbonated "thinning." However, we have achieved these object, and the TBN is obtained (TBN of) more than 300 (more than 350 times) the composition while maintaining the desirable viscosity, a viscosity of 1000 centistokes (CST) is less than, by a molecule having at least 10 carbon 子的至少一个羧酸或其酸性衍生物掺入含有硫化烷基酚碱土金属盐的反应混合物中,从而避免了不溶性。 At least one carboxylic acid or a derivative thereof is incorporated in the reaction mixture containing sub-earth metal sulfurized alkylphenols, thereby avoiding insolubility.

在生产硫化烷基酚碱土金属盐时使用羧酸已不是新技术,参见美国专利US-A-4049560号和欧洲专利EP-A-0094814号。 Carboxylic acid in the production of alkaline earth metal sulfurized alkylphenols is not new, see U.S. Patent No. US-A-4049560 and European Patent No. EP-A-0094814.

美国专利US-A-4049560叙述了将二氧化碳通入反应混合物的方法生产高碱性镁洗涤剂,所说的反应混合物包括:(a)15-40%(重)的含有一个或多个烃基取代基的硫化酚或苯硫酚,或含有一个或多个烃基取代基的酚或苯硫酚,或含有一个或多个同硫一起的烃基取代基的所说酚或苯硫酚,(b)5-15%(重)的有机磺酸,有机磺酸盐或有机硫酸盐, U.S. Patent No. US-A-4049560 describes a carbon dioxide leads to the production method of the reaction mixture overbased magnesium detergent, said reaction mixture comprising: (a) 15-40% (weight) contains one or more hydrocarbyl substituted group sulfurized phenol or thiophenol or containing one or more hydrocarbyl substituted phenol or thiophenol groups or contain one or more hydrocarbyl substituents together with sulfur, the group of said phenol or thiophenol, (b) 5-15% (weight) organic sulfonic acid, an organic sulphonate or an organic sulphate,

(c)5-15%(重)的甘醇,C1-C5的一元链烷醇或C2-C4的烷氧基链烷醇,(d)2-15%(重)的氢氧化镁或活性氧化镁,(e)至少为0.1%(重)的C1-C18羧酸,及其酸酐,或其铵盐或胺盐,所说C1-C18羧酸的Ⅰ族金属盐或Ⅱ族金属盐,和(f)至少10%(重)的稀释油[包括存在于(a)和(b)组分中]。 (C) 5-15% (weight) glycols, C1-C5 monohydric alkanol or alkoxy group of C2-C4 alkanol, (d) 2-15% (weight) of magnesium hydroxide or active magnesium oxide, (e) at least 0.1% (a weight) of C1-C18 carboxylic acids, and anhydrides thereof, or ammonium salts or amine salts, or salts of said family ⅰ ⅱ metal salt of C1-C18 carboxylic acids, and (f) at least 10% (weight) of diluent oil [present in comprising (a) and (b) component].

羧酸的量[组分(e)]最好为0.5-2.0%(重),用这个反应制备的产物据说总碱值(TBN)约为200-250,例如约225。 The carboxylic acid [component (e)] is preferably 0.5 to 2.0% (weight), the product prepared by this reaction is said total base number (TBN of) approximately 200-250, for example about 225.

欧洲专利EP-A-0094814披露了掺入润滑油组合物的添加剂浓缩物,该浓缩物含有润滑油,和从10%(重)至90%(重)或在高碱性过程中或在高碱化过程后续步骤中处理过的高碱性硫化烃基酚碱土金属盐,以及0.1%(重)至10%(重),最好为2-6%(重)(基于添加剂浓度)的下式酸:R-CH-COOH (Ⅰ)R1(式中R是C10-C24的无支链烷基或链烯基,且R1是氢,C1-C4烷基或-CH2-COOH基)或基酸酐或其盐。 European Patent No. EP-A-0094814 discloses a lubricating oil composition incorporating an additive concentrate, the concentrate comprising lubricating oil, and from 10% (weight) to 90% (weight) or overbased or during high basification subsequent steps treated overbased alkaline earth metal sulfurized hydrocarbyl phenol, and 0.1% (weight) to 10% (weight), preferably 2-6% (weight) (based on additive concentration) of the formula acid: R-CH-COOH (ⅰ) R1 (wherein R is an unbranched alkyl or alkenyl group of C10-C24, and R1 is hydrogen, C1-C4 alkyl group or a -CH2-COOH) or an acid anhydride group or a salt thereof. 欧洲专利EP-A-0094814的发明目的是解决含有高碱性添加剂的许多添加剂浓缩物所遇到的问题,即引起沉积和发泡问题缺乏稳定性。 European Patent No. EP-A-0094814 the object of the invention is to solve the problems of many additive concentrates containing overbased additives encountered, i.e., deposition and foaming problems caused by a lack of stability. EP-A-0094814的问题不是制备具有TBN大于300的酚盐,和真的用该发明的方法制备和酚盐(尽管克服了稳定性及发泡问题),其总碱值(TBN)也低于300。 EP-A-0094814 the problem of not having a TBN greater than 300 Preparation phenate, and actually using the invention and methods of making phenate (although foam stability and overcoming the problems) which TBN (TBN) is low at 300.

可以断定,现有工艺中使用羧酸制备总碱值大于300并有适用粘度的高碱性硫化烷基酚碱土金属盐不会有什么问题。 It can be concluded that the prior processes using carboxylic acid prepared TBN greater than 300 and have a suitable viscosity overbased alkaline earth metal sulfurized alkylphenols not a problem.

因此,本发明的一个目的是提供一种适宜掺入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)润滑油能溶解的改良硫化烃基酚碱土金属盐,其掺入量(以下面或(ⅰ)或(ⅱ)的组合物为基准)大于2%(重)到35%(重),(ⅰ)是至少具有下式的一个羧酸:R-CH-COOH (Ⅰ)R1式中,R是C10-C24烷基或链烯基,且R1或是氢、C1-C4烷基或是-CH2-COOH基,或其酸酐,酰基氯或酯。 It is therefore an object of the present invention is to provide a suitable additive concentrate incorporated into a finished lubricating oil composition, the additive concentrate comprising: (a) lubricants (b) improved lubricating oil can be dissolved alkaline earth metal sulfurized hydrocarbyl phenol , which is incorporated in an amount (or the following (i) or (ii) a composition basis) greater than 2% (weight) to 35% (weight), (i) having at least one carboxylic acid of the formula: R- CH-COOH (ⅰ) R1 in the formula, R is a C10-C24 alkyl or alkenyl, and R1 is hydrogen or, C1-C4 alkyl or -CH2-COOH groups, or its anhydride, acid chloride or ester. (ⅱ)是含有36-100碳原子的二或多羧酸,或其酸酐,酰基氯或酯。 (Ii) a di- or polycarboxylic acids containing 36-100 carbon atoms, or an anhydride, acid chloride or ester. 上述组合物的总碱值大于300。 Total base value of the composition is greater than 300.

组合物的组分(a)是润滑油。 Component (a) is a lubricating oil composition. 适宜的润滑油可以是动物油,植物油或矿物油。 Suitable lubricating oil may be animal, vegetable or mineral oil. 适宜的润滑油可以是由石油衍生的润滑油,例如环烷基油,石蜡基油或混合基油。 Suitable lubricating oil may be a petroleum-derived lubricating oil, such as naphthenic oil, paraffinic oils or mixed base oil. 最好是溶剂中性油。 Preferably the solvent neutral oil. 另外,润滑油还可以是合成润滑油,适宜的合成润滑油包括合成酯类润滑油,这类油有合成双酯润滑油例如己二酸二辛酯,葵二酸二辛酯和己二酸十三酯,或聚合烃润滑油(例如液体聚异丁烯和聚α-烯烃。基于组合物的重量,适宜的润滑油含量可为10-90%,最好为10-70%。 Further, the lubricating oil may be a synthetic lubricating oil, suitable synthetic lubricating oils include synthetic ester lubricating oils, such oils with a synthetic diester lubricants e.g. dioctyl adipate, dioctyl Kwai adipate and ten triesters, or polymeric hydrocarbon lubricating oils (e.g. liquid polyisobutylene and α- olefin based on the weight of the composition, a suitable oil content of 10-90%, preferably 10-70%.

组分(b)是润滑油能溶解的改良硫化烃基酚碱土金属盐,其掺入量(基于或(ⅰ)或(ⅱ)组合物的重量)为大于2%至35%。 Component (b) is a lubricating oil capable of dissolving the modified alkaline earth metal sulfurized hydrocarbyl phenol, which amounts (or based on (i) or (ii) weight of the composition) of greater than 2-35%. 适宜的碱土金属可以是锶、钙、镁或钡,最好是钙、钡或镁,特别是钙。 Suitable alkaline earth metal may be strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, especially calcium.

硫化烃基酚碱土金属盐的烃基酚部分最好由至少一个烷基酚所衍生。 Sulfurized hydrocarbyl phenol portion alkaline earth metal hydrocarbyl phenol is preferably derived from at least one alkylphenol. 烷基酚的烷基可以是有支链或无支链的。 Alkylphenol alkyl group may be branched or unbranched. 适宜的烷基含有4-50,最好是9-28个碳原子。 Suitable alkyl group containing 4-50, preferably 9-28 carbon atoms. 最适宜的烷基酚是用四聚丙烯烷基化苯酚而得到的C12-烷基酚。 The most suitable alkylphenol is an alkylphenol C12- alkylated phenol with propylene tetramer obtained.

