CN103173266A - Method of reducing the rate of depletion of basicity of lubricating oil composition in use in engine - Google Patents

Method of reducing the rate of depletion of basicity of lubricating oil composition in use in engine Download PDF

Info

Publication number
CN103173266A
CN103173266A CN 201210557466 CN201210557466A CN103173266A CN 103173266 A CN103173266 A CN 103173266A CN 201210557466 CN201210557466 CN 201210557466 CN 201210557466 A CN201210557466 A CN 201210557466A CN 103173266 A CN103173266 A CN 103173266A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
preferably
oil
composition
lubricating
formula
Prior art date
Application number
CN 201210557466
Other languages
Chinese (zh)
Inventor
A·P·马施
N·J·米尔内
Original Assignee
英菲诺姆国际有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • 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
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16Ethers
    • 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
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/20Condensation polymers of aldehydes or ketones
    • 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
    • C10M165/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2210/00Nature of the metal present as such or in compounds, i.e. in salts
    • C10N2210/02Group II, e.g. Mg, Ca, Ba, Zn, Cd, Hg
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/52Base number (TBN)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines

Abstract

Disclosed is a method of reducing the rate of depletion of basicity (as determined by ASTM D2896) of a lubricating oil composition in use in an engine. The lubricating oil composition includes at least one overbased alkali or alkaline earth metal detergent. The method comprises adding to the lubricating oil composition one or more compounds of Formula (I): (see formula I) wherein: x is 1 to 50, preferably 1 to 40, more preferably 1 to 30; R1 and R2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; R is a hydrocarbyl group having 9 to 100, preferably 9 to 70, most preferably, 9 to 50, carbon atoms; and n is 0 to 10, or alkaline earth metal salts thereof. The compounds of formula (I) are preferably methylene-bridged alkyl phenols or ethoxylated methylene-bridged alkyl phenols.

Description

降低用于发动机中的润滑油组合物的碱度耗减速率的方法 A method for reducing the rate of depletion of alkalinity in the engine lubricating oil compositions

发明领域 Field of the Invention

[0001] 本发明涉及降低用于发动机中的润滑油组合物的碱度耗减速率(the rate ofdepletion of basicity)(通过ASTM D2896测定)的方法,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂。 [0001] The present invention relates to a method for reducing the rate of depletion of alkalinity in the engine lubricating oil composition (the rate ofdepletion of basicity) (measured by ASTM D2896) of the lubricating oil composition comprises at least one oil-soluble overbased alkali metal or alkaline earth metal detergents. 特别地,本发明涉及降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)而不提高硫酸化灰分(sulphated ash)含量(SASH)的方法,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂。 In particular, the present invention relates to reducing the rate of depletion of alkalinity in an engine lubricating oil composition (as determined by ASTM D2896) content of the method (the SASH) sulfated ash (sulphated ash) without increasing, the lubricating oil composition It comprises at least one oil-soluble overbased alkali or alkaline earth metal detergents. 优选润滑油组合物为船用气缸润滑剂、筒状活塞式发动机油、气体发动机油或曲轴箱润滑油组合物(包括客车机油和重型柴油机油)。 Preferably the lubricating oil composition is a marine cylinder lubricants, trunk piston engine oils, gas oil or the engine crankcase lubricating oil composition (including passenger car motor oils and heavy duty diesel oil).

[0002] 发明背景 [0002] Background of the Invention

[0003] 润滑油组合物包含油溶性过碱性清净剂以提供碱度以中和由高硫燃料产生的含硫酸。 [0003] The lubricating oil composition comprising an oil-soluble overbased detergents containing sulfuric acid to provide alkalinity to neutralize generated by the high sulfur fuels. 它们还防止可能导致发动机熄火和维修的有害的碳和淤渣沉积。 They also may cause harmful prevent engine stall and maintenance of carbon and sludge deposits. 过碱性清净剂通常具有50-500,优选250-450mg K0H/g(ASTM D2896)的TBN,且通常为过碱性碱土金属清净齐IJ,例如过碱性磺酸钙、苯酚钙和水杨酸钙。 Overbased detergents generally have 50-500, preferably 250-450mg K0H / g (ASTM D2896) of the TBN of, and usually overbased alkaline earth metal detergent together IJ, e.g. overbased calcium sulfonate, calcium phenate and salicyl calcium. 重要的是,过碱性清净剂提供的碱度尽可能长时间保留,因为这确保更长的油寿命和发动机更好的保护更长时期。 Importantly, the alkalinity overbased detergents provide long retained as much as possible, as this ensures longer life and better protection of engine oil longer term. 重要的还有灰分含量不提高,因为过高的硫酸化灰分含量可导致活塞和废气回路(包括热量回收系统和后处理装置)上提高的沉积物。 It is also important not to increase the ash content, because of the high sulfated ash content can cause the piston and an exhaust circuit (including heat recovery system and the aftertreatment device) is improved sediment.

[0004] 本发明涉及降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTMD2896测定)的问题。 [0004] The present invention relates to reducing the rate of depletion of alkalinity for an engine lubricating oil composition in question (measured by ASTMD2896) of. 本发明还涉及降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)而不提高硫酸化灰分含量的问题。 The present invention further relates to reducing the rate of depletion problem basicity engine lubricating oil composition (as determined by ASTM D2896) without increasing the sulfated ash content.

[0005] 发明概述 [0005] Summary of the Invention

[0006] 根据本发明第一方面,提供降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)的方法,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂,所述方法包括向润滑油组合物中加入一种或多种式(I)化合物或式(I)化合物的碱土金属盐: [0006] According to a first aspect of the present invention, there is provided a method for reducing the rate of depletion of alkalinity in the engine lubricating oil composition (as determined by ASTM D2896) of the lubricating oil composition comprises at least one oil-soluble overbased alkali metal or alkaline earth metal detergent, said method comprising adding one or more alkaline earth metal salt compound of formula (I) compound (I) or formula to a lubricating oil composition:

[0007] [0007]

Figure CN103173266AD00041

[0008]其中: [0008] wherein:

[0009] X 为1-50,优选1-40,更优选1-30 ;[0010] R1和R2为H、具有1-12个碳原子的烃基,或具有1_12个碳原子和至少一个杂原子的经基;[0011] R为具有9-100,优选9-70,最优选9-50个碳原子的烃基;且 [0009] X is 1-50, preferably 1-40, more preferably 1-30; [0010] R1 and R2 is H, a hydrocarbon group having 1 to 12 carbon atoms, or an 1_12 carbon atoms and at least one heteroatom by group; [0011] R having 9-100, preferably 9-70, most preferably a hydrocarbon group of 9-50 carbon atoms; and

[0012] η 为0-10。 [0012] η 0-10.

[0013] 在式⑴化合物中,η优选为O。 [0013] In the compounds of formula ⑴, η preferably is O. 在式⑴化合物中,X优选为I。 In the compounds of formula ⑴, X is preferably I. 在式⑴化合物中,R优选是9-20个碳原子,更优选9-15个碳原子的。 In formula ⑴ compounds, R is preferably 9 to 20 carbon atoms, more preferably 9-15 carbon atoms. 在式(I)化合物中,R优选为支化的。 In the compound of formula (I), R is preferably a branched.

[0014] 在式⑴化合物中,R1优选为H,R2优选为H,且R优选在基团- O - [CH2CH20]nH的对位上。 [0014] In the compound of formula ⑴, R1 is preferably H, R2 is preferably H, and R is preferably the group - on [CH2CH20] nH para - O.

[0015] 式(I)化合物优选为亚甲基桥联烷基苯酚或乙氧基化亚甲基桥联烷基苯酚。 Compound [0015] Formula (I) is preferably a methylene-bridged alkyl phenols or ethoxylated methylene-bridged alkyl phenols.

[0016] 式⑴化合物优选包含小于I摩尔%,更优选小于0.5摩尔%,最优选小于0.1摩尔%未反应的烷基苯酚。 [0016] Preferred compounds of formula ⑴ comprises less than I mole%, more preferably less than 0.5 mol%, most preferably less than 0.1 mol% of unreacted alkylphenol.

[0017] 在式(I)化合物中,优选对于多于60,更优选多于70,甚至优选多于80,甚至优选多于90,或最优选多于95摩尔%,n=l。 [0017] In the compound of formula (I), preferred for more than 60, more preferably more than 70, even more preferably more than 80, even more preferably more than 90, or most preferably more than 95 mol%, n = l.

[0018] 在式⑴化合物中,优选对于小于5摩尔%,η彡2,例如二烷氧基化、三烷氧基化和四烧氧基化的。 [0018] In the compounds of formula ⑴, preferably for less than 5 mol%, η San 2, for example, two alkoxylated, tri and tetra-alkoxylated alkoxylated burning.

[0019] 式(I)化合物的碱土金属盐例如为钙、镁、钡或锶盐。 Alkaline earth metal compounds [0019] Formula (I), for example, calcium, magnesium, barium or strontium salt. 优选钙或镁盐;尤其优选钙盐。 Preferably calcium or magnesium salts; especially preferred calcium salt.

[0020] 润滑油组合物优选为船用气缸润滑剂、筒状活塞式发动机油、气体发动机油或曲轴箱润滑油组合物(包括客车机油和重型柴油机油)。 [0020] The lubricating oil composition preferably is a marine cylinder lubricants, trunk piston engine oils, gas oil or the engine crankcase lubricating oil composition (including passenger car motor oils and heavy duty diesel oil).

[0021] 当润滑油组合物为船用气缸润滑剂时,TBN(通过ASTM D2896测定)优选为至少20,更优选至少40至约70mgK0H/g。 [0021] When the lubricating oil composition is a marine cylinder lubricants, TBN of (as determined by ASTM D2896) is preferably at least 20, more preferably at least about 40 to 70mgK0H / g.

[0022] 当润滑油组合物为筒状活塞式发动机油时,TBN(通过ASTM D2896测定)优选为至少10,更优选至少20,最优选30至55mgK0H/g。 [0022] When the lubricating oil composition is a trunk piston engine oils, (as determined by ASTM D2896) TBN preferably at least 10, more preferably at least 20, most preferably 30 to 55mgK0H / g.

[0023] 当润滑油组合物为气体发动机油时,TBN(通过ASTM D2896测定)优选为至少4,更优选5至15mgK0H/g。 [0023] When the lubricating oil composition is a gas engine oil, TBN of (as determined by ASTM D2896) is preferably at least 4, more preferably 5 to 15mgK0H / g.

[0024] 当润滑油组合物为曲轴箱油时,TBN(通过ASTM D2896测定)优选为至少5,更优选至少6至18mgK0H/g。 [0024] When the lubricating oil composition is a crankcase oil, (measured by ASTM D2896) TBN preferably at least 5, more preferably at least 6 to 18mgK0H / g.

[0025] 润滑油组合物优选为船用气缸润滑剂。 [0025] The lubricating oil composition preferably is a marine cylinder lubricant.

[0026] 根据本发明,还提供一种或多种式(I)化合物或其碱土金属盐降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)的用途: [0026] The present invention also provides the use of one or more compounds of formula (I) compound or alkaline earth metal salt alkalinity is reduced rate of depletion of the lubricating oil composition used in the engine (as measured by ASTM D2896) of:

[0027] [0027]

Figure CN103173266AD00061

[0028] 其中:x为1-50,优选1-40,更优选1-30 J1和R2为H、具有1_12个碳原子的烃基,或具有1-12个碳原子和至少一个杂原子的烃基;R为具有9-100,优选9-70,最优选9_50个碳原子的烃基;n为0-10,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂。 [0028] wherein: x is 1-50, preferably 1-40, more preferably 1-30 J1 and R2 is H, a hydrocarbon group having 1_12 carbon atoms, or 12 carbon atoms and having at least one hetero atom hydrocarbyl ; R & lt having 9-100, preferably 9-70, most preferably hydrocarbon 9_50 carbon atoms; n is 0 to 10, the lubricating oil composition comprises at least one oil-soluble overbased alkali or alkaline earth metal detergent .

