CN1029006C

CN1029006C - Lubricant compositions for autotraction

Info

Publication number: CN1029006C
Application number: CN91109939A
Authority: CN
Inventors: G·菲西卡罗; G·格巴兹
Original assignee: Agip Petroli SA
Current assignee: Agip Petroli SA; Agip Petroli SpA
Priority date: 1990-10-19
Filing date: 1991-10-19
Publication date: 1995-06-21
Anticipated expiration: 2006-10-19
Also published as: CA2053691A1; DE69101047T2; KR920008172A; IT9021812A1; PL292090A1; RU2012591C1; BR9104532A; HUT59180A; CA2053691C; ATE100488T1; PT99284B; EP0482693B1; EP0482693A1; AU640823B2; IT1243858B; AU8561591A; KR940008391B1; CN1060866A; HU913300D0; JPH04339895A

Abstract

A lubricant composition comprises: a) a mineral base oil; b) a synthetic base oil; c) a long-chain dialkyl carbonate; d) a parcel of usual additives; and e) viscosity index and pour point improvement additives. Component c) is the product of transesterification of a lower dialkyl carbonate with an alcoholic mixture consisting of at least 98% by weight of aliphatic alcohols with a linear or essentially linear hydrocarbon chain carrying a -CH2-OH group on a non-terminal carbon atom, the total number of carbon atoms in the molecule varying from 10 to 18 and preferably from 13 to 16.

Description

Lubricant compositions for autotraction

The present invention relates to a kind of improved lubricant compositions that supplies oil engine to use.

The synthetic base oil of employing prepares single grade and many grades type lubricant compositions is technical known.In this respect, synthetic base oil can be eliminated or alleviate at least in the unfavorable factor that only adopts the mineral base oil to run into often, only the lubricant compositions with the mineral base oil requires 1) very lubricated cut is arranged to obtain gratifying low temperature viscosity and to limit its volatility, 2) viscosity index improver of high per-cent is arranged to improve the initial viscosity index; 3) can satisfy other additives of all other lubricant properties requirements.

The lubricant compositions of using for oil engine must possess certain performance.Be that thermostability, oxidation-resistance, low volatility and this class viscosity one temperature profile are to provide the performance of the effectively lubricating under cold-starting and the maximum operating temperature.

Proposed to comprise that for the lubricant compositions of this practical use containing the senior dialkyl of carbonic acid adds mineral oil and common additives.U.S. Pat 2,387,999, US2,758,975, US3,642,858 and european patent application 89,709 in this based composition has been described, compare with the composition that by carboxylicesters is major constituent, they are improving thermostability especially; Aspect such as stability to hydrolysis and oxidative stability obtains various improvement.

Have been found that a kind of carbonic acid higher alkyl esters of special kinds now, in containing the lubricant compositions of this ester, make comprehensive rheological property and motor performance that improvement has been arranged; Thereby make this lubricant compositions be suitable for use as the high performance lubricant composition of four-stroke gasoline and diesel motor.

Lubricant compositions provided by the invention comprises:

A) mineral base oil 0-90%(weight);

B) synthetic base oil 0-90%(weight);

C) carbonic acid long-chain dialkyl 5-50%(weight);

D) one group of common additives 6-12%(weight);

E) viscosity index 0-15%(weight) and pour point improve additive;

Said composition is characterised in that amount of component b) be the transesterification products of carbonic acid lower dialkyl ester and a kind of alcohol mixture.This alcohol mixture is by 98%(weight at least) fatty alcohol form, this alcohol is to have-CH on the non-end group carbon atom ₂The straight chain of OH base or the hydrocarbon chain of straight chain basically, the total number of carbon atoms in this alcohol molecule changes between 10-18, better is between 13-16.

In preferred embodiments, component content a) is 0-60%(weight), components b) be 20-60%(weight), amount of component b) be 15-30%(weight), component d) be 8-10%(weight), component e is a 5-10%(weight).

Can be used as present composition component lubricating oil a) is the oil product of originating with the mineral after solvent treatment and/or the hydrofining subsequently by petroleum distillation.Usually viscosity index is 102-108, and pour point is-12 ℃--6 ℃, Noack vaporization losses is 12-42%.

The components b that can be used as composition of the present invention) synthetic base oil be synthetic source and by terminal olefine or internal olefin polymerization subsequent purificn, or by the synthetic oil product of petroleum fractions isomerization and/or alkylation subsequent purificn.