硫化烃基酚碱土金属盐通过掺入或(ⅰ)或(ⅱ)得到改良。 Alkaline earth metal sulfurized hydrocarbyl phenol obtained or improved by the incorporation of (i) or (ii). 关于(ⅰ),至少这是一个有化学式(Ⅰ)或其酸酐,酰基氯或酯的羧酸。 On (i), or at least it is an acid anhydride, acid chloride or carboxylic acid esters of the formula (Ⅰ). 化学式(Ⅰ)中的R最好是无支链的烷基或链烯基。 In formula (Ⅰ) R is preferably an unbranched alkyl or alkenyl group. 化学式(Ⅰ)的优选酸是其中R为C10-C24,最好为C18-C24直链烷基,且R1是氢的那些酸。 Preferably the acid of formula (Ⅰ) are those wherein R is a C10-C24, preferably C18-C24 straight chain alkyl, and R1 is hydrogen, those acids. 适宜的化学式(Ⅰ)饱和羧酸的例子有癸酸、月桂酸、十四烷酸、棕榈酸、硬脂酸、花生酸、山萮酸和二十四烷酸。 Examples (Ⅰ) suitable saturated carboxylic acids of formula capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. 化学式(Ⅰ)的适宜不饱和酸的例子有:月桂烯酸、肉豆蔻脑酸、棕榈油酸、油酸、顺式9-二十碳烯酸、芥酸、蓖麻油酸、亚油酸和亚麻酸。 Examples of suitable chemical formula (Ⅰ) unsaturated acids are: lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic carbon acid, erucic acid, ricinoleic acid, linoleic acid, and linolenic acid. 还可以使用酸的混合物,例如菜子油(rapetop)脂肪酸,最适宜的混合酸是含有一系列酸的商品级那些酸,包括饱和酸和不饱和酸二种。 Mixtures of acids may also be used, such as rapeseed oil (rapetop) fatty acids are the most suitable mixing those commercial grades containing a range of acids acids include saturated acids and unsaturated acid species. 这些混合物可由合成法获得,或由天然产物得到,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、向日葵油、鲱鱼油、沙丁油和动物脂油。 These mixtures are obtained by synthesis or obtained from natural products such as 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. 硫化的酸和酸的混合物也可以使用,除了羧酸外,还可以使用酸酐,酰基氯或酸的酯衍生物,但酸酐最佳。 Acids and sulfurized mixtures of acids may also be used, in addition to a carboxylic acid, may be used acid anhydrides, acid chloride or ester derivative of the acid, but the optimum acid anhydride. 然而最好使用羧酸或羧酸的混合物。 Preferably, however, a mixture of a carboxylic acid or carboxylic acid. 优选的化学式(Ⅰ)的羧酸是硬脂酸。 Preferred acids of formula (Ⅰ) is stearic acid.

除了(ⅰ)外,硫化烃基酚碱土金属盐也可以掺入(ⅱ)来改良。 In addition to (i), the alkaline earth metal sulphurised hydrocarbyl phenols may also be incorporated (ii) be improved. 所说的(ⅱ)是含有36-100个碳原子的二或聚羧酸或基酸酐,酰基氯或酯衍生物,最好是其酸酐。 He said (ii) is a di- or polycarboxylic acid containing or acid anhydride group, acid chloride or ester derivative 36-100 carbon atoms, preferably anhydrides. 优选的(ⅱ)是聚异丁烯丁二酸或聚异丁烯丁二酸酐。 Preferred (ii) is a polyisobutene succinic acid or a polyisobutene succinic anhydride.

化学式(Ⅰ)的羧酸,及其二或聚羧酸,或酸酐,酰基氯或酯的优选掺入量基于组合物的重量为大于10%到35%,最好为约12%-20%,例如约16%。 A carboxylic acid of formula (Ⅰ) and their di- or polycarboxylic acid or anhydride, preferably the acid chloride or ester incorporated in an amount based on the weight of the composition is more than 10% to 35%, preferably from about 12% -20% , for example about 16%. 羧酸或其衍生物的掺入量大于10%的优点通常是浓缩物的粘度较低。 Amount of more carboxylic acid or derivative is 10% of the advantage is generally lower viscosity concentrate.

适宜的碱土金属存在于组合物中的量,基于组合物的重量可以是10%(重)-20%(重)。 Suitable alkaline earth metal is present in the composition in an amount, based on the weight of the composition may be 10% (weight) to 20% (weight).

适宜的硫存在于组合物中的量,基于组合物的重量可以为10%(重)-6%(重),最好为1.5%(重)-3%(重)。 Suitable sulfur is present in the composition in an amount, based on the weight of the composition may be 10% (weight) to 6% (weight), preferably 1.5% (weight) to 3% (weight).

适宜的二氧化碳存在于组合物中的量,基于组合物的重量可以是5%(重)-20%(重),最好为9%(重)-15%(重)。 Suitable carbon dioxide present in the composition in an amount, based on the weight of the composition may be 5% (weight) to 20% (weight), preferably 9% (weight) to 15% (weight).

组合物的优选总碱值(TBN)大于350,最好大于400。 Preferably the TBN of the composition (TBN of) greater than 350, preferably greater than 400.

适宜的组合物所具有的粘度在100℃时测量应小于1000厘沲,最好小于750厘沲,尤其是小于500厘沲。 Suitable compositions have a viscosity measured at 100 ℃ should be less than 1000 centistokes, preferably less than 750 centistokes, in particular less than 500 centistokes.

本发明的另一个目的是提供一种适于掺入成品润滑油的添加剂浓缩物,该浓缩物可由高温下的反应来获得。 Another object of the present invention is to provide an additive concentrate suitable for incorporation into a finished lubricating oil which concentrate the reaction at a high temperature can be obtained. (A)硫化烃基酚碱土金属盐所具有的总碱值(TBN)小于最终添加剂浓缩物的总碱值,(B)在反应过程的中间时刻将碱土金属碱或一次加入或分多次加入,(C)或加入具有2-4个碳原子的多元醇,二或三(C2-C4)乙二醇、亚烷基乙二醇烷基醚或聚二醇烷基醚,(D)加入润滑油,(E)每加入一次组分(B)后通入一次二氧化碳,和(F)足以提供从大于2%(重)到35%(重)(基于或(ⅰ)或(ⅱ)浓缩物重量)由或(ⅰ)或(ⅱ)构成的浓缩物,(ⅰ)是具有化学式(Ⅰ)的羧酸或其酸酐,酰基氯或酯,(ⅱ)是含有36-100个碳原子的二或聚羧酸,或其酸酐,酰基氯或酯。 (A) sulfurized alkaline earth metal hydrocarbyl phenol has a TBN (TBN of) less than the final TBN additive concentrate, (B) the reaction time in the middle of the process or the alkaline earth metal base added in one or multiple additions, (C2-C4) (C) or adding a polyol having 2-4 carbon atoms, di- or triethylene glycol, alkylene glycol alkyl ethers or polyethylene glycol alkyl ether, (D) was added lubrication oil, (E) is added after each time component (B) introduced into a carbon dioxide, and (F) sufficient to provide from greater than 2% (weight) into 35% (weight) (or based on (i) or (ii) a concentrate by weight), or by the (i) or (ii) a concentrate consisting of, (i) having the formula (ⅰ) carboxylic acid or an anhydride, acid chloride or ester, (ii) containing two carbon atoms 36-100 or polycarboxylic acid, or anhydride, acid chloride or ester. 组分(A)对(F)的重量比是制备总碱值(TBN)大于300的浓缩物的重量比。 By weight of component (A) by weight of (F) ratio is prepared TBN (TBN of) the concentrate is greater than 300 ratio.

本发明的第三个目的是提供一种掺入成品润滑油中添加剂浓缩物的制备方法,该方法包括在高温下进行上述组分(A)至(F)的反应,组分(A)对(F)的重量比是制备具有总碱值(TBN)大于300浓缩物的重量比。 A third object of the present invention is to provide a method for preparing the finished lubricating oil additive concentrate incorporated, the method comprising the above components (A) at an elevated temperature to (F) of the reaction, component (A) of by weight of (F) by weight is prepared having a total base number (TBN of) the concentrate is greater than 300 ratio.

本发明的方法是优异的,因为它提供了一种提高现有工艺中低TBN产物质量的方法,或将不符合质量的产物变成具有适用粘度的高总碱值(TBN)产物。 The method of the present invention is excellent, because it provides a way to improve the quality of the product is low in prior art the TBN, or will not meet the high quality of the product becomes suitable viscosity having a total base number (TBN) of product. 此外,由于在本发明工艺的操作期间不放出硫化氢,相反,在制备硫烷基酚碱土金属盐的工艺中包含着烷基酚与硫的反应,按最普通的路线,硫化氢的排放问题可以避免,因此,可以在周围环境敏感的地区生产加工而无需使用高级精细工厂。 Further, since during operation of the process of the present invention does not release the hydrogen sulfide, the opposite, comprising the reaction of an alkylphenol with sulfur in the process for preparing the alkaline earth metal salt of alkylphenol sulfur, according to the most common routes, emissions of hydrogen sulfide can be avoided, therefore, can be produced in the processing of sensitive areas surrounding environment without the use of advanced fine factory.

反应组合物的组分(A)是具有总碱值低于最终产物(即通常低于300)的硫化烃基酚碱土金属盐。 Component (A) is a reaction composition of sulfurized alkaline earth metal hydrocarbyl phenol TBN lower than the final product (i.e., typically less than 300). 任何硫化烃基酚碱土金属盐都可以使用。 Any alkaline earth metal sulfurized hydrocarbyl phenol may be used. 硫化烃基酚碱土金属盐可以碳酸化或非碳酸化。 Alkaline earth metal sulfurized hydrocarbyl phenol may be carbonated or non-carbonated. 硫化烃基酚碱土金属盐的碱土金属部分和烃基酸部分可用前述的那些。 Alkaline earth metal hydrocarbyl moiety and the acid moiety of the alkaline earth metal sulfurized hydrocarbyl phenol those previously available. 制备硫化烃基酚碱土金属盐的方法在所属领域是熟知的。 Preparation of sulfurized alkaline earth metal hydrocarbyl phenol methods are well known in the art. 另外,硫化烃基酚碱土金属盐的前身,即非硫化烃基酚碱土金属盐和硫也可以使用。 Further, alkaline earth metal sulfurized hydrocarbyl phenol predecessor, i.e. non-sulfurized alkaline earth metal hydrocarbyl phenol and sulfur may also be used.