[0029] 发明详述 [0029] DETAILED DESCRIPTION

[0030] 式⑴化合物显示于下面: [0030] ⑴ compound of the formula are shown below:

[0031] [0031]

Figure CN103173266AD00062

[0032] X 为1-50,优选1-40,更优选1-30 ; [0032] X is 1-50, preferably 1-40, more preferably 1-30;

[0033] R1和R2为H、具有1-12个碳原子的烃基,或具有1_12个碳原子和至少一个杂原子的经基; [0033] R1 and R2 is H, a hydrocarbon group having 1 to 12 carbon atoms, or an 1_12 carbon atoms and at least one hetero atom via a group;

[0034] R为具有9-100,优选9-70,最优选9_50个碳原子的烃基;且 [0034] R having 9-100, preferably 9-70, most preferably hydrocarbon 9_50 carbon atoms;

[0035] η为0-10,或其碱土金属盐。 [0035] η 0-10, or alkaline earth metal salt.

[0036] 式(I)化合物的碱土金属盐例如为钙、镁、钡或锶盐。 Alkaline earth metal compounds [0036] Formula (I), for example, calcium, magnesium, barium or strontium salt. 优选钙或镁盐;尤其优选钙盐。 Preferably calcium or magnesium salts; especially preferred calcium salt.

[0037] 在式⑴化合物中,η优选为O。 [0037] In the compounds of formula ⑴, η preferably is O. 在式⑴化合物中,X优选为I。 In the compounds of formula ⑴, X is preferably I. 在式⑴化合物中,R优选为9-20个碳原子,更优选9-15。 In the compounds of formula ⑴, R is preferably 9 to 20 carbon atoms, more preferably 9-15. 在式(I)化合物中,R优选为支化的。 In the compound of formula (I), R is preferably a branched. 在式(I)化合物中,R1和R2优选为H。 In the compounds of formula (I), R1 and R2 is preferably H.

[0038] 在式⑴化合物中,R1优选为H,R2优选为H,R优选在基团- O - [CH2CH20]nH的对位上,且η优选为I或更大,优选1-10。 [0038] In the compound of formula ⑴, R1 is preferably H, R2 is preferably H, R is preferably a group - on [CH2CH20] nH of bits, and η is preferably I or more, preferably 1-10 - O. 关于当η为I或更大时式(I)化合物的其它细节,参考ΕΡ2374866Α(将其内容并入本文中)。 Further details regarding when η is a compound of formula I or of formula (I) larger reference ΕΡ2374866Α (the contents of which are incorporated herein by reference). 在式(I)化合物中,优选对于多于60,更优选多于70,甚至优选多于80,甚至优选多于90,或最优选多于95摩尔%,η=1。 In the compound of formula (I), preferred for more than 60, more preferably more than 70, even more preferably more than 80, even more preferably more than 90, or most preferably more than 95 mol%, η = 1. 在式(I)化合物中,优选对于小于5摩尔%,优选n ^ 2,例如二烷氧基化、三烷氧基化和四烷氧基化的。 In the compound of formula (I), preferably to less than 5 mol%, preferably n ^ 2, for example, two alkoxylated, tri and tetra-alkoxylated alkoxylated.

[0039] 式(I)化合物优选包含小于I摩尔%,更优选小于0.5摩尔%,最优选小于0.1摩 [0039] Formula (I) compound preferably comprises less than I mole%, more preferably less than 0.5 mol%, most preferably less than 0.1 mole

尔%未反应的烷基苯酚。 % Unreacted alkylphenol of Seoul.

[0040] 式⑴化合物的优点是不含金属。 [0040] The advantages of the compounds of formula ⑴ metal-free. 此外,它们不显示与分散剂的负面作用(negative interaction)。 Furthermore, they do not adversely effect the dispersing agent (negative interaction) display.

[0041] 式(I)化合物优选为烃基苯酚甲醛缩合物。 Compound [0041] Formula (I) is preferably a hydrocarbyl phenol formaldehyde condensates. 如本文所用术语“烃基”意指R主要由氢和碳原子组成且借助碳原子连接在分子的其余部分上,但不排除不足以减损基团的实质烃特征的比例的其它原子或基团的存在。 As used herein, the term "hydrocarbyl" means a R mainly hydrogen and carbon atoms and is attached to the rest of the molecule via a carbon atom, but do not preclude substantial hydrocarbon character of the group is not detracted proportion of other atoms or groups in exist. 烃基优选仅由氢和碳原子组成。 Hydrocarbon group preferably only hydrogen and carbon atoms. 有利地,烃基为脂族基团,优选烷基或亚烷基,尤其是烷基,其可以为线性或支化的。 Advantageously, the hydrocarbyl group is an aliphatic group, preferably alkyl or alkylene groups, especially alkyl which may be linear or branched. R优选为烷基或亚烷基。 R is preferably alkyl or alkylene group. R优选为支化的。 R is preferably branched.

[0042] 烃基苯酚醛缩合物优选具有通过GPC测量的1000至小于6000,优选小于4000的重均分子量(Mw)。 [0042] The hydrocarbyl phenol novolak condensate preferably has a weight of 1000 to less than 6000, preferably less than 4000 measured by GPC weight average molecular weight (Mw). 烃基苯酚醛缩合物优选具有通过GPC测量的900至小于4000,例如3000的数均分子量(Mn)。 Hydrocarbyl phenol aldehyde condensate preferably has a benzene measured by GPC of 900 to less than 4000, such as the number-average molecular weight of 3000 (Mn). Mw/Mn优选为1.10-1.60。 Mw / Mn is preferably 1.10-1.60.

[0043] 烃基苯酚醛缩合物优选为通过至少一种醛或酮或其反应性等价物与至少一种烃基苯酚之间在酸催化剂如烷基苯磺酸的存在下缩合反应而得到的。 [0043] The benzene hydrocarbon is preferably a phenol condensate by at least one aldehyde or ketone or reactive equivalent thereof and at least one hydrocarbyl between phenol condensation reaction in the presence of an acid catalyst such as alkylbenzene sulfonic acid is obtained. 优选使产物经受汽提以除去任何未反应的烃基苯酚,优选至小于5质量%,更优选至小于3质量%,甚至更优选至小于I质量%未反应的烃基苯酹。 The product is preferably subjected to steam stripping to remove any unreacted phenol hydrocarbyl, preferably to less than 5% by mass, more preferably to less than 3% by mass, and even more preferably to less than alkylbenzenes sprinkle mass% I unreacted. 最优选,产物包含小于0.5质量%,例如小于0.1质量%未反应的烃基苯酚。 Most preferably, the product comprises less than 0.5 mass%, such as less than 0.1 mass% hydrocarbyl phenol unreacted.

[0044] 尽管可使用碱性催化剂,但优选酸催化剂。 [0044] Although the basic catalyst may be used, but is preferably an acid catalyst. 酸催化剂可选自多种酸性化合物,例如磷酸、硫酸、磺酸、草酸和盐酸。 An acid catalyst selected from a variety of acidic compounds such as phosphoric acid, sulfuric acid, oxalic acid and hydrochloric acid. 酸可作为固体材料如酸处理粘土的组分存在。 Acid as a solid material such as acid treated clay component is present. 所用催化剂的量可以为总反应混合物的0.05至10质量%或更多,例如0.1至I质量%。 The amount of catalyst may be from 0.05 to 10% by mass of the total reaction mixture or more, for example, I to 0.1% by mass.

[0045] 当式(I)中η为I或更大时,化合物优选通过将烃基苯酚缩合物用碳酸亚乙酯(其为优选的)、碳酸亚丙酯或碳酸亚丁酯烷氧基化而制备。 [0045] When in formula (I) or I [eta] is greater when the compound is preferably by a hydrocarbyl phenol condensate with ethylene carbonate (which is preferred), propylene carbonate or butylene carbonate alkoxylation preparation. 发现碳酸酯在烷氧基化反应中的使用产生与使用氧化乙烯或氧化丙烯相比对“η”值和量的好得多地控制。 A carbonate found in the alkoxylation reaction in the generation and use of ethylene oxide or propylene oxide as compared to "η" value and the amount of the better controlled. 此外,催化剂的适当选择可提供基本完全由单烷氧基(即η=1)内容物组成的产物。 In addition, proper selection of the catalyst may be provided substantially entirely by a single alkoxy group (i.e., η = 1) content of the product composition. 优选钠盐,尤其是氢氧化物和羧酸盐,例如硬脂酸盐。 Preferably sodium salts, especially the hydroxide and carboxylates, such as stearate.

[0046] 特别地,烃基苯酚醛缩合物优选为支化十二烷基苯酚甲醛缩合物,例如四丙烯基四聚物苯酚甲醛缩合物。 [0046] In particular, phenol novolak condensate hydrocarbon preferably branched dodecyl phenol formaldehyde condensates, such as a four-propenyl tetramer phenol formaldehyde condensates.

[0047] 烃基苯酚醛缩合物优选以基于浓缩物的质量为约0.1-20质量%,优选约0.1-15质量%,更优选约0.1-12质量%的量存在于添加剂浓缩物中。 [0047] The hydrocarbon condensate is preferably phenol novolak based on the mass of the concentrate is about 0.1 to 20 mass%, preferably from about 0.1 to 15% by mass, and more preferably from about 0.1 to 12 mass% in the additive concentrate.

[0048] 本发明润滑油组合物包含主要量的具有润滑粘度的油和次要量的式I化合物。 The compounds of formula I [0048] The lubricating oil composition of the present invention comprises a major amount of an oil of lubricating viscosity and a minor amount.

[0049] 用于本发明上下文中的具有润滑粘度的油可选自天然润滑油、合成润滑油及其混合物。 [0049] The oil used in the context of the present invention having a lubricating viscosity selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof. 润滑油在粘度方面可从轻馏分矿物油至重质润滑油变化,例如汽油发动机油、矿物润滑油和重型柴油。 Lubricating oil may range in viscosity from light distillate mineral oils to heavy lubricating oil changes, such as gasoline engine oils, mineral lubricating oils and heavy duty diesel. 一般而言,油的粘度在100°c下测量为约2至约40厘沲,尤其是约4至约20厘沲。 Generally, the viscosity of the oil is measured at 100 ° c of from about 2 to about 40 centistokes, especially from about 4 to about 20 centistokes.

[0050] 天然油包括动物油和植物油(例如蓖麻油、猪油);液体石油以及链烷烃、环烷烃和混合链烷烃-环烷烃型的加氢精制、溶剂处理或酸处理的矿物油。 [0050] Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and paraffinic, naphthenic and mixed paraffinic - naphthenic type hydrorefining, solvent-treated or acid-treated mineral oils. 衍生自煤或页岩的具有润滑粘度的油也用作有用的基油。 Derived from coal or shale oil of lubricating viscosity also serve as useful base oils.

[0051] 合成润滑油包括烃油和卤素取代的烃油,例如聚合和共聚烯烃(例如聚丁烯、聚丙烯、丙烯-异丁烯共聚物、氯化聚丁烯、聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯));烷基苯(例如十二烷基苯、十四烷基苯、二壬基苯、二(2-乙基己基)苯);聚苯(例如联苯、三联苯、烷基化多酚);及烷基化二苯醚和烷基化二苯硫及其衍生物、类似物和同系物。 [0051] Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene - isobutylene copolymers, chlorinated polybutylenes, poly (1-hexene), poly (1-octenes), poly (1-decene)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzene); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof. 有用的还有由费托合成烃的气至液方法得到的合成油,其通常称为气至液或“GTL”基油。 Also useful are the Fischer-Tropsch synthesis gas to liquid hydrocarbon synthetic oil obtained by the method, which is commonly referred to as gas to liquid or "GTL" base oils.

[0052] 其中末端羟基已通过酯化、醚化等改性的氧化烯聚合物和共聚物及其衍生物构成另一类已知的合成润滑油。 [0052] where the terminal hydroxyl groups have been by esterification, etherification, etc., modified alkylene oxide polymers and interpolymers and derivatives thereof constitute another class of known synthetic lubricating oils. 这些通过如下例证:通过氧化乙烯或氧化丙烯聚合而制备的聚氧化烯聚合物,及聚氧化烯聚合物的烷基和芳基醚(例如分子量为1000的甲基-聚异丙二醇醚或分子量为1000-1500的聚乙二醇二苯基醚);及其单-和多羧酸酯,例如四甘醇的乙酸酯、混合C3-C8脂肪酸酯和C13含氧酸二酯。 These exemplified by: polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl molecular weight of 1000 - or poly propylene glycol ether having a molecular weight of diphenyl ether of polyethylene glycol 1000-1500); and mono - and polycarboxylic esters thereof, for example, tetraethylene glycol acetate, mixed C3-C8 fatty acid esters and C13 oxo acid diester.