Can be used as preparation present composition amount of component b) alcohol be to contain 98% at least to contain 99% fatty alcohol preferably at least, this alcohol is to have-CH on the non-chain end carbon atom ₂The straight chain of OH base or the hydrocarbon chain of straight chain basically, the total number of carbon atoms in this alcohol molecule is 10-18, better is 13-16.More particularly, be applicable to that this purpose alcohol is the alcohol that is limited by following formula:

M is an integer in the formula, and n is 0 or integer, and condition is that the total number of carbon atoms in the molecule is 10-18, better is 13-16.Preferred mixture is those-CH ₂The OH base is the alcohol of valence link on 2 of chain in advance.

Be suitable for containing in the mixture of alcohols (I) of this purposes handlebar have the straight chain of the internal double bond of statistics or terminal double bond or basically linear olefin under the situation that cobalt or rhodium catalyst are arranged with CO and H ₂The branched part of the oxo alcohol that carbonylation makes.This band chain portion.This band chain portion can be separated with fractionation crystallization and linear fraction under the situation that hydrocarbon or ether solvent are arranged, and U.S. Pat 4,670 is described this in 606.According to this patent, the oxo alcohol of straight chain and side chain is dissolved in the liquid hydrocarbon solvent that contains 3-5 carbon atom in the molecule, or is dissolved in the methyl tertiary butyl ether.Solution is cooled to-20--52 ℃, and make the solid phase that contains the straight chain oxo alcohol be dissolved in liquid phase separation in the selected solvent with containing the side chain oxo alcohol.The side chain oxo alcohol is generally separated from solvent with 95% purity, and through the further crystallization and purification mixture with the alcohols (I) that obtains being suitable for purposes of the present invention, its purity surpasses 98%, better surpasses 99%.

Make the mixture and the carbonic acid lower dialkyl ester generation transesterification of this alcohols (I) then, generate the amount of component b of the present composition).Realize that this reaction is technically to know, european patent application discloses among 89,709 the embodiment description, that is: reactant is in contact with one another having under the situation of basic catalyst; The rudimentary aliphatic alcohol of emitting with the form of byproduct of reaction is removed in operation under high temperature and decompression.Preferred carbonic acid lower dialkyl ester is methylcarbonate and diethyl carbonate.The active ester groups transfer catalyst that can be used for this purpose is sodium methylate and sodium ethylate.When transesterification finishes, reclaim the combination c of carbonic acid long-chain dialkyl as the present composition), its characteristic parameter is usually following numerical range (general and preferred):

The preferred 420-510 of molecular-weight average: 340-560()

100 ℃ of centistokes of viscosity (cSt) (ASTM D455): 3-12

(preferred 4-8)

Viscosity-30 ℃ centipoise (cP) (ASTM D2602): 800-5000

Viscosity index V.I.（ASTMD2270）：120-140

Pour point (℃) (ASTM D97) :-60--30

Flash-point COC(℃) (ASTMD92): 220-350

NoacK volatility (%) is (DIN51581): 15-2

Copper corrosion test (ASTM D130): 1a-1b

The TAN(total acid value) (mgKOH/g) (ASTMD974): 0.01-0.05.

This dialkyl carbonate also has the desirable characteristic that relates to following aspect: cryogenic flow variate, oxidative stability, elastomer compatibility, biological degradability and toxicity.

The component d of the present composition) is generally used for lubricant additive by one group and forms, dispersing additive is specifically arranged, wear preventive additive and rust-inhibiting additive, metal passivator and copper passivator, detergent additive (overbasic and neutral) and oxidation inhibitor.These additives are selected from following classes of compounds usually: alkyl/alkenyl succinimide, succinate; Alkyl zinc dithiophosphate and alkene; Ethoxylate, the ester and the half ester of replacement succsinic acid; Undersaturated or the carbonyl compound of sequestering action; Heterogeneous ring compound; The metallic salt of alkyl and aryl sulfonic acid (neutral and overbasic), Whitfield's ointment, phenols and substituted phenol; Hindered amine and Hinered phenols; The sulfurized compound.

The component e of the present composition) forms with the additive that reduces its pour point by one group of viscosity index that can improve the lubricant compositions that makes.These additives are selected from following classes of compounds usually: olefin copolymer, Sipacril 2739OF, alkene/Sipacril 2739OF.Except the fundamental property of viscosity index and pour point improver, this additive also has such as other performances such as oxidation inhibitor, dispersion agent and anti-wear agents.