适宜的碱土金属碱(组份B)可以是碱土金属氧化物或氢氧化物,最好是氢氧化物,例如氢氧化钙可以熟石灰的形式加入。 Suitable alkaline earth metal base (component B) may be an alkaline earth metal oxide or hydroxide, preferably a hydroxide, such as calcium hydroxide may be added 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. 对于组分(A),碱土金属碱的加入量须是足以制备出总碱值超过300,最好超过350的产物。 For component (A), the amount of alkaline earth metal base added should be sufficient to prepare a TBN of over 300, preferably over 350 products. 该加入量取决于多种因素,包括硫化烃基酚碱土金属盐的性能。 The amount depends on various factors, including the performance of the alkaline earth metal sulphurised hydrocarbyl phenol. 组分(B)与组分(A)的适宜重量比通常为0.1-50,最好为0.2-5。 Suitable weight of component (B) to component (A) it is usually from 0.1 to 50, preferably 0.2 to 5. 碱土金属碱(B)可以全部加入到初始反应物中,或部分地加入到初始反应物中,剩余部分可以分一次或多次加入到工艺中的后续步骤中。 Alkaline earth metal base (B) may be added in whole to the initial reactants, or in part to the initial reactants were added, the remaining portion may be added once or several times to the process in the subsequent steps. 组分(B)最好一次加入到初始反应物中。 Preferably a component (B) is added to the initial reactants.

组分(C)或是有2-4个碳原子的多元醇,二或三(C2-C4)乙二醇,亚烷基乙二醇烷基醚,或是聚二醇烷基醚。 Component (C) or polyol 2-4 carbon atoms, di- or tri- (C2-C4) glycol, an alkylene glycol alkyl ethers or polyethylene glycol alkyl ether. 适宜的多元醇可以是二元醇,例如乙二醇或丙二醇。 Suitable polyhydric alcohols may be dihydric alcohols such as ethylene glycol or propylene glycol. 也可以是三元醇、例如丙三醇。 It may be a triol, such as glycerol. 适宜的二或三(C2-C4)乙二醇可以是或二甘醇或三甘醇。 Suitable di- or tri (C2-C4) glycol may be diethylene glycol or triethylene glycol or. 适宜的亚烷基乙二醇烷基醚或聚二醇烷基醚具有下列化学式:R(OR1)XOR2(Ⅱ)式中R是C1-C6烷基,R1是亚烷基,R2是氢或C1-C6烷基,并且X是一个1-6的整数。 Suitable alkylene glycol alkyl ethers or polyethylene glycol alkyl ether has the following chemical formula: R (OR1) XOR2 (Ⅱ) wherein R is C1-C6 alkyl group, R1 is alkylene, R2 is hydrogen or C1-C6 alkyl, and X is an integer of 1-6. 具有化学式(Ⅱ)的适宜溶剂包括:乙二醇的一甲基醚或二甲基醚,二甘醇、三甘醇或四甘醇。 Suitable solvents having the formula (Ⅱ) comprises: ethylene glycol monomethyl ether or dimethyl ether, diethylene glycol, triethylene glycol or tetraethylene glycol. 最适宜的溶剂是甲基digol醇(CH3OCH2CH2OCH2CH2OH。乙二醇和化学式(Ⅱ)醇醚的混合物也可以使用。使用乙二醇或化学式(Ⅱ)的醇醚作为溶剂时最好结合使用与此有关的无机卤化物(例如氯化铵),和低级(即C1-C4)羧酸(如乙酸)。优选的组分(C)或是乙二醇或是甲基digol醇,后者结合氯化铵和乙酸使用。 The most suitable solvent is methyl digol alcohol (() was CH3OCH2CH2OCH2CH2OH. Ⅱ ethers of ethylene glycol, and the formula can also be used. Ethylene glycol or formula (Ⅱ) in ether as a solvent is preferably used in conjunction with this to an inorganic halide (e.g. chloride), and lower (i.e. C1-C4) carboxylic acids (e.g. acetic acid). the preferred component (C) either ethylene glycol or methyl digol alcohol, which combines chloride and acetic acid use.

组分(D)是前述的与浓缩物组合物有关的润滑油。 Component (D) is associated with the aforementioned concentrate composition lubricating oil.

组分(E)是二氧化碳,其可以用气态或固态形式加入,最好用气态形式加入,用气态形式适宜吹入反应混合物中。 Component (E) is carbon dioxide, which may be gaseous or solid form is added, preferably added with gaseous form, the gaseous reaction mixture is blown into a suitable form. 我们已发现通常二氧化碳的掺入量随着组分(F)浓度的增加而增加。 We have found that generally the amount of carbon dioxide incorporated increases with increasing component (F) concentration increases. 二氧化碳最好在组分(A)、(B)、(C)、(D)和(F)之间的反应完成后,并在每一次加入组分(B)后通入。 After carbon dioxide is preferably in the component (A), (B), (C), the reaction between (D) and (F) is completed, and after each addition of component (B) into.

与浓缩物组合物有关的组分(F)或是化学式(Ⅰ)的羧酸,含有36-100碳原子的二或聚羧酸,或是其酸酐,酰基氯或酯。 For concentrate compositions of the component (F) or the formula (Ⅰ) carboxylic acids, di- or polycarboxylic acid containing 36-100 carbon atoms, or an anhydride thereof, an acid chloride or an ester. 为提供大于2%(重)到35%(重)(基于浓缩物的重量)而所需的上述(F)组分量将是由浓缩物导出的一次近似值。 To provide more than 2% (weight) to 35% (a weight) (F) and the desired component of said group (based on the weight of the concentrate) will be derived from a concentrate of a first approximation. 例如在计算该量时应把羧酸中的失水考虑进去。 For example, when calculating the amount of the carboxylic acid in water loss into account.

该反应可以在稀释剂的存在下进行。 The reaction may be carried out in the presence of a diluent. 适宜的稀释剂是具有与工艺操作相一致的挥发性液体,即当反应完结时可从反应混合物中容易汽提出的挥发性液体。 Suitable diluents are consistent with a volatile liquid with the process operation, i.e. when the end of the reaction may be readily stripped from the reaction mixture of volatile liquid. 适宜稀释剂的例子有2-乙基己醇、异辛醇、异庚醇和十三醇。 Examples of suitable diluents are 2-ethylhexanol, iso-octanol, iso-heptanol and tridecyl alcohol. 额外的硫也可以加入到反应混合物中,并且这种附加硫已经作为组分(A)存在。 Additional sulfur may be added to reaction mixture, and such additional sulfur already present as component (A). 加入额外硫的优点是增加了浓缩物中硫的含量,这对某些应用来说是所希望的。 An additional advantage is to increase the sulfur content of the sulfur in the concentrate, which for some applications is desirable. 另一方面加入硫导致了硫化氢气体的排放,从而在某种程度上有损于本发明前述的那些优点。 On the other hand sulfur addition you lead to the emission of hydrogen sulfide gas, so that in a way detrimental to the advantages of the present invention.

最好反应在有附加组分的存在下进行,所说附加组分是用于反应的催化剂,可以使用的催化剂是无机卤化物,适宜的无机卤化物或是卤化氢、卤化铵或是金属卤化物,适宜金属卤化物的金属部可以是锌、铝或碱土金属、最好是钙。 The reaction is preferably carried out in the presence of an additional component, said additional component is a catalyst for the reaction, the catalyst may be used an inorganic halide, an inorganic halide or a suitable hydrogen halide, an ammonium halide or a metal halide It was suitable metal portion of the metal halide may be zinc, aluminum or an alkaline earth metal, preferably calcium. 所说的卤化物最好是氯化物。 He said halide is preferably chloride. 适宜的催化剂有氯化氢、氯化钙、氯化铵、氯化铝和氯化锌,最好是氯化钙。 Suitable catalysts include hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride. 催化剂适宜的使用量可以达到2.0%(重)/(重)。 Suitable catalysts can be used in an amount reaches 2.0% (weight) / (weight).

相应的组分(A)-(F)的反应以及碳酸化反应可以在120-200℃,最好在约130-165℃的高温下进行,但组分(A)-(F)的反应和碳酸化反应所选用的实际温度也是按需要而不同的。 The respective components (A) - The reaction (F) and the carbonation reaction may be 120-200 deg.] C, preferably at a high temperature of about 130-165 deg.] C, but the components (A) - The reaction (F), and carbonation reaction temperatures are chosen according to the actual needs of different. 压力可以是常压、低压或超计大气压。 Pressure can be atmospheric, reduced pressure or superatmospheric pressure.

浓缩物可以用常规法回收,例如组分(C)的蒸馏汽提和稀释(若有的话)。 Concentrate may be recovered by conventional methods, for example, component (C) and stripping distillation dilution (if any).

最后,最好过滤所得到的浓缩物。 Finally, preferably obtained was filtered and concentrated. 通常,本发明的工艺能制备合适粘度的浓缩物,即在100℃时其粘度小于1000厘沲,并能制备出在100℃时具有小于750或500厘沲粘度的浓缩物。 In general, the process of the invention concentrates suitable viscosity can be prepared, i.e. at 100 ℃ viscosity of less than 1000 cSt, and can be prepared having less than 750 or 500 cSt viscosity at 100 ℃ concentrate. 此外,浓缩物一般具有所期望的粘度指数性质。 In addition, we concentrate generally have desirable viscosity index properties. 由于浓缩物容易加工(包括过滤),所以该粘度性质是有益的。 Since the concentrate is easy processing (including filtration), so that the beneficial viscosity properties. 然而,通常在更高的总碱值时,也有可能制备具有更高粘度(如在100℃的粘度大于1000厘沲,的浓缩物,过滤该浓缩物时会出现问题,但可以在过滤前用加入稀释剂的方法来克服,并在过滤后将稀释剂用汽提法涂去。此外,浓缩物可用润滑油稀释并仍保持TBN超过300,尤其是当所制备浓缩物的总碱值高于400时更是如此。 However, generally at higher TBN, also possible to prepare concentrates having a higher viscosity (e.g., 100 deg.] C a viscosity greater than 1000 centistokes, problems occur when the concentrate is filtered, but may be used prior to filtration a method to overcome, and the filter after coating with a diluent to stripping. Further, the concentrate diluted with lubricating oil and still retain available TBN of more than 300, particularly if the TBN of the concentrate prepared above was added diluent 400 when even more so.