[0053] 另一类适合的合成润滑油包括二羧酸(例如苯二甲酸、琥珀酸、烷基琥珀酸和烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚物、丙二酸、烷基丙二酸、烯基丙二酸)与多种醇(例如丁醇、己醇、十二醇、2-乙基己基醇、乙二醇、二甘醇单醚、丙二醇)的酯。 [0053] Another suitable class of synthetic lubricating oils include dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethyl ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). 这种酯的具体实例包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二-正己基酯、癸二酸二辛酯、壬二酸二异辛基酯、壬二酸二异癸基酯、邻苯二甲酸二辛基酯、邻苯二甲酸二癸基酯、癸二酸双二十烷基酯、亚油酸二聚物的2-乙基己基二酯,和通过I摩尔癸二酸与2摩尔四甘醇和2摩尔2-乙基己酸反应形成的混合酯。 Specific examples of such esters include dibutyl adipate, sebacate, di (2-ethylhexyl) adipate, fumarate, di - n-hexyl, dioctyl sebacate, diisooctyl azelate, isooctyl ester, diisooctyl azelate, diisodecyl phthalate, dioctyl phthalate, didecyl sebacate bis eicosyl acrylate, 2-ethyl-linoleic acid dimer dihexyl esters, and mixed esters are formed by I mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0054] 用作合成油的酯还包括由C5-C12单羧酸和多元醇和多元醇酯如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和三季戊四醇制备的那些。 [0054] Esters useful as synthetic oils also include the C5-C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol prepared.

[0055] 硅基油如聚烷基_、聚芳基_、聚烷氧基-或聚芳氧基硅油和硅酸酯油组成另一类有用的合成润滑剂;这种油包括硅酸四乙酯、硅酸四异丙酯、硅酸四-(2-乙基己基)酯、硅酸四-(4-甲基-2-乙基己基)酯、硅酸四_(对-叔丁基-苯基)酯、六-(4-甲基-2-乙基己基)二硅氧烷、聚(甲基)硅氧烷和聚(甲基苯基)硅氧烷。 [0055] Silicon-based oils such as the polyalkyl- _, _ polyaryl-, polyalkoxy- - or polyaryloxysilicone oils and silicate oils another useful class of synthetic lubricants; such oils include tetraethyl ethyl silicate, tetraisopropyl silicate, tetra- - (2-ethylhexyl) silicate, tetra- - (4-methyl-2-ethylhexyl) silicate, tetra- _ (p - tert yl - phenyl) silicate, hexa- - (4-methyl-2-ethylhexyl) disiloxane, poly (methyl) siloxanes and poly (methylphenyl) siloxanes. 其他合成润滑油包括含磷酸的液体酯(例如磷酸三甲苯酯、磷酸`三辛基酯、癸基膦酸的二乙基酯)和聚四氢呋喃。 Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, `trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

[0056] 具有润滑粘度的油可包含组1、组II或组III基本油料或上述基本油料的基油共混物。 [0056] The oil of lubricating viscosity may comprise a Group 1, Group II or Group III base stock or base stocks above base oil blend. 优选具有润滑粘度的油为组II或组III基本油料或其混合物,或组I基本油料与一种或多种组II和组III基本油料的混合物。 Preferably, the oil of lubricating viscosity is a Group II or Group III base stocks or mixtures thereof, or mixtures III basestocks I base stock and one or more Group II and Group. 优选,主要量的具有润滑粘度的油为组I1、组 Preferably, a major amount of oil of lubricating viscosity is a Group I1, group

II1、组IV或组V基本油料或其混合物。 II1, Group IV or Group V base stock, or a mixture thereof. 基本油料或基本油料共混物优选具有至少65%,更优选至少75%,例如至少85%的饱和物含量。 Base stock or base stock blend preferably has at least 65%, more preferably at least 75%, such as at least 85% of the saturation content. 最优选,基本油料或基本油料共混物具有大于90%的饱和物含量。 Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%. 优选油或油共混物具有小于1%,优选小于0.6%,最优选小于0.4重量%的硫含量。 Preferably, the oil or oil blend has a sulfur content of less than 1%, preferably less than 0.6%, most preferably less than 0.4% by weight.

[0057] 通过Noack挥发性试验(ASTM D5880)测量,优选油或油共混物的挥发度小于或等于30%,优选小于或等于25%,更优选小于或等于20%,最优选小于或等于16%。 [0057] by the Noack volatility test (ASTM D5880) measuring, preferably an oil or oil blend volatility of less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal to 16%. 优选油或油共混物的粘度指数(VI)为至少85,优选至少100,最优选约105-140。 Preferably the viscosity index of the oil or oil blend (VI) is at least 85, preferably at least 100, most preferably from about 105-140.

[0058] 本发明中基本油料和基油的定义与American Petroleum Institute (API)出版物“Engine Oil Licensing and Certification System,,,Industry Services Department,第14版,1996年12月,附录1,1998年12月中找到的那些相同。所述出版物如下分类基本油料: [0058] The present invention is defined in the base stocks and base oils and American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System ,,, Industry Services Department, 14th edition, December 1996, Addendum 1, 1998 12 the same as those found in the mid publication categorizes base stocks:

[0059] a)使用表I所述测试方法,组I基本油料含有小于90%的饱和物和/或大于0.03%的硫,且粘度指数大于或等于80且小于120。 [0059] a) using the test method described in Table I, Group I base stocks contain less than 90 percent saturates and sulfur / or greater than 0.03 percent, and a viscosity index of greater than or equal to 80 and less than 120. [0060] b)使用表I所述测试方法,组II基本油料含有大于或等于90%的饱和物和小于或等于0.03%的硫,且粘度指数大于或等于80且小于120。 [0060] b) using the test method described in Table I, Group II base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120.

[0061] c)使用表I所述测试方法,组III基本油料含有大于或等于90%的饱和物和小于或等于0.03%的硫,且粘度指数大于或等于120。 [0061] c) using the test method described in Table I, Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120.

[0062] d)组IV基本油料为聚α烯烃(PAO)。 [0062] d) Group IV base stocks are poly-α-olefins (PAO).

[0063] e)组V基本油料包括不包括在组1、I1、III或IV中的所有其他基本油料。 [0063] e) Group V base stocks include all other base stocks not included in Group 1, I1, III or IV.

[0064] 表1-基本油料的分析方法 Analysis Method [0064] Table 1 basestock

[0065] [0065]

Figure CN103173266AD00091

[0066] 含金属或形成灰分的清净剂充当降低或除去沉积物的清净剂和酸中和剂或防锈齐U,由此减少磨损和腐蚀并延长发动机寿命。 [0066] The metal-containing or ash-forming detergents function as detergents to reduce or remove deposits and acid neutralizers or rust together U, thereby reducing wear and corrosion and extending engine life. 清净剂一般包含具有长疏水性尾的极性头,其中极性头包含酸性有机化合物的金属盐。 Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. 该盐可含含有基本化学计量量的金属,此时,它们通常称作正盐或中性盐,且总碱值或TBN(可通过ASTM D2896测量)通常为0_80。 The metal-containing salts may contain a substantially stoichiometric amount, in which case they are usually described as normal or neutral salts, and the total base number or TBN of (may be measured by ASTM D2896) is generally 0_80. 大量金属碱可通过过量金属化合物(如氧化物或氢氧化物)与酸性气体(如二氧化碳)反应而并入。 A large number of metal base may be incorporated by excess metal compound (e.g. oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). 所得过碱性清净剂包含中和清净剂作为金属碱(例如碳酸盐)胶束的外层。 The resulting overbased detergent comprises neutralized detergent as the metal base (e.g. carbonate) micelle layer. 这种过碱性清净剂的TBN可为150或更大,且TBN通常为250-500或更大。 Such overbased detergents may have a TBN of 150 or greater, and typically 250-500 or TBN greater.

[0067] 可使用的清净剂包括金属,特别是碱金属或碱土金属如钠、钾、锂、钙和镁的油溶性中性和过碱性磺酸盐、酚盐、硫化酚盐、硫代膦酸盐、水杨酸盐和环烷酸盐及其他油溶性羧酸盐。 [0067] The detergents may be used include a metal, particularly alkali metal or alkaline earth metal such as sodium, potassium, lithium, calcium and magnesium, oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thio phosphonate, salicylates, and naphthenates and other oil-soluble carboxylates. 最常用的金属为钙和镁,其两者都可以存在于用于润滑剂的清净剂中,及钙和/或镁与钠的混合物。 The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and / or magnesium with sodium. 特别便利的金属清净剂为TBN为20-500TBN的中性和过碱性磺酸钙,和TBN为50-450的中性和过碱性苯酚钙和硫化苯酚钙。 Is particularly convenient metal detergents having a TBN 20-500TBN neutral and overbased calcium sulfonate, TBN 50-450 and neutral and overbased calcium phenates and sulfurized phenates. 可使用清净剂的组合,无论是过碱性或中性或二者。 Detergents may be used in combination, whether overbased or neutral or both.

[0068] 磺酸盐可由通常通过烷基取代的芳族烃磺化得到的磺酸,例如由石油分馏或通过芳族烃烷基化得到的那些制备。 [0068] Sulfonates may typically such as those prepared by alkyl-substituted aromatic hydrocarbons sulfonated acids obtained from the fractionation of petroleum or obtained by alkylation of aromatic hydrocarbons. 实例包括通过将苯、甲苯、二甲苯、萘、联苯或它们的卤素衍生物如氯苯、氯甲苯或氯萘烷基化得到的那些。 Examples include those obtained by benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene or chloronaphthalene obtained alkylated. 烷基化可在催化剂的存在下进行,其中烷基化剂具有约3至大于70个碳原子。 The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. 烷芳基磺酸盐通常每烷基取代的芳族结构部分含有约9至约80或更多碳原子,优选约16至约60个碳原子。 Alkaryl sulfonates usually per alkyl substituted aromatic moiety containing from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms.

[0069] 可将油溶性磺酸盐或烷芳基磺酸用金属的氧化物、氢氧化物、醇盐、碳酸盐、羧酸盐、硫化物、氢硫化物、硝酸盐、硼酸盐和醚中和。 [0069] The oxide may be an oil-soluble sulfonates or alkaryl sulfonic acids with metal hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers, and. 金属化合物的量根据所需最终产物的TBN选择,但通常为化学计量要求的100-220质量% (优选至少125质量%)。 The amount of metal compound according to the desired TBN of the final product selection, but is generally required stoichiometrically 100-220 mass% (preferably at least 125 mass%).

[0070] 酚类和硫化酚类的金属盐通过与适合的金属化合物如氧化物或氢氧化物反应而制备,中性或过碱性产物可通过本领域已知方法得到。 [0070] metal salts of phenols and sulfurized phenols, neutral or overbased products may be obtained by methods known in the art are prepared with a suitable metal compound such as an oxide or hydroxide reaction. 硫化酚类可通过酚与硫或含硫化合物如硫化氢、单卤化硫或二卤化硫反应而制备,以形成通常为化合物混合物的产物,其中2种或更多种酚通过含硫桥桥联。 Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges .

[0071] 本发明润滑油组合物可进一步含有一种或多种无灰分散剂,其有效地降低当加入润滑油中时,在发动机中使用时沉积物的形成。 [0071] The lubricating oil composition of the present invention may further contain one or more ashless dispersants, which effectively reduce formation when added to lubricating oils when used in engine deposits. 用于本发明组合物中的无灰分散剂包含具有能够联合待分散粒子的官能团的油溶性聚合长链骨架。 Used in the compositions of the present invention are ashless dispersant comprises an oil soluble polymeric long chain backbone having functional groups capable of combined particles to be dispersed. 通常,这种分散剂包含通常经由桥接基团连接在聚合物骨架上的胺、醇、酰胺或酯极性结构部分。 Typically, such dispersants comprise amine, usually attached to the polymer backbone via a bridging group, alcohol, amide or ester polar moieties. 无灰分散剂可例如选自长链烃取代的单-和多羧酸或其酐的油溶性盐、酯、氨基酯、酰胺、酰亚胺和$恶唑啉;长链烃的硫代羧酸酯衍生物;具有多胺结构部分的长链脂族烃,其中多胺结构部分直接连接在长链脂族烃上;和通过长链取代苯酚与甲醛和聚亚烷基多胺缩合而形成的曼尼希缩合物。 Ashless dispersant may be selected, for example, long chain hydrocarbon-substituted mono - or polycarboxylic acids and oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines $ anhydride; long chain hydrocarbon thiocarboxylic acid ester derivative; long chain aliphatic hydrocarbons having a polyamine moiety, wherein the polyamine moieties attached directly to the long chain aliphatic hydrocarbon; and phenol with formaldehyde and polyalkylene polyamine condensates substituted with a long chain formed Mannich condensates. 最常用的分散剂为熟知的琥珀酰亚胺分散剂,其为烃基取代的琥珀酸酐和聚(亚烷基胺)的缩合产物。 The most commonly used dispersants are well known succinimide dispersant, which is a condensation product of hydrocarbyl-substituted succinic anhydride and a poly (alkylene amine). 单琥珀酰亚胺和双琥珀酰亚胺分散剂(及其混合物)是熟知的。 Both mono-succinimide and bis-succinimide dispersants (and mixtures thereof) are well known.