The ratio that is applicable to the following column weight amount of the typical lubricants composition percentage ratio of four-stroke gasoline and diesel motor contains each above-mentioned component:

Composition 123456

a） 60 40 20 0 0 0

b） 10 20 30 40 42 44

c） 10 20 30 40 42 44

d） 10 10 10 10 8 6

e） 10 10 10 10 8 6

As amount of component b in the lubricant compositions) carbonic acid long-chain dialkyl make the vehicle traction machine lubricant compositions of preparation have beyond thought effectively comprehensive rheological characteristics and engine operation characteristic.In this respect, special dialkyl carbonate ester structure can obtain high viscosity index (HVI) simultaneously, low pour point, low volatility.And the high polarity of carbonate group and structural performance thereof make and obtain the high-engine characteristic and reduce component d) addition become possibility.Especially high polarity causes the effective dissemination (making the dispersion agent in the lubricant compositions reduce about 30%) to engine sludge; produce lubricated (making the wear preventive additive in the lubricant compositions reduce about 20%) to standing abrasive metallic surface; and to ferrous metal and the antirust and electro-chemical protection effect (make rust-inhibiting additive, metal passivator and copper passivator reduce about 30%) of nonferrous metal surface generation.Amount of component b) high thermal stability and high oxidation stability make the antioxidant addn in the lubricant compositions reduce about 30%, because the acidic cpd from decomposing phenomenon does not make the high alkalinity detergent additive reduce about 20%, at last, almost be inert the amount of component b of composition) to ever-present elastomerics in the lubrication passages.Therefore, can be enough in the material of high nitrogen-containing, do not add special additive and prepare lubricant compositions, and by the strictest standard specifications, in the designed elastomer compatibility test of CCMC and VW standard specifications, add special additive usually to finish test.

Should be noted that it is the alcohols that is suitable for preparing the carbonic acid long-chain dialkyl that lubricant compositions uses that in known technology oxo alcohol is said to be, and will not separate linear fraction yet mention with a chain portion.According to the present invention, for the desired characteristic of lubricant compositions that obtains dialkyl carbonate and add this ester, it is critical adopting the mixture of the alcohols (I) with above-mentioned characteristic.This point illustrates better in the embodiments of the invention from behind and will see significantly.

Embodiment 1

Use has the oxo process alcohol mixture of following properties:

Carbonatoms 13-16

Molecular-weight average 220

Linear fraction 40%

Prop up chain portion 60%

This oxo process alcohol mixture is that linear olefin is having under the situation of catalyzer with CO and H basically ₂The product that carbonylation makes.

By U.S. Pat 4,670,606 described methods low temperature and have under the situation of varsol with fractionation crystallization said mixture in the same 95%(weight that contains of solid-state straight chain alcohol part) liquid portion of branched-chain alcoho separates.This liquid portion be similar to above-mentioned fractionation crystallization for the second time fractional crystallization purified, surpass 99%(weight to isolate branched-chain alcoho content) liquid portion.

Acquisition has the alcohols mixture of the formula I of following distribution after this manner;

C ₁₃Alcohol content 6%(weight)

C ₁₄Alcohol content 48%(weight)

C ₁₅Alcohol content 42%(weight)

C ₁₆Alcohol content 4%(weight)

Embodiment 2

Make the mixture of the side chain alcohols (I) of gained among the embodiment 1, under the situation that the sodium ethylate catalyzer is arranged, with methylcarbonate generation transesterification, as european patent application 89, described in 709, obtain molecular-weight average 470, have the dialkyl carbonate (I) of following properties

100 ℃ of cst 4.16 of viscosity

Viscosity-30 ℃ cp 1600

Viscosity index V.I. 125

Pour point (℃)-40

The COC flash-point (℃) 240

NoacK volatility (%) 13

Copper corrosion test 1a

The TAN(total acid value) (mgKOH/g) 0.05

Embodiment 3

For the purpose of contrasting, the straight chain that obtains in the carbonylation reaction and side chain oxo process alcohol mixture (without separating in advance), method according to embodiment 2 is made catalyzer and methylcarbonate generation transesterification with sodium ethylate, obtain molecular-weight average 470, viscosity index 130, the dialkyl carbonate (II) of pour point+12 ℃ and NoacK volatility 15%

Embodiment 4

According under the I of tabulating prepare lubricant compositions of the present invention (A) and control lubricant composition (B).

The table I

Preparation (A) (B)

Mineral base oil 43 43

Synthetic base oil 10 10

Dialkyl carbonate (I) 30-

Dialkyl carbonate (II)-30

Additive group 88

Viscosity index and pour point improve additive 99

Make composition (A) and (B) stand a series of rheological test and laboratory test, test objective is that the evaluation group compound satisfies two American-European degree that specification reached.One is the specification of the European program that is ranked of CCMC oil classification method planner, and another is the specification of the american procedure that is ranked of API oil classification method planner.It the results are shown in down the tabulation II.