本发明的最后一个目的是提供一种成品润滑油组合物,该组合物包含有润滑油和足够量的上述添加剂浓缩物,以提供一个TBN为0.5-120的范围。 A final object of the present invention is to provide a finished lubricating oil composition, which composition comprises a lubricating oil and a sufficient amount of the additive concentrate to provide a TBN of a range of 0.5-120.

优选的成品润滑油组合物含有足量的浓缩物组合物,以提供一个TBN为0.5-100的范围。 Preferably the concentrate composition the finished lubricating oil composition contains sufficient amount to provide a TBN in the range of 0.5 to 100.

存在于成品润滑油中浓缩物组合物的量将取决于最终使用的性质。 The amount present in the finished lubricating oil composition of the concentrate will depend on the nature of the final use. 因此,对于船用润滑油,浓缩物组合物的适宜存在量应足以提供总碱值(TBN)为9-100的范围,而对于汽车发动机润滑油,浓缩物适宜存在量应足以提供总碱值(TBN)为4-20的范围。 Thus, for marine lubricating oils, the presence of a suitable amount of the concentrate composition is sufficient to provide a total base number (TBN of) the range of 9 to 100 and for automobile engine lubricating oil concentrate suitable amount sufficient to provide a total base number is present ( TBN) in the range of 4-20.

成品润滑油中还可以含有有效量的一种或多种其它类型的常用润滑油添加剂,例如粘度指数改进剂,抗磨剂、抗氧剂、分散剂、防锈剂、降凝剂等等。 Finished lubricating oil may also contain an effective amount of one or more other types of conventional lubricating oil additives, for example viscosity index improvers, antiwear agents, antioxidants, dispersants, rust, pour point depressants and the like. 这些添加剂可以直接地掺入到成品润滑油组合物中,也可以通过浓缩物组合物作为中介物加入。 These additives may be directly incorporated into the finished lubricating oil composition, the composition may be added by the intermediary of the concentrate.

添加剂除了作掺入润滑油组合物的应用外,还发现本发明的浓缩物组合物也能够作燃料添加剂使用。 In addition to applying the additive as incorporated into the lubricating oil composition, but also found that concentrate compositions of the present invention can also be used as a fuel additive.

下面将用实施例来进一步说明本发明。 The use examples of the present invention is described further below.

在所有的实施例中都使用了术语“TBN”,TBN是总碱值(Total Base Nomber),用ASTMD2896方法测量,以mgKOH/g为计量单位。 In all of the embodiments use the term "TBN", TBN is the TBN (Total Base Nomber), a method of measuring ASTMD2896 to mgKOH / g units of measurement.

在所有的实施例中,除非另有说明外,所使用的均为市场上买到的由C12-烷基酚所制得的硫化烷基酚钙。 In all examples, unless otherwise stated, are available on the market by using C12- alkylphenol prepared sulfurized alkylphenol calcium. 该酚盐以润滑油溶液形式提供,其在组合物中的最为36-40%W/W。 The phenate lubricating oil provided in the form of a solution, which composition is most 36-40% W / W. 组合物的TBN为250,该组合物由下列组分组成:钙(9.25%W/W)、硫(3.25%W/W)和二氧化碳(4.6%W/W)。 TBN composition 250, the composition consists of the following components: calcium (9.25% W / W), sulfur (3.25% W / W) and carbon dioxide (4.6% W / W). 这里对于任何实施例中的“进料”所包括的润滑油是已存在于酚盐组合物中的附加成分。 Herein for any embodiment of the lubricating oil "feed" it is already included in the additional ingredients present in the phenate composition.

用ASTMD445的方法测量粘度。 The viscosity was measured by the method ASTMD445.

实施例1:提高硫化烷基酚钙的质量进料:润滑油 (57克)硫化烷基酚钙 (206克)石灰 (49克)硬脂酸 (70克)氯化钙 (4克)α-乙基己醇 (112克)将该进料加热到145-165℃/700mmHg同时加入36克乙二醇。 Example 1: Improving the quality sulfurized alkylphenol calcium Feed: oil (57 g) sulfurized calcium alkyl phenate (206 g) Lime (49 g) of stearic acid (70 g) Calcium chloride (4 g) [alpha] - ethyl hexanol (112 g) the feed was heated to 145-165 ℃ / 700mmHg simultaneously added 36 g of ethylene glycol. 然后维持其在165℃/700mmHg1小时,1个多小时在165℃下通入二氧化碳(50克)。 Which is deg.] C and then maintained at 165 / 700mmHg1 hour, at more than 1 hour at 165 ℃ into carbon dioxide (50 g). 将该产物冷却到125℃/700mmHg。 The product was cooled to 125 ℃ / 700mmHg. 加入石灰(33克)。 Addition of lime (33 g). 将温度升到165℃/700mmHg并使这个温度保持1小时。 The temperature was raised to 165 ℃ / 700mmHg and this temperature was maintained for 1 hour. 1个多小时在165℃通入二氧化碳(25克)。 More than one hour at 165 deg.] C, and carbon dioxide (25 g). 然后将该产物在200℃/10mmHg下汽提。 The product was then 200 ℃ / 10mmHg stripped. 最后将产物过滤。 Finally the product was filtered. 可以看到过滤速度是很快的。 We can see the filtration rate is very fast. 得到437克产物和167克馏出物。 To give 437 g product and 167 g distillate.

将该产物进行钙、硫和二氧化碳的分析。 The product was analyzed calcium, sulfur and carbon dioxide. 测得其在100℃时的TBN,BPHVISO和粘度。 Obtaining measured TBN, BPHVISO and viscosity at 100 ℃. BPHVISO测定法是一个溶解度试验。 BPHVISO assay is a solubility test. 这个试验的结果以刻度1(较高溶解性,通过)2(分界线)和3(未通过)表示。 The results of the tests to scale 1 (high solubility, by) 2 (boundary) and 3 represent (failed).

结果:钙:=13.9%W/W(相当于96%的保留在产物中的钙进料)硫:=1.5%W/W(相当于100%的保留在产物中的硫进料)二氧化碳:=12.3%W/W(相当于62%的保留在产物中的CO2进料)TBN=395V100=228厘沲(cst)BPHVISO=1A硬脂酸=16%W/W这个实施例说明了低的TBN产物通过本发明的方法可以转化成高的TBN产物并有一个可接受的粘度。 Results: Calcium: = 13.9% W / W (equivalent to 96% calcium retention in the product feed) Sulfur: = 1.5% W / W (corresponding to 100% retention of the feed sulfur in the product) of carbon dioxide: = 12.3% W / W (equivalent to 62% of the feed CO2 retention in the product) TBN = 395V100 = 228 centistokes (cst) BPHVISO = 1A stearic acid = 16% W / W this example illustrates the low TBN product can be converted by the process of the present invention to a high TBN product and has a acceptable viscosity.

实施例2:进料:硫化烷基酚钙: 230克润滑油: 26克氯化钙: 3克方法:(a)将进料加热到100℃/700mmHg。 Example 2: Feed: sulfurized calcium alkyl phenate: 230 g Lubricating oil: 26 g Calcium chloride: 3 g Method: (a) The charge was heated to 100 ℃ / 700mmHg. 加入硬脂酸(63克)并将混合物搅拌15分钟; Stearic acid (63 g) was added and the mixture was stirred for 15 minutes;

(b)在100-110℃/700mmHg时加入2-乙基己醇(190克); (B) adding 2-ethylhexanol (190 g) at 100-110 ℃ / 700mmHg;

(c)在110℃/700mmHg时加入石灰66克; (C) adding lime at 110 ℃ / 700mmHg 66 g;

(d)将上述混合物加入到165℃/700mmHg并快速加入(1分钟)乙二醇(32克); (D) To the above mixture was added to 165 ℃ / 700mmHg and added quickly (one minute) of ethylene glycol (32 g);

(e)将该混合物在165℃/700mmHg下维持5分钟; (E) maintaining the mixture at 165 ℃ / 700mmHg 5 min;

(f)然后在165℃/1bar时加入二氧化碳(66克); (F) Carbon dioxide is then added at 165 ℃ / 1bar (66 g);

(g)在200℃/10mmHg时回收溶剂,和(h)将汽提的产物过滤。 (G) recycling the solvent at 200 ℃ / 10mmHg, and (h) The stripped product was filtered.

产物重量:粗产物: 398克馏出物: 236克过滤后的产物组成:过滤的速度是很快的。 Weight of product: Crude product: 398 g distillate: 236 g product after filtration: Filtration speed is very fast.

钙 14.1%W/W硫 2.0%W/WCO212.9%W/WTBN 399V100 825厘沲(cst)硬脂酸 15.8%W/W实施例3进料:与实施例2相同。 Calcium 14.1% W / W Sulfur 2.0% W / WCO212.9% W / WTBN 399V100 825 centistokes (CST) Stearic acid 15.8% W / W Example 3 Feed: same as in Example 2.

方法:除了在步骤(d)、(e)和(f)中的温度用145℃代替165℃之外,其余与实施例2相同。 Method: except that the temperature in step (d), (e) and (f) in place of 165 deg.] C with 145 ℃, the rest as in Example 2.

产物重量: Weight of the product:

粗产物 402克馏出物:239克过滤后产物组成:钙 13.9%W/W硫 1.9%W/WCO213.9%W/WTBN 392V100 206厘沲(cst)硬脂酸 15.7%W/W实施例4进料:与实施例2相同。 The crude distillate product was 402 g: 239 g After filtration the product composition: Calcium 13.9% W / W Sulfur 1.9% W / WCO213.9% W / WTBN 392V100 206 centistokes (CST) Stearic acid 15.7% W / W Example feed 4: same as in Example 2.