[0072] 优选无灰分散剂为数均分子量(Mn)大于或等于4,000,例如4,000-20, 000的“高分子量”分散剂。 [0072] The ashless dispersant is preferably a number average molecular weight (Mn) greater than or equal to 4,000, e.g. 4,000-20, 000 "high molecular weight" dispersant. 精确的分子量范围取决于用于形成分散剂的聚合物的类型、存在的官能团的数目和所用极性官能团的类型。 The type of polymer depends on the precise molecular weight ranges used to form the dispersant, the type of number of functional groups and the presence of polar functional group employed. 例如对于聚异丁烯衍生的分散剂,高分子量分散剂为用数均分子量为约1680至约5600的聚合物骨架形成的。 For example, a polyisobutylene derivatized dispersant, the dispersant is a high molecular weight with a number average molecular weight of a polymer backbone formed from about 1680 to about 5600. 通常市售的聚异丁烯基分散剂含有数均分子量为约900至约2300、 通过马来酸酐(MW=98)官能化且用分子量为约100至约350的多胺衍生的聚异丁烯聚合物。 Typical commercially available polyisobutylene-based dispersants having a number average molecular weight of from about 900 to about 2300, maleic anhydride (MW = 98) with a molecular weight of functionalized polyamine and from about 100 to about 350 polyisobutylene derivatized polymers. 较低分子量的聚合物也可用于通过将多个聚合物链并入分散剂中而形成高分子量分散剂,这可使用本领域已知的方法实现。 Low molecular weight polymers may also be used by incorporating multiple polymer chains of the dispersing agent to form a high molecular weight dispersing agent, which may be used to achieve methods known in the art.

[0073] 优选的分散剂组包括多胺衍生的聚α -烯烃分散剂,特别是乙烯/ 丁烯α -烯烃和聚异丁烯基分散剂。 [0073] Preferred groups of dispersant include polyamine-derivatized poly α - olefin, dispersants, particularly ethylene / butene-α - olefin and polyisobutylene-based dispersants. 特别优选衍生自聚异丁烯的无灰分散剂,其中所述聚异丁烯用琥珀酸酐基团取代且与聚乙烯胺如聚乙二胺、四亚甲基五胺;或聚氧亚烷基多胺如聚氧丙二胺、三羟甲基氨基甲烷;羟基化合物如季戊四醇;及其组合反应。 Particularly preferably derived from polyisobutylene ashless dispersants, wherein the polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines such as polyethylene diamine, tetraethylene pentamine; or polyoxyalkylene polyamines such as poly polyoxypropylene diamine, tris; polyhydroxy compounds such as pentaerythritol; and combinations thereof reaction. 一个特别优选的分散剂组合为用琥珀酸酐基团取代且与(B)羟基化合物如季戊四醇;(C)聚氧亚烷基多胺如聚氧丙二胺,或(D)聚亚烷基二胺如聚乙二胺和四亚乙基五胺反应的聚异丁烯(A)的组合,其中每摩尔(A),使用约0.3至约2摩尔(B)、(C)和/或(D)。 A particularly preferred combination of dispersants and substituted with (B) a hydroxy compound, e.g., pentaerythritol with succinic anhydride groups; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene glycol amines such as polyisobutylene, tetraethylene pentamine and the reaction of ethylenediamine tetramethylene poly (a) a combination wherein (a), the use of from about 0.3 to about 2 moles (B) per mole of, (C) and / or (D) . 其他优选的分散剂组合包括(A)聚异丁烯琥珀酸酐与(B)聚亚烷基多胺如四亚乙基五胺,和(C)多元醇或多羟基取代的脂族伯胺如季戊四醇或三羟甲基氨基甲烷的组合,如美国专利N0.3,632,511所述。 Other preferred dispersant combination comprises (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine such as pentaerythritol or tris compositions, as described in U.S. Patent No. N0.3,632,511.

[0074] 另一类无灰分散剂包括曼尼希碱缩合产物。 [0074] Another class of ashless dispersants comprises Mannich base condensation products. 这些产物通常通过将约I摩尔烷基取代的单-或多羟基苯与约1-2.5摩尔羰基化合物(例如甲醛和低聚甲醛)和约0.5-2摩尔聚亚烷基多胺缩合而制备,例如美国专利N0.3,442,808中所公开的。 Or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compound (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine condensates are prepared, for example, - these products are approximately I mole of an alkyl substituted by mono- U.S. Patent No. N0.3,442,808 disclosed. 这种曼尼希碱缩合产物可包括作为苯基团上的取代基的金属茂催化聚合的聚合物产物,或可与含有这种在琥珀酸酐上取代的聚合物的化合物以类似于美国专利N0.3,442,808中所述的方式反应。 Such Mannich base condensation products may include as metallocene catalyzed substituent on the phenyl group of polymerized polymer product, containing such a compound or may be substituted on a succinic anhydride in a manner similar to U.S. Pat polymer N0 .3,442,808 reaction in the manner described. 使用金属茂催化剂体系合成的官能化和/或衍生的烯烃聚合物的实例描述于前述出版物中。 Synthesized using a metallocene catalyst system of functionalized and / or derivatized olefin polymers Examples are described in the publications.

[0075] 可将分散剂通过多种常规后处理如硼酸化而进一步后处理,如美国专利Nos.3,087,936和3,254,025通常教导的。 [0075] The dispersing agent can be by a variety of conventional post treatments such as boration further workup, as described in U.S. Patent Nos.3,087,936 and 3,254,025 generally teachings. 分散剂的硼酸化易于通过将酰基含氮分散剂用硼化合物如氧化硼、卤化硼、含硼酸和硼酸的酯以足以提供每摩尔乙酰化氮组合物约0.1至约20原子比硼的量处理而实现。 Borated dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound such as boron oxide, boron halide, boric acid and boronic acid ester containing sufficient to provide per mole of acylated nitrogen composition from about 0.1 to about 20 atomic handle than the amount of boron achieved. 有用的分散剂含有约0.05至约2.0质量%,例如约0.05至约0.7质量%硼。 Useful dispersants contain from about 0.05 to about 2.0 mass%, for example from about 0.05 to about 0.7 mass% boron. 作为脱水硼酸聚合物(主要是(HBO2)3)出现在产物中的硼被认为连接在作为铵盐的分散剂酰亚胺和二酰亚胺上,例如二酰亚胺的偏硼酸盐。 (3 mainly (of HBO2)) appears in the product as dehydrated boric acid polymers is believed to attach to the boron ammonium salt as the dispersant imides and diimides, e.g., the metaborate salt of the diimide. 硼酸化可如下进行:将约0.5-4质量%,例如约I至约3质量%(基于酰基氮化合物的质量)的硼化合物,优选硼酸通常作为浆料加入酰基氮化合物中并在约135°C至约190°C,例如140-170°C下搅拌加热约I至约5小时,之后进行氮气汽提。 Boration can be carried out as follows: Approximately 0.5 to 4 mass%, for example about I to about 3 mass% (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid usually as a slurry, to the acyl nitrogen compound and heating at about 135 ° C to about 190 ° C, e.g. stirred at 140-170 ° C for about I to about 5 hours, followed by nitrogen stripping. 作为选择,硼处理可通过将硼酸加入二羧酸原料与胺的热反应混合物中,同时除去水而进行。 Alternatively, the boron treatment can be conducted by adding boric acid starting material with an amine hot reaction mixture while removing water. 也可应用本领域通常已知的其他后反应方法。 Other reaction generally known in the art may be used.

[0076] 分散剂还可通过与所谓的“封端剂”反应而进一步后处理。 [0076] Dispersions can also be further post treated by reaction with a so-called "capping agent." 通常,将含氮分散剂“封端”以降低这种分散剂对含氟弹性体发动机密封件的不利作用。 Typically, the nitrogen-containing dispersants "capped" to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals. 大量封端剂和方法是已知的。 Numerous capping agents and methods are known. 在已知的“封端剂”中,将碱性分散剂氨基转化成非碱性结构部分(例如酰胺基或酰亚胺基)的那些最适合。 Of the known "capping agents", the conversion of basic dispersant amino groups to non-basic moieties (e.g., an amide group or an imide group) are most suitable. 含氮分散剂与乙酰乙酸烷基酯(例如乙酰乙酸乙酯(EAA))的反应例如描述于美国专利Nos.4,839,071 ;4,839,072和4,579,675中。 The reaction nitrogen-containing dispersant with alkyl acetoacetate (e.g., ethyl acetoacetate (EAA)) is described for example in U.S. Pat. Nos.4,839,071; 4,839,072 and 4,579,675 in. 含氮分散剂与甲酸的反应例如描述于美国专利Nos.3,185,704中。 The reaction of a nitrogen-containing dispersant and formic acid is described in, for example, in U.S. Patent Nos.3,185,704. 含氮分散剂与其他适合封端剂的反应产物描述于美国专利Nos.4,663,064 (羟基乙酸);4,612,132 ;5,334,321 ;5,356,552 ;5,716,912 ;5,849,676 ;5,861,363 (碳酸烷基和亚烷基酯,例如碳酸亚乙酯);5,328,622 (单环氧化物);5, 026,495 ;5,085,788 ;5,259,906 ;5,407,591 (聚(例如双)_ 环氧化物)和4,686,054(马来酸酐或琥珀酸酐)中。 Nitrogen-containing dispersant and other suitable capping agent reaction products are described in U.S. Patent Nos.4,663,064 (hydroxy acid); 4,612,132; 5,334,321; 5,356,552; 5,716 , 912; 5,849,676; 5,861,363 (alkyl and alkylene carbonates esters, such as ethylene carbonate); 5,328,622 (monoepoxide); 5, 026,495; 5 , 085,788; 5,259,906; 5,407,591 (poly (e.g., bis) _ epoxides) and 4,686,054 (maleic anhydride or succinic anhydride) in. 前列并非排他的,其他将含氮分散剂封端的方法为本领域熟练技术人员已知的。 Forefront not exclusively, the other methods of capping nitrogen-containing dispersants are known to those skilled in the art.

[0077] 对于足够的活塞沉积物控制,可将含氮分散剂以提供给润滑油组合物约0.03至约0.15质量%,优选约0.07至约0.12质量%氮的量加入。 [0077] For adequate piston deposit control, a nitrogen-containing dispersant can be supplied to the lubricating oil composition from about 0.03 to about 0.15 mass%, preferably from about 0.07 to about 0.12 mass% of nitrogen was added.

[0078] 无灰分散剂在性质上为碱性的,因此取决于极性基团的性质和分散剂是否被硼酸化或用封端剂处理,TBN可以为约5至约200mg KOH/g。 [0078] Ashless dispersants are basic in nature and therefore depends on the nature and dispersant polar group whether borated or treated with a capping agent, it may be TBN of from about 5 to about 200mg KOH / g. 然而,已知高碱性水平的分散剂氮对常用于形成发动机密封件的含氟弹性体材料具有有害作用,因此优选使用提供活塞沉积物控制所需的最小量分散剂和基本不使用分散剂,优选不使用TBN大于5的分散剂。 However, it is known overbased dispersant nitrogen level fluoroelastomer engine seal materials commonly used have a deleterious effect on formation, it is preferably used to provide piston deposit control of the minimum amount required to use substantially no dispersant and dispersant , preferably no dispersant TBN greater than 5. 优选所用分散剂的量赋予润滑油组合物不大于4,优选不大于3mg KOH/g的ΤΒΝ。 Preferably the amount of dispersant used to impart the lubricating oil composition is no greater than 4, preferably not more than 3mg KOH / g of ΤΒΝ. 另外优选分散剂提供给润滑油组合物不大于30,优选不大于25%的ΤΒΝ。 Further preferably ΤΒΝ dispersant provides the lubricating oil composition is no greater than 30, preferably not more than 25%.