The table II

Rheology assessment and Laboratory Evaluation

Property combination compositions scope ^*

（A）（B）

100 ℃ of (CSt) 13.5 13.7 12.5-16.3 of viscosity

Viscosity-25 ℃ (CPs) 3450＞6,000 3500 maximums

BPT(℃)-39-15-30 maximums

Stable pour-point (℃)-42-18-35 maximums

150 ℃ of HTS viscosity

10 ⁶Second ^-1(CPs) 3.6 3.6 3.5 minimums

NoacK volatility (%) 12 14 13 maximums

Elastomer compatibility is

Foaming does not have

* the 5W/40 classification range of technical specification API and CCMC

As seen satisfy whole specifications of U.S. API and European CCMC program according to lubricant compositions of the present invention (A) from above-mentioned data., control lubricant composition (B) but can not satisfy viscosity (25 ℃), BPT, stable pour-point, the specification of NoacK volatility.This behavior relates to the dialkyl carbonate (I) that is used for composition and the different physics-chem characteristics of (II).

Aspect the testing of engine that is ranked in U.S. API and European CCMC program, two kinds of lubricant compositions scope according to the rules satisfies Total Test according to grace period.Adopt lubricant compositions that dialkyl carbonate of the present invention (I) makes just aspect two of engine and rheologies, to have the best effort characteristic but have only.

Claims

1, a kind of lubricant compositions wherein, comprising:

A) the mineral base oil of 0-60% (weight);

B) the synthetic base oil of 10-44% (weight);

C) the carbonic acid long-chain dialkyl of 10-44% (weight);

D) one group of common additives of 6-10% (weight);

E) viscosity index of 6-10% (weight) and pour point improve additive;

Described composition is characterised in that amount of component b) be the transesterification products of carbonic acid lower dialkyl ester and a kind of alcohol mixture, this alcohol mixture is made up of the fatty alcohol of 98% (weight) at least, and this alcohol is to have-CH on the non-chain end carbon atom ₂The straight chain of OH base or the hydrocarbon chain of straight chain basically, the total number of carbon atoms in this alcohol molecule changes between 10-18.

2, the composition of claim 1 is characterized in that the total number of carbon atoms in the pure molecule changes between 13-16.

3, the composition of claim 1 is characterized in that component content a) is 0-40%(weight), components b) be 20-44%(weight), amount of component b) be 20-44%(weight), component d) be 8-10%(weight), component e) be 8-10%(weight).

4, the composition of claim 1 is characterized in that component is the lubricating oil that makes by petroleum distillation refining subsequently a), its viscosity index 102-108, and pour point-12 ℃--6 ℃, NoacK vaporization losses 12-42%.

5, the composition of claim 1 is characterized in that components b) be terminal olefine or internal olefin polymerized product, or petroleum fractions isomerization and/or alkylating product.

6, the composition of claim 1 is characterized in that amount of component b) be carbonic acid lower dialkyl ester and a kind of 98%(weight at least that contains) preferably contain 99%(weight) product of the mixture generation transesterification of fatty alcohol, this fatty alcohol can be limited by the formula I:

M is an integer in the formula, and n is 0 or integer, and condition is that the total number of carbon atoms in the molecule is 10-18, better is 13-16.

7, the composition of claim 6, the mixture that it is characterized in that this alcohol (1) be have the straight chain of the internal double bond of statistics or terminal double bond or basically linear olefin under the situation that cobalt or rhodium catalyst are arranged with CO and H ₂The branched part of the oxo alcohol that carbonylation makes, this branched part is separated with linear fraction with fractionation crystallization under the situation that hydrocarbon or ether solvent are arranged.

8, the composition of claim 1 is characterized in that described amount of component b has following properties:

The preferred 420-510 of molecular-weight average: 340-560()

100 ℃ of centistokes of viscosity (CSt) (ASTM D455): 3-12

(preferred 4-8)

Viscosity-30 ℃ centipoise CP(ASTM D2602): 800-5000

Viscosity index V ₀I.(ASTMD2270): 120-140

Pour point (℃) (ASTM D97) :-60--30

Flash-point COC(℃) (ASTMD92): 220-350

NoacK volatility (%) is (DIN51581): 15-2

Copper corrosion test (ASTM D130): 1a-1b

The TAN(total acid value) (mgKOH/g) (ASTM D974): 0.01-0.05.