方法:除了在步骤(d)、(e)和(f)中的温度用130℃代替165℃外,其余步骤与实施例2相同。 Method: except that the temperature in step (d), (e) and (f) in place of 165 deg.] C with 130 ℃, the remaining steps same as in Example 2.

产物重量:粗产物 377克馏出物:236克过滤后产物组成:钙 13.7%W/W硫 2.1%W/WCO213.2%W/WTBN 380V100 99厘沲(cst)硬脂酸 16.7%W/W实施例5进料:除了去掉氯化钙外,其余与实施例3相同。 Weight of product: 377 g of crude product distillate: 236 g After filtering the product composition: calcium 13.7% W / W Sulfur 2.1% W / WCO213.2% W / WTBN 380V100 99 centistokes (CST) Stearic acid 16.7% W / W Example 5 feed: In addition to removing the calcium chloride, the remaining the same as in Example 3.

方法:同实施例3产物重量:粗产物 388克馏出物:239克过滤后产物组成:钙 11.9%W/W硫 2.1%W/WCO29.0%W/WTBN 331V100 98cstVI 148硬脂酸 16.2%W/W过滤步骤(h)是很困难的。 Method: the same as Example 3 Weight of product: 388 g of crude product distillate: 239 g After filtering the product composition: Calcium 11.9% W / W Sulfur 2.1% W / WCO29.0% W / WTBN 331V100 98cstVI 148 Stearic acid 16.2% W / W filtration step (h) is very difficult.

与实施例3相比较该实施例说明了在本发明工艺中使用催化剂是合乎需要的。 This embodiment is described in comparison Example 3 using a catalyst in the process of the invention it is desirable. 在没有催化剂的情况下,尽管得到了较低的V100,但是这个结果却是在通过减少钙和二氧化碳混合物的代价下获得的,此外过滤变得困难了。 In the absence of catalyst, although a lower V100 obtained, but this result is obtained at the expense of reducing calcium and carbon dioxide mixture through the addition filter it becomes difficult.

实施例6进料:硫化烷基酚钙: 253克润滑油(100SN) 26克氯化钙 4克2-乙基己醇 190克硬脂酸 40克方法:(a)将进料加热到120℃/700mmHg,然后加入石灰(36克)(b)将该混合物加热到145-165℃,同时加入乙二醇(32克); Example 6 Feed: sulfurized calcium alkyl phenate: 253 g lubricant (100SN) 26 g Calcium chloride 4 g 2-ethyl hexanol 190 g Stearic acid 40 g Method: (a) The charge was heated to 120 ℃ / 700mmHg, followed by addition of lime (36 g) (b) heating the mixture to 145-165 ℃, while adding ethylene glycol (32 g);

(c)将该混合物在165/700mmHg下维持1小时; (C) the mixture was 165 / 700mmHg for 1 hour at;

(d)在165℃/1bar下加入二氧化碳(44克); (D) adding carbon dioxide at 165 ℃ / 1bar (44 g);

(e)将混合物冷却到120℃加入石灰(25克); (E) The mixture was cooled to 120 deg.] C was added lime (25 g);

(f)将该混合物在165℃/700mmHg下维持1小时; (F) The mixture was maintained at 165 ℃ / 700mmHg 1 h;

(g)在165℃/1bar下加入二氧化碳(22克); (G) adding carbon dioxide at 165 ℃ / 1bar (22 g);

(h)在200℃/10mmHg下汽提出溶剂,和(i)过滤产物,过滤速度很快。 (H) in / 10mmHg deg.] C at 200 is stripped of solvent, and (i) The product was filtered, the filter quickly.

产物重量:粗产物:401克馏出物:239克过滤后产物组成:钙 14.3%W/W硫 2.1%W/WCO211.3%W/WTBN 405V100 1483cst硬脂酸 10%W/W该实施例说明了可以制备出高总碱值的浓缩物,然而由于掺入10%W/W的硬脂酸,其粘度相对要高些。 Weight of product: Crude product: 401 g of distillate: 239 g After filtering the product composition: Calcium 14.3% W / W Sulfur 2.1% W / WCO211.3% W / WTBN 405V100 1483cst stearate 10% W / W of this embodiment It illustrates concentrate can be prepared a high TBN, however, due to the incorporation of stearic acid 10% W / W, which is relatively higher viscosity.

实施例7进料:除了酚盐从250克增加到268克,硬脂酸从40克增加到51克外,其余同实施例6。 Example 7 Feed: addition phenate increased from 250 g 268 g, stearic acid of from 40 grams to 51 grams, the remaining same as in Example 6.

方法:同实施例6。 Method: same as in Example 6.

产物重量: Weight of the product:

粗产物:396g馏出物:234g过滤后产物组成:钙 14.5%W/W硫 2.2%W/WCO213.1%W/WTBN 399V100 706cst硬脂酸 12.9%W/W该实施例表明,在硬脂酸含量为浓缩物的12.9%W/W时,可以制得与实施例6相比较低粘度的高TBN的浓缩物。 The crude product was: 396 g of distillate: 234g After filtration the product composition: Calcium 14.5% W / W Sulfur 2.2% W / WCO213.1% W / WTBN 399V100 706cst stearate 12.9% W / W This example shows that the stearin when the acid content of the concentrate of 12.9% W / W, can be prepared by a high TBN concentrate with lower viscosity as compared to Example 6.

实施例8进料:硫化烷基酚钙: 230g润滑油(SN100) 0g氯化钙: 3g方法:(a)将进料加热到100℃,然后加入硬脂酸(99g),该混合物搅拌15分钟。 Example 8 Feed: sulfurized calcium alkyl phenate: 230g lubricating oil (SN100) 0g Calcium chloride: 3g methods: (a) The charge was heated to 100 ℃, then the stearic acid (99g), and the mixture was stirred for 15 minute.

(b)在100-110℃加入2-乙基己醇(190g),(c)在110℃/2″Hg真空条件下,加入石灰(66g),(d)将该混合物加热到145℃/10″Hg,在20分钟内加入乙二醇(32g),(e)该混合物在145℃/10″Hg条件下静置5分钟,(f)在145℃加入二氧化碳(66g),(g)在200℃/30″Hg条件下,对产品进行汽提,(h)过滤产品,其过滤速度缓慢。 (B) adding at 100-110 ℃ 2- ethylhexanol (190g), (c) at 110 ℃ / 2 "Hg vacuum, addition of lime (66g), (d) and the mixture was heated to 145 ℃ / 10 "Hg, ethylene glycol was added over 20 minutes (32g), (e) and the mixture was at 145 ℃ / 10" Hg for 5 minutes the allowed to stand, (f) adding carbon dioxide (66g) at 145 ℃, (g) at 200 ℃ / 30 "Hg conditions, stripping the product, (h) filtering the product, which was filtered slow speed.

产物重量:粗产物: 398g馏出物: 209g过滤后产物组成:钙 11.95%W/W硫 1.65%W/WCO211.6%W/WTBN 349V100 100cstV40 947cst硬脂酸 24.9%W/W该实施例表明,在硬脂酸含量为24.9%W/W时,制得具有低粘度的高TBN浓缩物是可能的。 Weight of product: Crude product: 398g distillate: 209g After filtration the product composition: Calcium 11.95% W / W Sulfur 1.65% W / WCO211.6% W / WTBN 349V100 100cstV40 947cst stearate 24.9% W / W This example shows when stearic acid content of 24.9% W / W, to obtain a high TBN concentrate having a low viscosity are possible.

比较试验1进料:如同实施例3方法:与实施例3相同,只是在步骤(d)中添加乙二醇一步省略。 Comparison Test Feed 1: A method as in Example 3: the same as Example 3 except that ethylene glycol was added in the step of omitting step (d),.

产物重量:粗产物: 382g馏出物: 200g过滤后产物组成:钙 8.4%W/W硫 2.3%W/WCO24.4%W/WTBN 239V100 41cst在步骤(h)中过滤速度缓慢。 Weight of product: Crude product: 382g distillate: 200g After the product was filtered: the slow calcium 8.4% W / W Sulfur 2.3% W / WCO24.4% W / WTBN 239V100 41cst in step (h), the filtration rate.

这不是本发明的实施例,而是用来说明组分(c)的存在对于进行本发明的过程是必不可少的。 This is not an embodiment of the invention, but rather to illustrate the presence of component (c) for the process of the present invention is essential.

实施例9进料:如同实施例3方法:与实施例3相同,只是在步骤(d)中加入的乙二醇从32g降至16g。 Example 9 Feed: A method as in Example 3: the same as Example 3, except that the addition in step (d), ethylene glycol 32g dropped from 16g.

产物重量:粗产物: 399g馏出物: 225g过滤后产物组成:钙 13.7%W/W硫 2.0%W/WCO213.5%W/WTBN 395V100 182cst硬脂酸 15.8%W/W步骤(h)中的过滤速度缓慢。 Weight of product: Crude product: 399 g distillate: 225g After filtration the product composition: Calcium 13.7% W / W Sulfur 2.0% W / WCO213.5% W / WTBN 395V100 182cst stearate 15.8% W / W in step (h), the filtration is slow.

该实施例表明,与实施例3相比乙三醇的添加量可减少50%。 This Example shows that the amount added of Example 3 can be reduced compared to B 50% glycerol.

实施例10进料:硫化酚烷基钙 230g润滑油(100SN) 26g Example 10 Feed: 230g sulphurised calcium alkyl lubricants (100SN) 26g

氯化铵 4g乙酸 2g方法:与实施例3相同,只是在步骤(b)中不用2-乙基己醇(190g),代之以甲基二甘醇(130g),并且步骤(d)中加入乙二醇一步省略。 2g 4g ammonium acetate method: same as in Example 3, except that instead of 2-ethylhexanol (190g) in step (b), and replaced with diethylene glycol methyl (130g), and step (d), ethylene glycol step is omitted.