[0079] 可将其他添加剂并入本发明组合物中以使它们满足特殊要求。 [0079] Other additives may be incorporated into the compositions of the present invention is that they meet specific requirements. 可包括在润滑油组合物中的添加剂的实例为金属防锈剂、粘度指数改进剂、腐蚀抑制剂、氧化抑制剂、摩擦改进剂、其他分散剂、消泡剂、抗磨剂和倾点下降剂。 Examples of additives may include in the lubricating oil compositions are metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants, antifoaming agents, antiwear agents and pour point depressants agents. 一些在下面更详细地讨论。 Some are discussed in more detail below.

[0080] 二烃基二硫代磷酸金属盐通常用作抗磨剂和抗氧化剂。 [0080] The dihydrocarbyl dithiophosphate metal salts are commonly used as antiwear and antioxidant agents. 金属可以为碱金属或碱土金属,或铝、铅、锡、钥、锰、镍或铜。 The metal may be an alkali metal or alkaline earth metal, or aluminum, lead, tin, keyhole, manganese, nickel or copper. 锌盐最常以基于润滑油组合物的总重量为0.1-10重量%,优选0.2-2重量%的量用于润滑油中。 Zinc most often based on the total weight of the lubricating oil composition from 0.1 to 10 wt%, preferably from 0.2 to 2% by weight of the lubricating oil. 它们可根据已知技术如下制备:首先通常通过使一种或多种醇或酚与P2S2反应形成二烃基二硫代磷酸(DDPA),然后将形成的DDPA用锌化合物中和。 They can be prepared according to known techniques: typically by first reacting one or more alcohols or a phenol with P2S2 to form dihydrocarbyl dithiophosphoric acid (DDPA), and then neutralizing the formed DDPA with a zinc compound. 例如,二硫代磷酸可通过使伯和仲醇的混合物反应而制备。 For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols Reaction. 作为选择可制备多种二硫代磷酸,其中一种上的烃基在性质上完全为仲,其他上的烃基在性质上完全为伯。 Alternatively multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one kind are entirely secondary in character, on the other hydrocarbon group are entirely primary in character. 为制备锌盐,可使用任何碱性或中性锌化合物,但最通常使用氧化物、氢氧化物和碳酸盐。 To prepare the zinc salt, any basic or neutral zinc compound, but the most commonly used oxides, hydroxides and carbonates. 由于在中和反应中使用过量碱性锌化合物,商业添加剂通常含有过量锌。 The use of an excess of the basic zinc compound in the neutralization reaction, Commercial additives frequently contain an excess of zinc.

[0081] 优选的二烃基二硫代磷酸锌为二烃基二硫代磷酸的油溶性盐并可由下式表示: [0081] The preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:

[0082] [0082]

Figure CN103173266AD00121

[0083] 其中R和R'可以为相同或不同的烃基,其含有1-18,优选2-12个碳原子,并包括基团如烷基、烯基、芳基、芳烷基、烷芳基和脂环族基团。 [0083] wherein R and R 'may be the same or different hydrocarbon group containing 1-18, preferably 2-12 carbon atoms, and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl groups and cycloaliphatic groups. 特别优选作为R和R'基团的是具有2-8个碳原子的烷基。 Particularly preferred as R and R 'are alkyl radicals having 2-8 carbon atoms. 因此,基团可例如为乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十二烷基、十八烷基、2-乙基己基、苯基、丁基苯基、环己基、甲基环戊基、丙烯基、丁烯基。 Thus, the group may be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl , octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. 为了得到油溶性,二硫代磷酸中碳原子(即R和R')的总数一般为5或更大。 In order to obtain oil solubility, the total number of carbon atoms in the dithiophosphoric acid (i.e., R and R ') is generally 5 or more. 二烃基二硫代磷酸锌因此可包括二烷基二硫代磷酸锌。 Dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates. 当使用含有磷含量基于组合物的总质量为约0.02至约0.12质量%,例如约0.03至约0.10质量%,或约0.05至约0.08质量%的润滑剂组合物时,本发明可特别有用。 When containing phosphorus content based on the total mass of the composition is from about 0.02 to about 0.12 mass%, such as from about 0.03 to about 0.10 mass%, or from about 0.05 to about 0.08% by mass of the lubricant composition of the present invention may be particularly useful. 在一个优选的实施方案中,本发明润滑油组合物含有主要(例如50摩尔%以上,例如60摩尔%以上)衍生自仲醇的~二烷基~二硫代憐酸锋。 In a preferred embodiment, the lubricating oil compositions of the invention contain predominantly (e.g. more than 50 mol%, 60 mol% or more, for example) derived from a ~ ~ dialkyl dithiophosphoric acid pity front of a secondary alcohol.

[0084] 氧化抑制剂或抗氧化剂降低矿物油在使用中的劣化倾向。 [0084] Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in use. 氧化劣化可通过润滑剂中的淤渣、金属表面上的清漆状沉积物和粘度增加而证明。 Oxidative degradation by sludge in the lubricant, varnish-like deposits on the metal surfaces and increase the viscosity of the proof. 这种氧化抑制剂包括位阻酚,优选具有C5-C12烷基侧链的烷基苯酚硫酯的碱土金属盐,壬基酚硫化钙,油溶性酚盐和硫化酹盐,磷硫化或硫化烃,亚磷酯(phosphorous ester),硫代氨基甲酸金属盐,如美国专利N0.4,867,890中所述的油溶性铜化合物,和含钥化合物。 Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkyl phenols having preferably thioester C5-C12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized sprinkle salt, phosphosulfurized or sulfurized hydrocarbons , phosphorous esters (phosphorous ester), metal thiocarbamates, such as described in U.S. Patent No. N0.4,867,890 oil soluble copper compounds, and the key-containing compound.

[0085] 具有至少两个直接连接在一个胺氮上的芳族基团的典型油溶性芳族胺含有6-16个碳原子。 [0085] Typical oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms. 胺可含有多于两个芳族基团。 Amines may contain more than two aromatic groups. 具有总计至少3个芳族基团且其中两个芳族基团通过共价键或原子或基团(例如氧或硫原子,或-co-、-so2-或亚烷基)连接且两个直接连接在一个胺氮上的化合物也认为是具有至少两个直接连接在氮上的芳族基团的芳族胺。 Having a total of at least three aromatic groups in which two aromatic groups by a covalent bond or an atom or group (e.g., an oxygen or sulfur atom, or a -CO - SO2- or alkylene -,) and two are a compound attached directly to the amine nitrogen are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen. 芳环通常由选自烧基、环烧基、烧氧基、芳氧基、酸基、酸氣基、轻基和硝基的一个或多个取代基取代。 Aromatic rings are typically selected from the group burn, burn cycloalkyl group, a burning group, an aryloxy group, an acid group, an acid gas group, a nitro group, and a light or more substituents.

[0086] 通常组合使用多种抗氧化剂。 [0086] Generally in combination of more antioxidants. 在一个优选实施方案中,本发明润滑油组合物含有约0.1至约1.2质量%的胺类抗氧化剂和约0.1至约3质量%的酚类抗氧化剂。 In one preferred embodiment, lubricating oil compositions of the invention contain from about 0.1 to about 1.2 mass% of aminic antioxidant and from about 0.1 to about 3 mass% of phenolic antioxidant. 在另一优选实施方案中,本发明润滑油组合物含有约0.1至约1.2质量%的胺类抗氧化剂、约0.1至约3质量%的酚类抗氧化剂和提供给润滑油组合物约10至约IOOOppm钥的量的钥化合物。 In another preferred embodiment, lubricating oil compositions of the invention contain from about 0.1 to about 1.2 mass% of aminic antioxidant, from about 0.1 to about 3 mass% of phenolic antioxidant and provided the lubricating oil composition from about 10 to an amount of about IOOOppm key keyhole compound.

[0087] 合适粘度改进剂的代表性实例为聚异丁烯、乙烯与丙烯的共聚物、聚甲基丙烯酸酯、甲基丙烯酸酯共聚物、不饱和二羧酸与乙烯基化合物的共聚物、苯乙烯与丙烯酸酯的共聚物,及苯乙烯/异戊二烯、苯乙烯/ 丁二烯和异戊二烯/ 丁二烯的部分氢化共聚物,以及丁二烯和异戊二烯的部分氢化均聚物。 [0087] Suitable viscosity modifiers Representative examples are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, a styrene and copolymers of acrylic esters, and styrene / isoprene, styrene / butadiene and isoprene / butadiene copolymer, partially hydrogenated and partially hydrogenated butadiene and isoprene are polymers.

[0088] 还可包括与成品油的其他成分相容的摩擦改进剂和燃料节约试剂。 [0088] may also comprise compatible with the other ingredients of the final oil Friction modifiers and fuel economy agents. 这种材料的实例包括较高级脂肪酸的甘油基单酯,例如单油酸甘油酯;长链聚羧酸与二醇的酯,例如二聚不饱和脂肪酸的丁二醇酯恶唑啉化合物;和烷氧基化烷基取代的单胺、二胺和烷基醚胺,例如乙氧基化牛脂胺(ethoxylated tallow amine)和乙氧基化牛脂醚胺(ethoxylatedtallow ether amine)。 Examples of such materials include glyceryl monoesters of higher fatty acid esters, such as glyceryl mono-oleate; oxazoline compounds butylene glycol long chain esters of polycarboxylic acids with diols, for example dimerized unsaturated fatty acid; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallowamine (ethoxylated tallow amine) and ethoxylated tallow ether amine (ethoxylatedtallow ether amine). [0089] 其他已知的摩擦改进剂包括油溶性有机钥化合物。 [0089] Other known friction modifiers comprise oil-soluble organic compound key. 这种有机钥摩擦改进剂还提供给润滑油组合物抗氧化剂和抗磨剂责任。 This key organic friction modifiers provide the lubricating oil composition further antioxidant and antiwear agents responsibility. 这种油溶性有机钥化合物的实例包括二硫代氨基甲酸盐、二硫代磷酸盐、二硫代次膦酸盐、黄原酸盐、硫代黄原酸盐、硫化物等,及其混合物。 Examples of such oil-soluble organic compound key comprising two dithiocarbamates, dithiophosphates, dithiophosphoric acid salts, xanthates, xanthate thio, sulfide, and mixture. 特别优选二硫代氨基甲酸钥、二烷基二硫代磷酸钥、烷基黄原酸钥和烷基硫代黄原酸钥。 Particularly preferred dithiocarbamates key, key dialkyl dithiophosphate, alkyl xanthate key and key alkylthio xanthan.

[0090] 另外,钥化合物可为酸性钥化合物。 [0090] Further, the compound may be an acidic key key compound. 通过ASTM试验D-664或D-2896滴定程序测量,这些化合物与碱性氮化合物反应且通常为六价的。 By ASTM test D-664 or D-2896 titration procedure and measurement of these compounds with a basic nitrogen compound and typically hexavalent. 包括钥酸、钥酸铵、钥酸钠、钥酸钾和其他碱金属钥酸盐和其他钥盐,例如钥酸氢钠、Mo0C14、MoO2Br2^ Mo2O3Cl6、三氧化钥或类似的酸性钥化合物。 It includes keyhole acid, ammonium key, key, sodium, potassium and other alkali metals keys keys and other keys acid salts, e.g. sodium hydrogen key, Mo0C14, MoO2Br2 ^ Mo2O3Cl6, key trioxide or similar acidic compound key.

[0091] 用于本发明组合物中的钥化合物为下式的有机钥化合物: [0091] The key compounds for the compositions of the present invention is an organic compound of the formula key:

[0092] Mo (ROCS2) 4 和 [0092] Mo (ROCS2) 4 and

[0093] Mo (RSCS2)4, [0093] Mo (RSCS2) 4,

[0094] 其中R为选自烷基、芳基、芳烷基和烷氧基烷基、通常具有1-30个碳原子、优选2-12个碳原子的有机基团,最优选2-12个碳原子的烷基。 [0094] wherein R is selected from alkyl, aryl, aralkyl and alkoxyalkyl, generally having 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms, an organic group, most preferably 2-12 alkyl group carbon atoms. 尤其优选钥的二烷基二硫代氨基甲酸盐。 Particularly preferred key dialkyl dithiocarbamate.