产物重量:粗产物: 390g馏出物: 166g过滤后产物组成:钙 14.1%W/W硫 2.0%W/WCO214.2%W/WTBN 398V100 210cstV40 3821cstVI 170硬脂酸 16.2%W/W步骤(h)中的过滤速度快。 Weight of product: Crude product: 390 g of distillate: 166g After filtration the product composition: Calcium 14.1% W / W Sulfur 2.0% W / WCO214.2% W / WTBN 398V100 210cstV40 3821cstVI 170 Stearic acid 16.2% W / W of step (h fast) in the filtration rate.

该实施例表明甲基二甘醇作为组分(c)是有效的。 This example demonstrates that methyl diglycol as component (c) is effective.

实施例11进料:如同实施例3方法:与实施例3相同,只是在步骤(d)中压力为270mmHg。 Example 11 Feed: A method as in Example 3: the same as Example 3, except that in step (d), a pressure of 270mmHg.

产物重量:粗产物: 402g馏出物: 238g过滤后产物组成:钙 14.9%W/W硫 1.9%W/WCO214.4%W/WTBN 392V100 288cst硬脂酸 15.7%W/W实施例12进料:如同实施例3方法:与实施例3相同,只是190g2-乙基己醇改用40g。 Weight of product: Crude product: 402g distillate: 238g After filtration the product composition: Example 12 Feed Calcium 14.9% W / W Sulfur 1.9% W / WCO214.4% W / WTBN 392V100 288cst stearate 15.7% W / W embodiment : A method as in Example 3: the same as in Example 3, except 190g2- ethylhexanol switch 40g.

产物质量:粗产物: 399g馏出物: 90g过滤后产物组成:钙 13.9%W/W硫 1.9%W/WCO212.1%W/WTBN 408V100 387cstV40 7980cstVI 193硬脂酸 15.8%W/W实施例13进料:硫化烷基酚钙 230g硬脂酸 63g氯化钙 4gC18直链α-链烯26g2-乙基乙醇 90g方法:(a)将混合物加热到145-165℃/700mmHg,同时加入乙二醇(32g),(b)在165℃/700mmHg时,该混合物静置30分钟,(c)在165℃/1bar下,加入二氧化碳(38g),(d)将该混合物冷却到122℃,加入2-乙基乙醇(100g),(e)加入石灰(66g),(f)该混合物在165℃/700mmHg静置5分钟,(g)加入二氧化碳(66g),(h)在200℃/10mmHg下汽提回收溶剂,(i)对产物过滤。 Quality of the product: Crude product: 399 g distillate: After 90g filtered product composition: Calcium 13.9% W / W Sulfur 1.9% W / WCO212.1% W / WTBN 408V100 387cstV40 7980cstVI 193 Stearic acid 15.8% W / W Example 13 feed: 230g calcium sulfurized alkylphenol calcium stearate 63g 4gC18 linear α- olefin 26g2- ethyl alcohol 90g method: (a) the mixture was heated to 145-165 ℃ / 700mmHg, while adding ethylene glycol (32g), (b) at 165 ℃ / 700mmHg, and the mixture was allowed to stand for 30 minutes, (c) at 165 ℃ / 1bar, addition of carbon dioxide (38g), (d) the mixture was cooled to 122 ℃, was added 2 - ethyl alcohol (100g), (e) addition of lime (66g), (f) and the mixture was allowed to stand at 165 ℃ / 700mmHg 5 minutes, (g) adding carbon dioxide (66g), (h) in / 10mmHg at 200 ℃ stripped solvent is recovered, (i) The product was filtered.

产物重量:粗产物:385g馏出物:256g过滤后产物组成:钙 14.8%W/W硫 1.9%W/WCO213.4%W/WTBN 424V100 583cstV40 13,080cst Weight of product: Crude product: 385g distillate: 256g After filtration the product composition: Calcium 14.8% W / W Sulfur 1.9% W / WCO213.4% W / WTBN 424V100 583cstV40 13,080cst

VI 209硬脂酸 16.4%W/W步骤(ⅰ)中的过滤速度快。 VI 209 Stearic acid 16.4% W / W in step (i) in filtering speed.

该实施例表明润滑油可用长碳链α-链烯(这里为C18)取代。 This example demonstrates the lubricating oil available long chain α- olefin (here C18) substituted.

实施例14进料:来自C12/C22/C24烷基酚混合物的硫化烷基酚钙(250TBN) 233.5g润滑油(SN100) 26g氯化钙 3g方法:(a)将混合物加热到100℃,加入硬脂酸,该混合物进行搅拌15分钟。 Example 14 Feed: sulfurized calcium alkyl phenate (250TBN) 233.5g lubricating oil (SN100) 26g 3g calcium chloride method from a C12 / C22 / C24 alkyl phenol mixture of: (a) The mixture was heated to 100 ℃, was added stearic acid, the mixture was stirred for 15 minutes.

(b)在100-110℃加入2-乙基己醇,(c)在110℃/2″Hg真空下,加入石灰(66g),(d)将混合物加热到145℃/10″Hg,在20分钟内加入乙二醇(32g),(e)在145℃/10″Hg下,该混合物静置5分钟,(f)加入二氧化碳(66g),(g)在200℃/30″Hg下,对产物进行汽提,(h)过滤产物。 (B) 2-ethylhexanol was added at 100-110 ℃, (c) at 110 ℃ / 2 "Hg vacuum under addition of lime (66g), (d) heating the mixture to 145 ℃ / 10" Hg, in ethylene glycol was added over 20 minutes (32g), (e) at 145 ℃ / 10 "at Hg, the mixture was allowed to stand for 5 minutes, (f) adding carbon dioxide (66g), (g) at 200 ℃ / 30" Hg at , The product was stripped, (h) filtered product.

产物重量:粗产物:385g馏出物:250g过滤后产物组成:钙 14.0%W/W硫 1.84%W/WCO212.9%W/WTBN 401V100 381cstV40 8385cstVI 186硬脂酸 16.4%W/W该实施例表明从C12/C22/C24烷基酚混合物中获得的硫化烷基酚钙可得到改进。 Weight of product: Crude product: 385g distillate: 250g After filtration the product composition: Calcium 14.0% W / W Sulfur 1.84% W / WCO212.9% W / WTBN 401V100 381cstV40 8385cstVI 186 Stearic acid 16.4% W / W of this embodiment sulfurized alkylphenol calcium showed obtained from C12 / C22 / C24 alkyl phenol mixture can be improved.

实施例15进料:硫化烷基酚钙 181g润滑油(SN100) 50g氯化钙 4g菜油脂肪酸 62g2-乙基己醇 190g方法:(a)将混合物加热到120℃,(b)在120℃/2″Hg真空下,加入石灰(43g),(c)在145-165℃/2″Hg下,加入乙二醇(32g),(d)混合物在165℃/2″Hg下静置1小时,(e)加入二氧化碳(44g),(f)将混合物冷却到130℃,在130℃/2″Hg时加入石灰(29g)。 Example 15 Feed: 181g sulfurized calcium alkyl phenate lubricating oil (SN100) 50g Calcium chloride 4g rapeseed oil fatty acid ethyl hexanol 190g 62g2- methods: (a) The mixture was heated to 120 ℃, (b) at 120 ℃ / 2 'Hg vacuum under addition of lime (43g), (c) at 145-165 ℃ / 2 "Hg for, ethylene glycol (32g), (d) the mixture was allowed to stand at 165 ℃ / 2" Hg 1 hours , (e) adding carbon dioxide (44g), (f) the mixture was cooled to 130 ℃, at 130 ℃ / 2 "Hg lime (29g) time.

(g)混合物在165℃/2″Hg下静置1小时,(h)在165℃时加入石灰(22g),(i)在200℃/30″Hg下,对产物进行汽提,(j)过滤产物。 (G) a mixture "was allowed to stand at Hg 1 hours, (h) Lime was added at 165 ℃ (22g), (i) at / 30 200 ℃" at 165 ℃ / 2 at Hg, the product was stripped, (j ) The product was filtered.

产物质量:粗产物:382g馏出物:230g过滤后产物组成:钙 14.0%W/W硫 1.8%W/WCO212.3%W/WTBN 374V100 176cstV40 2826cstVI 172羧酸含量 16.2%W/W该实施例表明,本发明可以使用菜油脂肪酸。 The product quality: The crude product was: 382g distillate: 230g After filtration the product composition: Calcium 14.0% W / W Sulfur 1.8% W / WCO212.3% W / WTBN 374V100 176cstV40 2826cstVI 172 carboxylic acid content of 16.2% W / W of this embodiment It shows that the present invention may be used vegetable oil fatty acids.

实施例16进料:硫化烷基酚钙 230g润滑油(SH100) 26g氯化钙 3g方法:与实施例2相同,只是步骤(a)中不用硬脂酸(63g),而代之以妥尔油脂肪酸(63g)。 Example 16 feed: 230g sulfurized calcium alkyl phenate lubricating oil (SH100) 26g 3g calcium chloride method: same as in Example 2, except that in step (a) is not stearate (63g), but instead tall oil fatty acid (63g).

产物重量:粗产物 380g馏出物 223g过滤后产物组成: Weight of product: 380g crude product was filtered by distilling off the product composition was 223g:

钙 14.0%W/W硫 2.09%W/WCO29.7%W/WTBN 380V100 263cst羧酸含量 16.6%W/W(为产品重量)该实施例表明在本发明的过程中可以使用妥尔油脂肪酸。 Calcium 14.0% W / W Sulfur 2.09% W / WCO29.7% W / WTBN 380V100 263cst carboxylic acid content of 16.6% W / W (weight of product) This example shows tall oil fatty acid may be used in the process of the present invention.

实施例17进料:如同实施例16方法:与实施例16相同,只是在SN100润滑油(TBN=60mgKOH/g)和硬脂酸(47g)的混合物中用52g聚异丁烯琥珀酸酐(PIBSA)取代妥尔油脂肪酸(63g)。 Example 17 Feed: as in example 16: the same as in Example 16, except substitution SN100 lubricating oil (TBN = 60mgKOH / g) and stearic acid (47g) with 52g of a mixture of polyisobutylene succinic anhydride (of PIBSA) tall oil fatty acid (63g).

产物质量:粗产物:390g馏出物:219g过滤后产物组成:钙 13.1%W/W硫 1.8%W/WCO212.5%W/WTBN 360V100 416cstV40 12,690cstVI 164羧酸含量 12.1%W/W以产物重量酸酐含量 7.2%W/W为基础该实施例表明,在本发明的过程中,羧酸可以部分被PIBSA取代。 Quality of the product: Crude product: 390 g of distillate: 219g After filtration the product composition: Calcium 13.1% W / W Sulfur 1.8% W / WCO212.5% ​​W / WTBN 360V100 416cstV40 12,690cstVI 164 carboxylic acid content of 12.1% W / W in by weight of acid anhydride content in the product 7.2% W / W basis this example shows that, in the process of the present invention, the carboxylic acid may be partially substituted with PIBSA.

实施例18进料:如同实施例16方法:与实施例16相同,只是用山萮酸(16g)取代妥尔油脂肪酸(63g)。 Example 18 Feed: as in example 16: the same as Example 16 except that a substituted tall oil fatty acid (63g) with behenic acid (16g).

产物质量:粗产物:402g馏出物:247g过滤后产物组成:钙 12.4%W/W硫 1.9%W/WCO211.4%W/WTBN 354V100 141cst山酸 15.7%W/W该实施例表明,在本发明过程中,可用山萮酸作为羧酸。 The product quality: The crude product was: 402g distillate: 247g After filtration the product composition: Calcium 12.4% W / W Sulfur 1.9% W / WCO211.4% W / WTBN 354V100 141cst behenic acid 15.7% W / W This example shows that, in process of the present invention, can be used as the carboxylic acid behenic acid.

实施例19进料:与实施例15相同,只是用棕榈酸(56.2g)取代菜油脂肪酸(62g)。 Example 19 Feed: same as in Example 15 except that a substituted vegetable oil fatty acid (62g) with palmitic acid (56.2g).

方法:与实施例15相同,只是步骤(f)、(g)和(h)省略。 Method: the same as in Example 15 except that in step (f), (g) is omitted, and (h).

产物重量:粗产物:312g馏出物:222g过滤后产物组成:钙 11.7%W/W硫 1.9%W/WCO28.2%W/WTBN 332V100 70cstV40 831cstVI 156棕榈酸 18.0%W/W该实施例表明,本发明的过程中可以使用棕榈酸。 Weight of product: Crude product: 312g distillate: 222g After filtration the product composition: Calcium 11.7% W / W Sulfur 1.9% W / WCO28.2% W / WTBN 332V100 70cstV40 831cstVI 156 palmitic acid, 18.0% W / W This example shows the process of the present invention may be used in palmitic acid.

实施例20进料:如同实施例15,方法:与实施例15相同,只是省略步骤(f)、(g)和(h)。 Example 20 Feed: 15, as in example: same as Example 15, except omitting step (f), (g) and (h).

产物重量粗产物:334g馏出物:234g过滤后产物组成钙 11.8%W/W硫 1.8%W/WCO210.9%W/WTBN 321V100 168cstV40 1009cstVI 286羧酸含量 占产品重量的18.6% The crude product Weight of product: 334g distillate: 234g product composition after filtration Calcium 11.8% W / W Sulfur 1.8% W / WCO210.9% W / WTBN 321V100 168cstV40 1009cstVI 286 carboxylic acid content of 18.6% by weight of the product

对比试验2进料:硫化烷基酚钙: 230g润滑油: 26g氯化钙: 3g方法:(a)将混合物加热到100℃,加入2-乙基己醇(190g),(b)加入乙酸(14g),(c)混合物变稠,不均匀,并出现设想的绿色,搅拌不起作用,反应是非连续的。 Comparative Test 2 Feed: sulfurized calcium alkyl phenate: 230g Lubricant: Calcium chloride 26g: 3g methods: (a) The mixture was heated to 100 ℃, was added 2-ethylhexanol (190g), (b) Acetic acid (14g), (c) thickening of the mixture, uneven, and the emergence of green envisaged stirred ineffective, non-continuous reaction.

该试验不是本发明的实施例,只是用来说明在本发明过程中不能使用低级羧酸,在这里指乙酸。 The test is not an embodiment of the present invention, but can not be used to illustrate a lower carboxylic acid in the process of the present invention, referred to herein as the acid.

实施例21进料:与实施例16相同,只是用非碳酸化的、商业上可获得的硫化C12-烷基酚钙(145TBN)取代商业上可获得的硫化烷基酚钙。 Example 21 Feed: same as in Example 16 except that a substituted sulfurized alkylphenol calcium commercially available non-carbonated, commercially available sulfurized alkylphenol calcium C12- (145TBN).

方法:与实施例16相同,只是步骤(c)中石灰量从6g增加到83g,步骤(f)中二氧化碳的量从66g增加到83g。 Method: the same as Example 16, except the amount of step (c) the amount of lime added to 83 g of from 6g, step (f) of carbon dioxide increases from 66g 83g.

产物重量粗产物: 421g馏出物: 246g过滤后产物组成钙 13.7%W/W硫 1.9%W/WCO210.3%W/WTBN 383V100 137cstV40 2119cstVI 163羧酸 15.0%W/W该实施例表明,本发明的过程可以使用非碳酸的低TBN的硫化烷基酚钙。 The crude product Weight of product: 421g distillate: 246g After the composition of the product was filtered Calcium 13.7% W / W Sulfur 1.9% W / WCO210.3% W / WTBN 383V100 137cstV40 2119cstVI 163-carboxylic acid 15.0% W / W This example shows that the present process invention may use non-carbonated low TBN sulfurized calcium alkyl phenate.

实施例22进料碳酸化的硫化烷基酚钙(150TBN) 253g硬脂酸 40g2-乙基己醇 90g氯化钙 4g方法:(a)将混合物从145℃加热到165℃/700mmHg,同时加入乙二醇(32g),(b)混合物在165℃/700mmHg时静置30分钟,(c)在165℃/1bar下加入二氧化碳(38g),(d)将混合物冷却到120℃,加入2-乙基己醇(100g)和石灰(76g),(e)在165℃/700mmHg时,混合物静置60分钟,(f)在165℃/1bar时,加入二氧化碳(82g),(g)在200℃/10mmHg,回收溶剂,(h)过滤产品。 Example 22 feeds carbonated sulfurized alkylphenol calcium (150TBN) 90g 253g calcium stearate 4g method 40g2- ethylhexanol: (a) heating the mixture from 145 deg.] C to 165 ℃ / 700mmHg, while adding ethylene glycol (32g), (b) the mixture was allowed to stand at 165 ℃ / 700mmHg 30 minutes, (c) adding carbon dioxide (38g) at 165 ℃ / 1bar, (d) the mixture was cooled to 120 ℃, was added 2- ethylhexanol (100g) and lime (76g), (e) at 165 ℃ / 700mmHg, the mixture was allowed to stand for 60 minutes, (f) at 165 ℃ / 1bar, addition of carbon dioxide (82g), (g) 200 ℃ / 10mmHg, recovered solvent, (h) filtering the product.

产物质量产物重量: 390g过滤后产物组成钙 14.4%W/W硫 2.3%W/WCO211.6%W/WTBN 402V100 674cst硬脂酸 10.3%W/W该实施例表明,低TBN的硫化烷基酚钙可改进为高TBN的产品。 The product quality of the product weight: 390g After the composition of the product was filtered Calcium 14.4% W / W Sulfur 2.3% W / WCO211.6% W / WTBN 402V100 674cst stearate 10.3% W / W This example shows that a low TBN sulfurized alkyl calcium can be improved to a high TBN products.

实施例23进料:与实施例14相同,只是不使用从烷基酚混合物得到的硫化烷基酚钙,而代之以从C12-烷基酚(250TBN)得到的硫化烷基酚钙(商业上可获得)。 Example 23 Feed: same as in Example 14, except that no sulfurized calcium alkyl phenate derived from a mixture of alkylphenol, sulfurized alkylphenol calcium and instead obtained from C12- alkyl phenol (250 TBN) (commercial on available).

方法:与实施例14相同,只是步骤(b)使用异庚醇(190g)代替2-乙基己醇(194g),步骤(d)中快速加入乙二醇(1分钟内)。 Method: same as in Example 14 except that in step (b) using iso-heptanol (190g) in place of 2-ethylhexanol (194 g of), step (d) of ethylene glycol was added quickly (within 1 minute).

产物重量:粗产物:402g馏出物:239g过滤后产物组成:钙 13.9%W/W硫 1.9%W/WCO212.0%W/WTBN 391V100 313cst Weight of product: Crude product: 402g distillate: 239g After filtration the product composition: Calcium 13.9% W / W Sulfur 1.9% W / WCO212.0% W / WTBN 391V100 313cst

V40 6700cstVI 177硬脂酸 15.7%W/W过滤速度快。 V40 6700cstVI 177 Stearic acid 15.7% W / W filtering speed.

该实施例表明,在本发明的过程中,可将异庚醇用作溶剂。 This example shows that, in the process of the invention, the iso-heptanol may be used as the solvent.