[0095] 用于本发明润滑组合物中的另一组有机钥化合物为三核钥化合物,尤其是式Mo3SkLnQz的那些及其混合物,其中L独立地选自具有有机基团的配体,所述有机基团具有足以赋予化合物可溶或可分散在油中的碳原子数,η为1-4,k为4-7,Q选自中性给电子化合物如水、胺、醇、膦和醚,且z为0-5且包括非化学计量值。 [0095] Another group of organo key compound in the lubricating compositions of this invention are trinuclear key compounds, especially those of the formula Mo3SkLnQz and mixtures thereof wherein the L are independently selected ligands having organo groups, the an organic group having a sufficient number of carbon atoms to impart compound soluble or dispersible in oil, [eta] is 1-4, k is 4-7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is 0 to 5 and includes non-stoichiometric values. 在所有配体有机基团中应总共存在至少21个碳原子,例如至少25、至少30或至少35个碳原子。 It should be present among all the ligand organo groups in total at least 21 carbon atoms, such as at least 25, at least 30 or at least 35 carbon atoms.

[0096]分散剂-粘度指数改进剂充当粘度指数改进剂和分散剂。 [0096] a dispersant - viscosity index improver serving as a viscosity index improver and as a dispersant. 分散剂-粘度指数改进剂的实例包括胺,例如多胺与烃基取代的单羧酸或二羧酸的反应产物,其中烃基取代基包含足够长的链以赋予化合物粘度指数改进性能。 Examples of dispersant - viscosity index improvers include amines, for example, reaction products of polyamines with hydrocarbyl-substituted mono- or dicarboxylic acid in which the hydrocarbyl substituent comprises a chain of sufficient length to impart viscosity index improving properties of the compound. 一般而言,粘度指数改进剂分散剂可例如为乙烯醇的C4-C24不饱和酯或C3-Cltl不饱和单羧酸或C4-Cltl 二羧酸与具有4-20个碳原子的不饱和含氮单体的聚合物;C2-C2(I烯烃与用胺、羟胺或醇中和的不饱和C3-Cltl单羧酸或二羧酸的聚合物;或乙烯与C3-C2tl烯烃的聚合物,其通过C4-C2tl不饱和含氮单体接枝其上或通过不饱和酸接枝在该聚合物骨架上,然后使接枝酸的羧酸基团与胺、羟胺或醇反应而进一步反应。 In general, the viscosity index improver dispersant may be, for example, C4-C24 unsaturated ester of vinyl alcohol or C3-Cltl unsaturated monocarboxylic acid or C4-Cltl dicarboxylic acid having 4-20 carbon atoms containing an unsaturated polymers of nitrogen monomer; C2-C2 (I olefin with with an amine, hydroxyamine or an alcohol and an unsaturated C3-Cltl polymer mono- or dicarboxylic acid; or ethylene with C3-C2tl olefin polymer, thereon or by grafting an unsaturated acid grafted onto the polymer backbone, and then the reaction of the carboxylic acid groups of the grafted acid with an amine, hydroxyamine or an alcohol and further reaction of C4-C2tl unsaturated nitrogen-containing monomers.

[0097] 另外称作润滑油流动改进剂(LOFI)的倾点下降剂降低流体流动或可倒出的最小温度。 [0097] Also known as lube oil flow improvers (LOFIs) pour point depressant or decreasing the minimum temperature of the fluid flow can be poured. 这种添加剂是熟知的。 Such additives are well known. 改进流体低温流动性的那些添加剂通常为富马酸C8-C18二烷基酯/乙酸乙烯酯共聚物,和聚甲基丙烯酸酯。 Additives that improve the low temperature fluidity of the fluid is typically C8-C18 dialkyl fumarate ester / vinyl acetate copolymers, and polymethacrylates. 泡沫控制可通过聚硅氧烷类型的消泡剂如硅油或聚二甲基硅氧烷提供。 Foam control may be such as silicone oil or polydimethyl siloxane of the type provided by the silicone antifoaming agent.

[0098] 一些上述添加剂可提供多种效果;因此例如单一添加剂可充当分散剂-氧化抑制齐U。 [0098] Some of the above additives can provide a variety of effects; thus for example, a single additive may act as a dispersant - Homogeneous oxidation inhibiting U. 该路线是熟知的,在这里不需要进一步详述。 The route is well known and need not be further detailed.

[0099] 在本发明中,还可优选包含保持共混物粘度稳定性的添加剂。 [0099] In the present invention, it may preferably comprise an additive which maintains the stability of the viscosity of the blend. 因此,尽管含有极性基团的添加剂在预混合阶段中实现适当的低粘度,已观察到当长时间储存时一些组合物粘度提高。 Thus, although polar group-containing additives achieve a suitably low viscosity in the pre-blending stage it has been observed that when stored for prolonged periods of some compositions increase in viscosity. 在控制该粘度提高中有效的添加剂包括长链烃,所述长链烃通过与如前文所述的制备无灰分散剂中使用的单-或二羧酸或酐反应而官能化。 Effective additives include long chain hydrocarbons, long-chain hydrocarbons in the increase in viscosity by controlling the use and preparation of ashless dispersants as hereinbefore described in mono - functionalized reactions or dicarboxylic acid or anhydride.

[0100] 当润滑组合物包含一种或多种上述添加剂时,各添加剂通常以能使添加剂提供其理想功能的量混入基油中。 [0100] When lubricating compositions contain one or more of the above additives, each additive is typically present in an amount that enables the additive to provide its desired function blended into the base oil. 用于不同润滑剂中时这类添加剂的典型有效量列于下文中。 Such additives typically used for different effective amount of a lubricant are listed below. 所有所列值作为质量%活性成分描述。 All listed values ​​described as mass% active ingredient.

[0101] 船用气缸润滑剂(“MDCL”) [0101] marine cylinder lubricant ( "MDCL")

[0102] 船用气缸润滑剂可使用10-35质量%,优选13-30质量%,最优选16_24质量%的浓缩物或添加剂包,其余为基本油料。 [0102] Lubricants that can be used marine cylinder 10-35% by mass, preferably 13-30% by mass, most preferably 16_24 mass% of the concentrate or additive package, the remainder being base stock. 它优选包含基于MDCL的总质量为至少50质量%,更优选至少60质量%,甚至更优选至少70质量%的具有润滑粘度的油。 It preferably comprises at least 50% by mass based on the total mass of the MDCL, and more preferably at least 60% by mass, and even more preferably at least 70% by mass of oil of lubricating viscosity.

[0103] 完全配制的MDCL优选具有至少20,例如约30至约IOOmg KOH/g的TBN (ASTMD2896)。 [0103] Fully formulated MDCL preferably at least 20, for example from about 30 to about IOOmg KOH / g of TBN (ASTMD2896). 更优选,组合物具有至少40,例如约40至约70mgK0H/g的TBN。 More preferably, the composition has at least 40, for example from about 40 to about 70mgK0H / g of TBN.

[0104] MDCL优选具有约12质量%或更少,优选约11质量%或更少,更优选约10质量%或更少,例如9质量%或更少的硫酸化灰分(SASH)含量(ASTM D-874)。 [0104] MDCL preferably about 12 mass% or less, preferably about 11 mass% or less, more preferably about 10 mass% or less, for example, 9% or less by mass of sulfated ash (the SASH) content (ASTM D-874).

[0105] 以下可作为MDCL中添加剂的典型比例的实例提到: [0105] The following may be mentioned as examples of typical additives in MDCL proportions:

[0106] [0106]

Figure CN103173266AD00141

[0107] 筒状活寒式发动机油(“ΤΡΕ0”) [0107] Live cylindrical cold engine oil ( "ΤΡΕ0")

[0108] 筒状活塞式发动机油可使用7-35质量%,优选10-28质量%,更优选12_24质量%的浓缩物或添加剂包,其余为基本油料。 [0108] trunk piston engine oil may be used 7-35% by mass, preferably 10-28% by mass, and more preferably 12_24 mass% of the concentrate or additive package, the remainder being base stock.

[0109] 完全配制的筒状活塞式发动机油优选具有至少10,例如约15至约60mg KOH/g的TBN (ASTM D2896)。 [0109] Fully formulated trunk piston engine oils preferably have at least 10, such as from about 15 to about 60mg KOH / g of TBN (ASTM D2896). 更优选,组合物具有至少20,例如约30至约55mg KOH/g的TBN。 More preferably, the composition has at least 20, for example from about 30 to about 55mg KOH / g of TBN.

[0110] 完全配制的筒状活塞式发动机油优选具有约7质量%或更少,优选约6.5质量%或更少,例如6.3质量%或更少的硫酸化灰分(SASH)含量(ASTMD-874)。 [0110] Fully formulated trunk piston engine oils having preferably from about 7 mass% or less, preferably about 6.5 mass% or less, for example 6.3% or less by mass of sulfated ash (the SASH) content (ASTMD-874 ).

[0111] 以下可作为TPEO中添加剂的典型比例的实例提到: [0111] The following may be mentioned as examples of typical additives in proportions TPEO:

[0112] [0112]

Figure CN103173266AD00142
Figure CN103173266AD00151

[0113]曲轴箱润滑剂 [0113] crankcase lubricants

[0114] 完全配制的曲轴箱润滑油组合物优选具有至少6,例如约6至约18mgK0H/g的TBN(ASTM D2896)。 [0114] Fully formulated crankcase lubricating oil composition preferably has at least 6, such as from about 6 to about 18mgK0H / g of TBN (ASTM D2896). 更优选,组合物具有至少8.5,例如约8.5或9至约18mg KOH/g的TBN。 More preferably, the composition has at least 8.5, for example about 8.5 or about 9 to 18mg KOH / g of TBN.

[0115] 完全配制的曲轴箱润滑油组合物优选具有约1.1质量%或更少,优选约1.0质量%或更少,更优选约0.8质量%或更少,例如0.5质量%或更少的硫酸化灰分(SASH)含量(ASTM D-874)。 Sulfate [0115] Fully formulated crankcase lubricating oil composition is preferably about 1.1 mass% or less, preferably about 1.0% by mass or less, more preferably about 0.8 mass% or less, such as 0.5 mass% or less ash (the SASH) content (ASTM D-874).

[0116] 以下可作为曲轴箱润滑剂(包括客车基油和重型柴油机油)中添加剂的典型比例的实例提到: [0116] The following may be mentioned as an example of a typical crankcase lubricant proportions (including passenger car and heavy duty diesel oil base oil) additives:

[0117] [0117]

Figure CN103173266AD00152

[0118] 完全配制的本发明润滑油组合物优选具有少于约0.4质量%的硫含量。 [0118] Fully formulated lubricating oil compositions of the present invention preferably has a sulfur content of less than about 0.4% by mass. 对于曲轴箱应用,完全配制的润滑油组合物优选具有少于约0.35质量%,更优选少于约0.3质量%,例如少于约0.20质量%的硫含量。 For crankcase applications, fully formulated lubricating oil compositions preferably have less than about 0.35 mass%, more preferably less than about 0.3% by mass, for example a sulfur content of less than about 0.20% by mass. 优选完全配制的润滑油组合物(具有润滑粘度的油加所有添加剂和添加剂稀释剂)的Noack挥发度(ASTM D5880)不大于13,例如不大于12,优选不大于10。 Preferably fully formulated lubricating oil composition (oil of lubricating viscosity plus all additives and additive diluent) Noack volatility (ASTM D5880) not greater than 13, such as no greater than 12, preferably not more than 10. 完全配制的本发明润滑油组合物优选具有不大于1200ppm的磷,例如不大于IOOOppm的磷,或不大于800ppm的磷,例如不大于600ppm的磷,或者不大于500或400ppm的磷。 Fully formulated lubricating oil compositions of the present invention preferably have no greater than 1200ppm P, for example no greater than IOOOppm phosphorus, or no greater than 800ppm of phosphorus, such as no greater than 600ppm of phosphorus, or no greater than 500 or 400ppm of phosphorous. [0119] 尽管不是必需的,但理想的是制备一种或多种包含添加剂的添加剂浓缩物(浓缩物有时称作添加剂包),由此可将几种添加剂同时加入油中以形成润滑油组合物。 [0119] Although not required, it is desirable to prepare one or more additive concentrates comprising additives (concentrates sometimes being referred to as additive packages) whereby several additives can be added simultaneously to the oil to form the lubricating oil composition thereof. 制备本发明润滑油组合物的浓缩物可例如含有约0.1至约30质量%,优选0.5-30质量%的一种或多种式⑴化合物;约10至约40质量%的含氮分散剂;约2至约20质量%的胺类抗氧化剂、酚类抗氧化剂、钥化合物或其混合物;约5-40质量%的清净剂;和约2至约20质量%的二烃基二硫代磷酸金属盐。 Preparation of lubricating oil composition of the present invention, for example, concentrates may contain from about 0.1 to about 30% by mass, preferably 0.5 to 30 mass% of one or more compounds of formula ⑴; from about 10 to about 40 mass% of a nitrogen-containing dispersant; from about 2 to about 20 mass% of aminic antioxidant, a phenolic antioxidant, a key or mixtures thereof; about 5-40% by weight of a detergent; and about 2 to about 20% by mass of the metal dihydrocarbyl dithiophosphate .

[0120] 最终组合物可使用5-25质量%,优选5-18质量%,通常10_15质量%的浓缩物,其余为具有润滑粘度的油和粘度改进剂。 [0120] The final composition may employ from 5 to 25 mass%, preferably 5 to 18 mass%, typically 10_15 mass% of the concentrate, the remainder being oil of lubricating viscosity modifier and viscosity.

[0121] 本文表述的所有重量(和质量)百分数(除非另有指出)均基于添加剂、和/或添加剂包的活性成分(A.1.)含量,不包括任何相关稀释剂。 [0121] All weights expressed herein (and mass) percents (unless otherwise indicated) are based on additives and / or active ingredients of the additive package (A.1.) Content, exclusive of any diluent. 然而,清净剂通常在稀释油中形成,所述稀释油不从产物中除去,且清净剂的TBN通常供给相关稀释油中的活性清净剂。 However, detergents are conventionally formed in diluent oil, the diluent oil is not removed from the product, and the TBN of a detergent active detergents usually supplied in the associated diluent oil. 因此,当涉及清净剂时,重量(和质量)百分数(除非另有指出)为活性成分和相关稀释油的总重量(或质量)百分数。 Thus, when referring to detergents, weight (and mass) percents (unless otherwise indicated) total weight (or mass) percent of active ingredient and associated diluent oil.

[0122] 参考以下实施例进一步理解本发明,其中除非另有指出,所有份为重量(或质量)份。 [0122] reference to the following examples further understanding of the invention, in which, unless otherwise indicated, all parts are by weight (or mass).

实施例 Example

[0123] 重要的是将碱度引入润滑油组合物中保持尽可能长的时间。 [0123] is important that the lubricating oil composition is introduced basicity held as long as possible. 重要的还有TBN和TAN水平相交的时间尽可能长。 It is also important TBN and TAN levels intersect as long as possible. 这些措施都确保更长的油寿命和经更长时期更好的发动机保护。 These measures are to ensure the longer term and better engine protection and longer oil life by.

[0124] 对三种润滑油组合物进行烧杯试验:参比油、实施例1和实施例2。 [0124] the lubricating oil composition was subjected to the three tests beaker: Oil Reference Example 1 and Example 2. 参比油包含在基油中2.475重量%的TBN为425mgK0H/g的过碱性磺酸钙清净剂。 Reference oil in a base oil comprising 2.475 wt% of the TBN of 425mgK0H / g overbased calcium sulfonate detergent. 实施例1包含在基油中2.475重量%的TBN为425mgK0H/g的过碱性磺酸钙清净剂和1.369重量%的聚{[2-羟基-5-(四丙烯基)-1,3-亚苯基]亚甲基}。 Example 1 contained 2.475% by weight in the base oil a TBN of 425mgK0H / g overbased calcium sulfonate detergent and 1.369% by weight of poly {[2-hydroxy-5- (four-propenyl) -1,3- phenylene] methylene}. 实施例2包含在基油中2.475重量%的TBN为425mgK0H/g的过碱性磺酸钙清净剂和1.369重量%的聚{[2-羟基乙氧基_5_(四丙烯基)-1,3-亚苯基]亚甲基}。 Example 2 Poly included in the base oil was 2.475 wt.% Of the TBN 425mgK0H / g overbased calcium sulfonate detergent and 1.369 wt% of {[2-hydroxyethoxy _5_ (four-propenyl) -1, 3-phenyl] methylene}. 所有三种润滑油组合物具有10.5mgK0H/g的TBN(ASTMD2896)。 TBN (ASTMD2896) lubricating oil composition having all three 10.5mgK0H / g of.

[0125] 聚{[2-羟基-5-(四丙烯基)-1,3-亚苯基]亚甲基}如下制备: [0125] Poly {[2-hydroxy-5- (four-propenyl) -1,3-phenylene] methylene} was prepared as follows:

[0126] 将对-四丙烯基苯酚(称为“TPP” ) (I摩尔当量,市售的)、烷基苯磺酸(相对于TPP,0.0033摩尔%)和甲苯(相对于TPP,30质量%)装入装配有顶部搅拌器(overheadstirrer)和迪安-斯达克回流装置的隔板式反应器中。 [0126] will be - tetrapropenylphenol (referred to as "TPP") (I molar equivalents, commercially available), alkylbenzene sulfonic acid (with respect to the TPP, 0.0033 mol%) and toluene (with respect to the TPP, 30 mass %) fitted with an overhead stirrer was charged (overheadstirrer) and Dean - Stark reflux baffled reactor apparatus. 始终使用氮气层。 Always use a nitrogen blanket. 将搅拌提高至160-170rpm且温度经40分钟上升至110°C。 The stirring and the temperature was increased to 160-170rpm increased to 110 ° C over 40 minutes. 经2小时以恒定速率装入36.5%甲醛溶液(相对于所用TPP,1.18当量摩尔甲醛)。 2 hours 36.5% formaldehyde solution was charged at a constant rate (with respect to the TPP, 1.18 equiv moles of formaldehyde). 在整个添加中温度保持在110°C。 Throughout the addition the temperature was maintained at 110 ° C. 当甲醛添加完成时,将温度提高至120°C并保持I小时以除去其余水。 When the formaldehyde addition was complete, the temperature was increased to 120 ° C and held I the remaining hours to remove water. 将反应冷却至90°C,然后经0.5小时装入50%氢氧化钠溶液(相对于烷基苯磺酸,1.25摩尔当量)。 The reaction was cooled to 90 ° C, over 0.5 h and then charged with 50% sodium hydroxide solution (with respect to the alkylbenzene sulfonic acid, 1.25 molar equivalents). 温度经0.5小时上升至130°C并保持另外I小时以除去水。 Temperature rise over 0.5 hours to 130 ° C and held for an additional I hour to remove water. 用建立用于蒸馏的设备,将中间物在真空下经I小时加热至130°C以除去甲苯。 Establishing a distillation apparatus for the intermediate was heated under vacuum for I hour to 130 ° C to remove toluene. 使用矿物油将产物稀释至50%活性成分。 The product was diluted with mineral oil to 50% active ingredient.

[0127] 如下制备聚{[2-羟基乙氧基-5-(四丙烯基)-1,3-亚苯基]亚甲基}: [0127] Preparation of poly {as [2-hydroxy-ethoxy-5- (four-propenyl) -1,3-phenylene] methylene}:

[0128] 将对-四丙烯基苯酚(称为“TPP”)(1摩尔当量,市售的)、烷基苯磺酸(相对于TPP, 0.0033摩尔%)和甲苯(相对于TPP,30质量%)装入装配有顶部搅拌器和迪安-斯达克回流装置的隔板式反应器中。 [0128] will be - tetrapropenylphenol (referred to as "TPP") (1 molar equivalent, commercially available), alkylbenzene sulfonic acid (with respect to the TPP, 0.0033 mol%) and toluene (with respect to the TPP, 30 mass %) charged fitted with an overhead stirrer and Dean - Stark reflux baffled reactor apparatus. 始终使用氮气层。 Always use a nitrogen blanket. 将搅拌速率提高至160-170rpm。 The stirring rate was increased to 160-170rpm. 温度经40分钟上升至110°C。 Temperature is increased to 110 ° C over 40 minutes. 经2小时以恒定速率装入36.5%甲醛溶液(相对于所用TPP,1.18当量摩尔甲醛)。 2 hours 36.5% formaldehyde solution was charged at a constant rate (with respect to the TPP, 1.18 equiv moles of formaldehyde). 在整个添加中温度保持在110°c。 Throughout the addition the temperature was maintained at 110 ° c. 当甲醛添加完成时,将温度提高至120°c并保持I小时以除去其余水。 When the formaldehyde addition was complete, the temperature was increased to 120 ° c and I held the remaining hours to remove water. 将反应冷却至90°C,然后经0.5小时装入50%氢氧化钠溶液(相对于TPP,2.22质量%)。 The reaction was cooled to 90 ° C, over 0.5 h and then charged with 50% sodium hydroxide solution (with respect to the TPP, 2.22% by mass). 温度经0.5小时上升至130°C并保持另外I小时以除去水。 Temperature rise over 0.5 hours to 130 ° C and held for an additional I hour to remove water. 用建立用于蒸馏的设备,将中间物在真空下经I小时加热至130°C以除去甲苯。 Establishing a distillation apparatus for the intermediate was heated under vacuum for I hour to 130 ° C to remove toluene. 装入二甲苯(相对于TPP,30质量%),同时冷却至90°C。 Xylene was charged (with respect to the TPP, 30% by mass), while cooling to 90 ° C. 将迪安-斯达克设备从蒸馏转换成回流。 The Dean - Stark apparatus by distillation from the conversion to reflux. 使用滴液漏斗经0.5小时装入碳酸亚乙酯(相对于TPP,1.02当量摩尔)。 0.5 hours using a dropping funnel was charged ethylene carbonate (with respect to the TPP, 1.02 mol equiv) was. 温度经I小时上升至165°C的回流点。 Temperature is increased to the reflux point of 165 ° C over I hour. 使用IR分析测定碳酸亚乙酯完全消耗的时间(通常在2.5小时以后)。 Determination of the time complete consumption of ethylene carbonate using IR (normally after 2.5 hours). 温度保持在165°C,并使用真空蒸馏除去二甲苯。 Temperature was maintained at 165 ° C, and xylene was removed using vacuum distillation. 使用矿物油将产物稀释至50%活性成分。 The product was diluted with mineral oil to 50% active ingredient.

[0129] 烧杯试验包括用1.0M硫酸滴定油配制剂,并分析TAN和TBN。 [0129] beaker was washed with 1.0M sulfuric acid titration assays include oil formulations, and analyzing TAN and TBN. 酸的流速为IOml/hr,油的量为250g,搅拌速率为300rpm,且油温为95°C。 The acid flow rate of IOml / hr, the amount of oil was 250g, agitation rate of 300rpm, and an oil temperature of 95 ° C.

[0130] 在测试各个试样以后,在油分析以前使用离心步骤除去不溶性固体。 [0130] After each test specimen used previously centrifugation step to remove insoluble solids in the oil analysis.

[0131] 结果如下: [0131] Results are as follows:

[0132] [0132]

Figure CN103173266AD00171

[0135] [0135]

Figure CN103173266AD00181

[0136] 结果也显示于附图中。 [0136] The results are also shown in the accompanying drawings.

[0137] 结果显示参比油比实施例1和2更早地达到TAN和TBN交叉。 [0137] The results show that reference oil in Example 1 and 2 than earlier and reached TBN TAN cross. 因此,参比油中的碱比实施例1和2中的碱更快地贫化。 Accordingly, the reference oil base depleted faster than the base 1 and Example 2. 事实上,实施例1和2甚至在2.5小时时在试验结束时也不显示TAN和TBN交叉。 Indeed, Example 1 and 2 are not displayed even when the end of the test and 2.5 hours TBN TAN cross. 当润滑油组合物显示出TAN和TBN交叉时,组合物具有不足以中和发动机产生的任何酸的碱水平,这导致发动机磨损。 When the lubricating oil composition exhibits cross TBN and TAN when the composition has any base and insufficient acid levels generated by the engine, which leads to engine wear. 这些结果是令人惊讶的,因为实施例I和2在开始试验时不包含比参比油更多的碱(即所有实施例以10.5mgK0H/g的TBN开始烧杯试验)。 These results are surprising, because Example I and 2 are not included in the beginning of the test more than the reference oil base (i.e., in all embodiments 10.5mgK0H / g of TBN start jar test).