Claims (26)

1.一种适用于掺入成品润滑油组合物中的添加剂浓缩物的生产方法,所说的浓缩物的TBN值大于300,在100℃下粘度小于1000cst,该方法包括在高温下使下列物质发生反应:(A)具有小于最终添加剂浓缩物的TBN值的硫化碱土金属烃基酚盐,(B)碱土金属碱,在该方法中或者一次将其加入到反应剂中,或者部分地加入到反应剂中,并且将剩余部分以一部分或多部分在后续阶段中加入,(C)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)润滑油,(E)二氧化碳,随(B)组分的加入或每次加入后添加,和(F)提供大于2-35%(重量)(以浓缩物重量为基)的(i)至少一种具有下列通式(Ⅰ)的羧酸或其酐或酯,R1其中R为C10-C24的烷基或链烯基,R1为氢、C1-C4的烷基或-CH2COOH基团或(ii)具有36-100个碳原子的二元或多元羧酸或其酐或酯,(G)无机卤化物 A suitable method of producing additive concentrates incorporating a finished lubricating oil composition, the TBN of the value of said concentrate is greater than 300, at 100 deg.] C viscosity of less than 1000 cSt, the method comprising the following materials at high temperatures reacting: (a) less than TBN value of the final additive concentrate of sulfurized alkaline earth metal hydrocarbyl phenate, (B) alkaline earth metal base, in the method or once added to the reactants, or in part added to the reaction agent, and the remaining portion added to a portion or portions in subsequent stages, (C) a polyhydric alcohol having 2 to 4 carbon atoms, di or tri (b to D) glycols, alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) the lubricating oil, (E) carbon dioxide, with (B) component was added or added after each addition, to provide greater than 2 to 35% (by weight, and (F) ) (concentrate weight basis) of (i) at least one of the following general formula (ⅰ) carboxylic acid or anhydride or ester, R1 wherein R is a C10-C24 alkyl or alkenyl group, R1 is hydrogen (G) an inorganic halide, an alkyl group or a C1-C4 -CH2COOH or (ii) a di- or polycarboxylic acid number 36-100, or anhydride or ester carbon atoms, 分(A)对(F)的重量比要使产生的浓缩物具有大于300的TBN值。 Component (A) by weight of (F) is having a TBN greater than 300 to make the ratio of concentrate produced.
2.根据权利要求1的方法,其中润滑油占组合物的10-90%(重量)。 2. The method according to claim 1, wherein 10-90% (wt) of the composition of the lubricating oil.
3.根据权利要求1的方法,其中的碱土金属碱的钙、镁或钡的氧化物或氢氧化物。 3. The method according to claim 1, wherein the alkaline earth metal base is calcium, magnesium or barium oxides or hydroxides.
4.根据权利要求3的方法,其中的碱土金属碱为钙的氧化物或氢氧化物。 4. A method according to claim 3, wherein the alkaline earth metal base is calcium oxide or hydroxide.
5.根据权利要求1的方法,其中硫化碱土金属烃基酚盐衍生自至少一个烷基酚、烷基或烷基酚基团或含9-28个碳原子的酯。 5. The method of claim 1, wherein the sulfurized alkaline earth metal hydrocarbyl phenate is derived from at least one alkyl phenol, alkyl phenol or alkyl ester group or containing 9-28 carbon atoms.
6.根据权利要求5的方法,其中的硫化碱土金属烃基酚盐衍生自苯酚与四聚丙烯烷基化得到的C12-烷基酚。 6. The method according to claim 5, wherein the sulfurized alkaline earth metal hydrocarbyl phenate is derived from C12- alkylphenols alkylated phenol with propylene tetramer obtained.
7.根据权利要求1的方法,其中R为无支链的烷基或链烯基。 7. A method according to claim 1, wherein R is a non-branched alkyl group or alkenyl group.
8.根据权利要求7的方法,其中R为C10-C24的直链烷基,R1为H。 8. A method according to claim 7, wherein R is a linear alkyl group of C10-C24, Rl is H.
9.根据权利要求1的方法,其中(F)为通式(Ⅰ)的羧酸的混合物,该混合物为商品等级的,含有一系列饱和和不饱和的酸。 A method according to claim 1 wherein the mixture of carboxylic acids (F) of general formula (Ⅰ) requirements, and the mixture was commercial grade containing a range of saturated and unsaturated acids.
10.根据权利要求1的方法,其中(F)为硬脂酸。 The method of claim 1, wherein (F) of stearic acid.
11.根据权利要求1的方法,其中(F)为二元羧酸或含有36-100个碳原子的聚羧酸或其酸酐。 11. The method of claim 1, wherein (F) is a dicarboxylic acid containing 36-100 carbon atoms or polycarboxylic acids or anhydrides thereof.
12.根据权利要求11的方法,其中(F)为聚异丁烯琥珀酸或聚异丁烯琥珀酸酐。 12. The method according to claim 11, wherein (F) is polyisobutylene succinic acid or polyisobutylene succinic anhydride.
13.根据权利要求1的方法,其中(F)足以提供大于10-35%(重量)的(ⅰ)或(ⅱ)(以浓缩物重量为基)。 13. The method of claim 1, wherein the (F) sufficient to provide from greater than 10 to 35% (by weight) of (i) or (ii) (based in weight of the concentrate).
14.根据权利要求1的方法,其中(F)足以提供12-20%(重量)的(ⅰ)或(ⅱ)(以浓缩物重量为基)。 14. The method of claim 1, wherein the (F) sufficient to provide 12-20% (by weight) of (i) or (ii) (based in weight of the concentrate).
15.根据权利要求1的方法,其中所说的浓缩物的TBN值大于350。 15. The method according to claim 1, wherein said concentrate is a TBN greater than 350.
16.根据权利要求1的方法,其中所说的浓缩物的TBN值大于400。 16. The method according to claim 1, wherein said concentrate is a TBN greater than 400.
17.根据权利要求1的方法,其中在100℃下所说浓缩物的粘度小于500cst。 17. The method of claim 1, wherein said viscosity of the concentrate at 100 deg.] C of less than 500cst.
18.根据权利要求1的方法,其中(B)为石灰。 18. The method according to claim 1, wherein (B) is lime.
19.根据权利要求1的方法,其中(B)与(A)的重量比为0.2-5。 19. The method according to claim 1, wherein (B) to (A) weight ratio of 0.2-5.
20.根据权利要求1的方法,其中(C)为乙二醇。 20. The method of claim 1, wherein (C) is ethylene glycol.
21.根据权利要求1的方法,其中(C)为甲基digol。 21. The method according to claim 1, wherein (C) is methyl digol.
22.根据权利要求1的方法,其中在(A)-(D)和(F)之间的反应结束时,继单独加入(B)之后加入二氧化碳(E)。 22. The method according to claim 1, wherein (A) - at the end of the reaction between (D) and (F), following addition of (B) separately adding carbon dioxide (E).
23.根据权利要求1的方法,其中存在稀释剂。 23. The method according to claim 1, wherein the presence of a diluent.
24.根据权利要求1的方法,其中通过加入(A)将已存于其中的附加的硫加入到反应混合物中。 24. The method according to claim 1, wherein by the addition of (A) will be saved in which additional sulfur was added to the reaction mixture.
25.根据权利要求1的方法,其中所说的反应在催化剂存在下进行。 25. The method according to claim 1, wherein said reaction is carried out in the presence of a catalyst.
26.根据权利要求25的方法,其中所说的催化剂为氯化钙。 26. The method according to claim 25, wherein said catalyst is calcium chloride.
CN87108344A 1986-11-29 1987-11-29 Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereof CN1012074B (en)

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JPH01501399A (en) 1989-05-18
FI883502D0 (en)
KR897000159A (en) 1989-03-10
DE3781126D1 (en) 1992-09-17
ZA8708938B (en) 1989-07-26
FI93653B (en) 1995-01-31
DE3781126T2 (en) 1993-03-04
NO302763B1 (en) 1998-04-20
GB8628609D0 (en) 1987-01-07
DE3781118T2 (en) 1992-12-17
DE3781118D1 (en) 1992-09-17
AU608792B2 (en) 1991-04-18
NO883349D0 (en) 1988-07-28
JPH0631384B2 (en) 1994-04-27
JPH01501400A (en) 1989-05-18
MX169105B (en) 1993-06-22
AU8238087A (en) 1988-06-16
SG101092G (en) 1992-12-04
GR3006112T3 (en) 1993-06-21
CN87108344A (en) 1988-06-22
GR3006075T3 (en) 1993-06-21
EP0271262A1 (en) 1988-06-15
JPH0631383B2 (en) 1994-04-27
FI883502A0 (en) 1988-07-25
EP0271262B2 (en) 2002-05-29
FI883503D0 (en)
AT79396T (en) 1992-08-15
MX169106B (en) 1993-06-22
EP0273588B1 (en) 1992-08-12
DK419788A (en) 1988-07-27
FI93654C (en) 1995-05-10
KR960010991B1 (en) 1996-08-14
EP0273588A1 (en) 1988-07-06
BR8707550A (en) 1989-03-14
AU609075B2 (en) 1991-04-26
DE3781118T3 (en) 2002-08-14
CA1305696C (en) 1992-07-28
KR960010992B1 (en) 1996-08-14
WO1988003944A1 (en) 1988-06-02
FI883503A (en) 1988-07-25
DK419788D0 (en) 1988-07-27
FI93653C (en) 1995-05-10
NO883348L (en) 1988-09-14
IN172581B (en) 1993-10-16
SG101192G (en) 1992-12-04
BR8707551A (en) 1989-03-14
IN169547B (en) 1991-11-09
NO883349L (en) 1988-09-22
CN87108239A (en) 1988-06-15
KR890700158A (en) 1989-03-10
DK419888A (en) 1988-07-27
DK419888D0 (en) 1988-07-27
FI93654B (en) 1995-01-31
EP0271262B1 (en) 1992-08-12
NO176147B (en) 1994-10-31
ES2051751T3 (en) 1994-07-01
AT79395T (en) 1992-08-15
CN1015642B (en) 1992-02-26
ZA8708939B (en) 1989-07-26
EP0273588B2 (en) 2001-03-28
FI883502A (en) 1988-07-25
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DK175287B1 (en) 2004-08-09
CA1305697C (en) 1992-07-28
AU8237287A (en) 1988-06-16
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NO176147C (en) 1995-02-08
FI883503A0 (en) 1988-07-25

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