Claims (14)

  1. 1.降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)的方法,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂,所述方法包括向润滑油组合物中加入一种或多种式(I)化合物或其碱土金属盐: A method for reducing the rate of depletion of alkalinity in the engine lubricating oil composition (as determined by ASTM D2896) of the lubricating oil composition comprises at least one oil-soluble overbased alkali or alkaline earth metal detergent, the method comprises adding one or more lubricating oil composition of formula (I) or a compound of alkaline earth metal salts:
    Figure CN103173266AC00021
    其中: X为1-50,优选1-40,更优选1-30 ; R1和R2为H、具有1-12个碳原子的烃基或具有1-12个碳原子和至少一个杂原子的烃基;· R为具有9-100,优选9-70,最优选9 -50个碳原子的烃基;且η 为0-10。 Wherein: X is 1-50, preferably 1-40, more preferably 1-30; R1 and R2 is H, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms and having at least one hetero atoms; · R having 9-100, preferably 9-70, most preferably a hydrocarbon group of 9-50 carbon atoms; and η is 0-10.
  2. 2.根据权利要求1的方法,其中式⑴中的η为O。 2. The method according to claim 1, wherein in the formula ⑴ η is O.
  3. 3.根据前述权利要求中任一项的方法,其中式(I)中的X为I。 3. The method according to any of the preceding claims, wherein in the formula (I) X is I.
  4. 4.根据前述权利要求中任一项的方法,其中式(I)中的R是9-20个碳原子,优选9-15个碳原子的。 4. A method according to any one of the preceding claims, wherein in the formula (I) R is a 9-20 carbon atoms, preferably 9-15 carbon atoms.
  5. 5.根据前述权利要求中任一项的方法,其中式(I)中的R为支化的。 The method according to any one of the preceding claims, wherein in the formula (I) R is branched.
  6. 6.根据前述权利要求中任一项的方法,其中在式⑴中,R1=H, R2=H且R在基团- 0-[CH2CH2OJnH的对位上。 6. A method according to any one of the preceding claims, wherein in the formula ⑴, R1 = H, R2 = H and R is the group - the para 0- [CH2CH2OJnH of.
  7. 7.根据前述权利要求中任一项的方法,其中式(I)化合物包含小于I摩尔%,优选小于0.5摩尔%,最优选小于0.1摩尔%的未反应烷基苯酚。 7. A method according to any of the preceding claims, wherein formula (I) compound comprises less than I mole%, preferably less than 0.5 mol%, most preferably less than 0.1 mol% of unreacted alkylphenol.
  8. 8.根据前述权利要求中任一项的方法,其中对于多于60,优选多于7O,优选多于80,优选多于90,或最优选多于95摩尔%的式(I)化合物,η=1。 8. A method according to any one of the preceding claims, wherein for more than 60, preferably more than 7O, preferably more than 80, preferably more than 90, or most preferably more than 95 mol% of the compound of formula (I), η = 1.
  9. 9.根据前述权利要求中任一项的方法,其中式(I)化合物的碱土金属盐为钙或镁盐。 9. A method according to any of the preceding claims, alkaline earth metal salts of the compound (I) wherein the formula is the calcium or magnesium salt.
  10. 10.根据前述权利要求中任一项的方法,其中对于小于5摩尔%的式(I)化合物,η >2,例如二烷氧基化、三烷氧基化和四烷氧基化的。 10. The method of any of the preceding claims wherein for any of Formula (I) compound is less than 5 mol%, η> 2, for example, two alkoxylated, tri and tetra-alkoxylated alkoxylated requirements.
  11. 11.根据前述权利要求中任一项的方法,其中式(I)化合物为亚甲基桥联烷基苯酚或乙氧基化亚甲基桥联烧基苯酌.。 11. The method according to any one of the preceding claims, wherein the compound of formula (I) is methylene-bridged alkyl phenols or ethoxylated methylene-bridged benzene burning discretion ..
  12. 12.根据前述权利要求中任一项的方法,其中润滑油组合物具有通过ASTM D2896测量的4-100的ΤΒΝ,优选5-75,甚至更优选6_70的ΤΒΝ。 12. A method according to any of the preceding claims, wherein the lubricating oil composition has ΤΒΝ measured by ASTM D2896 of 4-100, preferably 5-75, and even more preferably of ΤΒΝ 6_70.
  13. 13.根据前述权利要求中任一项的方法,其中润滑油组合物为船用气缸润滑剂、筒状活塞式发动机油、气体发动机油或曲轴箱润滑油组合物(包括客车机油和重型柴油机油)。 13. The method according to any one of the preceding claims, wherein the lubricating oil composition is a marine cylinder lubricants, trunk piston engine oils, gas oil or the engine crankcase lubricating oil composition (including passenger car motor oils and heavy duty diesel oil) .
  14. 14.一种或多种式(I)化合物或其碱土金属盐降低用于发动机中的润滑油组合物的碱度耗减速率(通过ASTM D2896测定)的用途: 14. The one or more compounds of formula (I) or a compound of alkaline earth metal to reduce the rate of depletion of basicity engine lubricating oil composition (as determined by ASTM D2896) for Use:
    Figure CN103173266AC00031
    其中:x为1-50,优选1-40,更优选1-30 ;RJ和R2为H、具有1_12个碳原子的烃基或具有1-12个碳原子和至少一个杂原子的烃基;R为具有9-100,优选9-70,最优选9_50个碳原子的烃基;且11为0-10,所述润滑油组合物包含至少一种油溶性过碱性碱金属或碱土金属清净剂。 Wherein: x is 1-50, preferably 1-40, more preferably 1-30; RJ and R2 is H, a hydrocarbon group having 1_12 carbon atoms or having 12 carbon atoms and at least one hetero atom of a hydrocarbon group; R & lt is having 9-100, preferably 9-70, most preferably a hydrocarbon group 9_50 carbon atoms; 0-10 and 11, the lubricating oil composition comprises at least one oil-soluble overbased alkali or alkaline earth metal detergents.
CN 201210557466 2011-12-21 2012-12-20 Method of reducing the rate of depletion of basicity of lubricating oil composition in use in engine CN103173266A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11194915.2 2011-12-21
EP11194915 2011-12-21

Publications (1)

Publication Number Publication Date
CN103173266A true true CN103173266A (en) 2013-06-26

Family

ID=47630952

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201210557466 CN103173266A (en) 2011-12-21 2012-12-20 Method of reducing the rate of depletion of basicity of lubricating oil composition in use in engine

Country Status (9)

Country Link
US (1) US20140011725A1 (en)
JP (1) JP2013129832A (en)
CN (1) CN103173266A (en)
BE (1) BE1020644A3 (en)
CA (1) CA2799378A1 (en)
DE (1) DE102012223638A1 (en)
FR (1) FR2984919A1 (en)
GB (1) GB201222834D0 (en)
NL (1) NL2010022C (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5259967A (en) * 1992-06-17 1993-11-09 The Lubrizol Corporation Low ash lubricant composition
CN1740291A (en) * 2004-08-26 2006-03-01 英菲诺姆国际有限公司 Lubricating oil compositions
CN102212409A (en) * 2010-04-06 2011-10-12 英菲诺姆国际有限公司 Lubricating oil composition

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US849676A (en) 1906-04-02 1907-04-09 John B Gordon Display-stand.
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3185704A (en) 1962-09-04 1965-05-25 Exxon Research Engineering Co Formamide of mono-alkenyl succinimide
US3442808A (en) 1966-11-01 1969-05-06 Standard Oil Co Lubricating oil additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
US4686054A (en) 1981-08-17 1987-08-11 Exxon Research & Engineering Co. Succinimide lubricating oil dispersant
US4579675A (en) 1983-11-09 1986-04-01 Texaco Inc. N-substituted enaminones and oleaginous compositions containing same
US4612132A (en) 1984-07-20 1986-09-16 Chevron Research Company Modified succinimides
US4663064A (en) 1986-03-28 1987-05-05 Texaco Inc. Dibaisic acid lubricating oil dispersant and viton seal additives
US4839071A (en) 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in lubricating oil compositions
US4839072A (en) 1987-05-18 1989-06-13 Exxon Chemical Patents Inc. Polyolefinic succinimide polyamine alkyl acetoacetate adducts
US5085788A (en) 1987-11-19 1992-02-04 Exxon Chemical Patents Inc. Oil soluble dispersant additives useful in oleaginous compositions
US5026495A (en) 1987-11-19 1991-06-25 Exxon Chemical Patents Inc. Oil soluble dispersant additives useful in oleaginous compositions
CA2008258C (en) 1989-01-30 2001-09-11 Jacob Emert Oil soluble dispersant additives modified with monoepoxy monounsaturated compounds
US5259906A (en) 1992-04-20 1993-11-09 Wallace Computer Services, Inc. Method of making and using a combined shipping label product information device
US5356552A (en) 1993-03-09 1994-10-18 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free lubricating oils having modified high molecular weight succinimides
US5334321A (en) 1993-03-09 1994-08-02 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Modified high molecular weight succinimides
US5716912A (en) 1996-04-09 1998-02-10 Chevron Chemical Company Polyalkylene succinimides and post-treated derivatives thereof
US5861363A (en) 1998-01-29 1999-01-19 Chevron Chemical Company Llc Polyalkylene succinimide composition useful in internal combustion engines
CA2509735C (en) * 2004-06-11 2012-09-25 Infineum International Limited Detergent additives for lubricating oil compositions
EP1642956A1 (en) * 2004-06-11 2006-04-05 Infineum International Limited Detergent additive combination for lubricating compositions
EP1997870A1 (en) * 2004-08-26 2008-12-03 Infineum International Limited Lubricating oil compositions
EP1657292A1 (en) * 2004-11-16 2006-05-17 Infineum International Limited Lubricating oil additive concentrates
EP1798278B1 (en) * 2005-12-15 2015-07-29 Infineum International Limited Use of a rust inhibitor in a lubricating oil composition
EP1889896A3 (en) * 2006-08-08 2008-09-10 Infineum International Limited Lubricating oil composition containing detergent additives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5259967A (en) * 1992-06-17 1993-11-09 The Lubrizol Corporation Low ash lubricant composition
CN1740291A (en) * 2004-08-26 2006-03-01 英菲诺姆国际有限公司 Lubricating oil compositions
CN102212409A (en) * 2010-04-06 2011-10-12 英菲诺姆国际有限公司 Lubricating oil composition

Also Published As

Publication number Publication date Type
CA2799378A1 (en) 2013-06-21 application
JP2013129832A (en) 2013-07-04 application
US20140011725A1 (en) 2014-01-09 application
GB2498635A (en) 2013-07-24 application
FR2984919A1 (en) 2013-06-28 application
NL2010022C (en) 2013-09-18 grant
NL2010022A (en) 2013-06-24 application
BE1020644A3 (en) 2014-02-04 grant
GB201222834D0 (en) 2013-01-30 grant
DE102012223638A1 (en) 2013-06-27 application

Similar Documents

Publication Publication Date Title
US7727943B2 (en) Titanium compounds and complexes as additives in lubricants
US20040077506A1 (en) Lubricating oil compositions
US20040029747A1 (en) Modified detergents and lubricating oil compositions containing same
US20060116299A1 (en) Lubricating oil compositions
US20050137100A1 (en) Lubricating oil composition containing an alkali metal detergent
US20070006855A1 (en) EGR equipped diesel engines and lubricating oil compositions
US20070111908A1 (en) Titanium-containing lubricating oil composition
US20080139429A1 (en) Titanium-containing lubricating oil composition
US20030224948A1 (en) Lubricating oil additive comprising EC-treated succinimide, borated dispersant and corrosion inhibitor
US20080020950A1 (en) Lubricating Oil Composition
US20110077182A1 (en) System oil formulation for marine two-stroke engines
US6734148B2 (en) Dispersants and lubricating oil compositions containing same
US20070111905A1 (en) Low sulfur and low phosphorus heavy duty diesel engine lubricating oil composition
EP2071009A1 (en) Trunk piston engine lubricating oil compositions
US20080039349A1 (en) Lubricating oil composition
US20060276353A1 (en) Lubricating oil composition
US20100062957A1 (en) Method of Reducing Asphaltene Precipitation in an Engine
US7585820B2 (en) Detergent composition for a low sulfur, low sulfated ash and low phosphorus lubricating oil for heavy duty diesel engines
US4548723A (en) Ortho-carboxy phenylphenone lubricating oil additives
EP1195426A1 (en) Lubricating oil composition for gas-fuelled engines
US7935664B2 (en) Lubricating oil composition
US6645923B2 (en) Lubricating oil composition
US20080020955A1 (en) Lubricating oil compositions
EP2319904A1 (en) Lubrication and lubricating oil compositions comprising phenylene diamines
US20090281009A1 (en) Lubricating oil composition and method for use with low sulfur marine residual fuel

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance