CN108003983A

CN108003983A - Diesel engine lubricating oil composite and preparation method thereof

Info

Publication number: CN108003983A
Application number: CN201610959653.1A
Authority: CN
Inventors: 徐杰; 张耀; 段庆华; 武志强; 张倩; 刘依农; 夏青虹; 张峰; 孙文斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-27
Filing date: 2016-10-27
Publication date: 2018-05-08
Anticipated expiration: 2036-10-27
Also published as: CN108003983B

Abstract

The present invention provides a kind of diesel engine lubricating oil composite and preparation method thereof.The diesel engine lubricating oil composite of the present invention, including following components：A ＞ acrylate based copolymer pour-point depressants, containing as the first monomer shown in formula (1) and a variety of copolymers that proportionally graded is copolymerized of the second comonomer shown in formula (2)；

Description

Diesel engine lubricating oil composite and preparation method thereof

Technical field

The present invention relates to a kind of lubricant oil composite, more particularly to a kind of lubricating oil composition suitable for diesel engine Thing.

Background technology

Environmentally friendly and energy saving requirement promotes the development of engine technology, and the continuous upgrading for also promoting diesel engine oil is changed The performance requirement of each side such as generation, oil product disperses in soot, antioxygen, wear-resistant, high temperature is peace and quiet is also higher and higher.Bavin currently on the market The highest quality level of oil turbine lubricating oil is the CJ-4 ranks that American Petroleum Institute (API) (API) formulates.

In past more than 20 years, to avoid winter vehicle launch from unsuccessfully causing catastrophic failure, low temperature pumpmg quality one It is directly an important indicator of engine oil, but initially all just for fresh oil.Resist oil product due to the continuous progress of engine The increase of oxygen load, the soot load of diesel engine oil is continuously increased, cause lubricating oil the actual use phase later stage low temperature pumpmg quality Can be unqualified, make vehicle occur burning the accidents such as car.These problems cause pass of the industrial quarters to the low-temperature pumpability of lubricating oil Note and claim.For diesel engine oil, the CI-4 specifications regulation Mack T-10A engine test 75h waste oil put into effect for 2002 At -20 DEG C, MRV-TP1 dynamic viscosities are not more than 25000mPas, and without yield stress.The CJ-4 specifications rule put into effect for 2006 Determine Mack T-11A engine test 180h waste oil MRV-TP1 dynamic viscosities at -20 DEG C and be not more than 25000mPas, and nothing Yield stress.

In oil formula exploitation, pour-point depressant is used to improve the cryogenic property of oil product.The kind of commercially available pour depressant for lubricating oil Class is more, wherein, (methyl) acrylate copolymer has superpower adaptability in structure, composition and preparation process, in base There is excellent pour point depression performance in plinth oil, be the important component in domestic and international pour-point depressant market.Generally, it is considered that poly- (methyl) third The alkyl side chain of olefin(e) acid ester pour-point depressant has similar structure to paraffin hydrocarbon in oil product, it suppresses wax crystalline form by absorption or eutectic Into network structure, so as to achieve the purpose that to improve base oil cryogenic property.A variety of poly- (methyl) acrylic acid are sent out out at present Ester pour-point depressant.

For example, US6458749 is disclosed by by (methyl) acrylic acid (C16-C24) Arrcostab containing 0-25 weight % The high molecular weight of low-molecular weight copolymer and (methyl) acrylic acid (C16-C24) Arrcostab containing 25-70 weight % be copolymerized Thing improves lubricant oil composite low temperature flow.US5368761 discloses a kind of random copolymer, which contains (methyl) acrylic acid (C8-C15) Arrcostab of 15-67mol%, (methyl) acrylic acid (C16-C24) alkyl of 3-40mol% (methyl) acrylic acid (C1-C4) Arrcostab copolymerization of ester, 30-65mol% is prepared.CN101535355A discloses a kind of poly- Methacrylate copolymer, it contains the methacrylic acid C12-C16 Arrcostabs of 60-96 weight % and about 4-40 weights Measure the methacrylic acid C18-C30 Arrcostabs of %.CN101679902A discloses a kind of pour point depressant for lubricant, it is by (first Base) mixture of alkyl acrylate based copolymer (A) and (methyl) alkyl acrylate based copolymer (B) formed, (the first Base) alkyl acrylate based copolymer (A) by with average carbon atom number (CA) the alkyl of the scope of 12.5-13.8 (first Base) alkyl acrylate composition, (methyl) the alkyl acrylate based copolymer (B) with average carbon atom number (CB) by existing (methyl) alkyl acrylate of the alkyl of the scope of 13.9-15.5 is formed.It is unsaturated single that US6403745 discloses a kind of olefinic The gradient copolymer of body composition, (methyl) acrylic acid (C1-C5) Arrcostab, (methyl) of 10-98wt% containing 0-40wt% (methyl) acrylic acid (C16-C30) Arrcostab of acrylic acid (C6-C15) Arrcostab and 0-80wt%, the gradient copolymer are Obtained by the way that polymerized monomer is carried out in two steps polymerisation, specifically, a part of monomer or monomer mixture are first reacted For a period of time, then the reaction was continued for addition remainder monomer or monomer mixture.WO 2015/110340 discloses one kind two The mixture of kind alkyl (methyl) acrylate copolymer, can improve the low temperature pumpmg quality of engine oil after aging.

Effect of the pour-point depressant in full formula engine oil is influenced be subject to viscosity index improver and functional additive, is led to The compounding between additive is crossed, balances the performance of oil product each side, meets increasingly stringenter oil low-temperature performance requirement, is ten Divide necessary.

The content of the invention

The present invention provides a kind of diesel engine lubricating oil composite and preparation method thereof.

The diesel engine lubricating oil composite of the present invention includes following components：

A ＞ acrylate based copolymer pour-point depressants, containing as second shown in the first monomer shown in formula (1) and formula (2) Monomer a variety of copolymers that proportionally graded is copolymerized；

Wherein, R₁For C₆-C₁₈Alkyl, R₂For C₈-C₂₀Alkyl, R in first monomer₁Average valueIt is less than R in the second comonomer₂Average valueAnd R₃And R₄It is each independent Ground is hydrogen or methyl；

B ＞ viscosity index improvers；

C ＞ dispersants；

The mixture of D ＞ alkylsalicylates and alkyl monosulfide phenates；

E ＞ zinc dialkyl dithiophosphates；

F ＞ dialkyl dithio amino formates；

G ＞ auxiliary antioxidants；

The lube base oil of H ＞ surpluses.

Specifically, lubricant oil composite of the invention includes following component：

Wherein, R₁For C₆-C₁₈Alkyl, R₂For C₈-C₂₀Alkyl, R in first monomer₁Average valueIt is less than R in the second comonomer₂Average valueAnd R₃And R₄Independently of one another For hydrogen or methyl.

The preparation method of the acrylate based copolymer pour-point depressant comprises the following steps：

(a) under the conditions of olefinic polyreaction, the first monomer, initiator and molecular-weight adjusting shown in formula (1) will be contained First mixture of agent is added dropwise in the reactor equipped with flux oil, and the initial drop rate of first mixture is X₀；Institute State the first mixture and the drop rate X of preliminary stage is being added dropwise₁-X_n/2Remain constant, be incremented by or successively decrease, mid-term rank is being added dropwise The drop rate X of section_n/2Meet 4/5X₀<X_n/2<5/4X₀, the drop rate X in stage phase after the drop wise addition_n/2-X_nSuccessively decrease, tied when being added dropwise Drop rate X during beam_nMeet 1/10X_n/2<X_n<4/5X_n/2；Total time for adding of first mixture is t1；

(b) while first mixture is added dropwise, second comonomer, initiator and molecular weight shown in formula (2) will be contained Second mixture of conditioning agent is added dropwise in above-mentioned reactor, and the initial drop rate of second mixture is Y₀；Described The drop rate Y of preliminary stage is being added dropwise in two mixtures₁-Y_n/2It is incremented by, the drop rate Y of mid-term stage is being added dropwise_n/2Meet Y₀< Y_n/2<5Y₀, the drop rate Y in stage phase after the drop wise addition_n/2-Y_nRemain constant, be incremented by or successively decrease, the dropwise addition when completion of dropwise addition Speed Y_nMeet 4/5Y_n/2<Y_n<6/5Y_n/2；Total time for adding of second mixture is t2, and t1=t2；

Wherein, R₁For C₆-C₁₈Alkyl, R₂For C₈-C₂₀Alkyl, R in first monomer₁Average valueLess than described R in second comonomer₂Average valueAndIt is preferred that It is preferred that ∑ R₂=14.0-15.6；R₃And R₄It is each independently hydrogen or methyl.

Acrylate based copolymer provided by the invention can make lubricant oil composite have excellent cryogenic property, especially It can make the low-temperature pumpability of the lubricating oil containing soot after aging be improved.

The preparation method of acrylate based copolymer pour-point depressant provided by the invention will be described in detail in subsequent section.

Component A accounts for the 0.01%-2% of lubricant oil composite gross mass of the present invention, preferably 0.05%-1.5%.

B ＞ viscosity index improvers are selected from amorphous ethylene propylene copolymer, polymethacrylates, poly- alkyl methyl third Olefin(e) acid ester, methacrylate copolymer, the copolymer of styrene and acrylate, styrene/isoprene, styrene/fourth The partially hydrogenated copolymer of diene, isoprene/butadiene, and butadiene and isoprene, isoprene/divinyl The partially hydrogenated homopolymer of benzene.

So-called amorphous ethylene propylene copolymer refers to the ethylene propylene copolymer of non-crystalline type or semicrystalline, typically The ethylene contents of amorphous ethylene propylene copolymer are in 25Wt%-60Wt%, the present invention amorphous ethylene-propylene copolymer selected Crystallinity is in 0%-2.5%, preferably 0-2%, more preferably 0-1.5%.

The common trade names of component B viscosity index improvers have Lubrizol companies LZ7070, LZ7065, LZ7067, LZ7077, SV260, SV261 of Infineum companies etc..

Component B accounts for the 0.1%-25% of lubricant oil composite gross mass of the present invention, preferably 0.5%-20%.

C ＞ dispersants are selected from polyisobutene succinimide ashless dispersant and/or antioxidant polyisobutene succinyl is sub- Amine ashless dispersant.

The polyisobutene succinimide ashless dispersant can select single polyisobutene succinimide, double focusing isobutyl One or more in alkene succimide, more polyisobutene succinimides and macromolecule polyisobutene succinimide, its The number-average molecular weight of middle polyisobutene (PIB) part is 800-4000, preferably 900-3000, preferably 1000-2400, Ke Yixuan T151, the T152 produced with Wuxi south additive Co., Ltd, the T161 of Suzhou specialty oil factory production, Jinzhou Petrochemical Company point public affairs T155, T161A, T161B of additive factory production, the LZL157 of Lu Borun Lan Lian additives Co., Ltd production are taken charge of, Hitec646 of LZ6418, LZ6420 of Lubrizol Corporation productions, Afton Corporation production etc..

The antioxidant polyisobutene succinimide ashless dispersant is that the nitrogen on polyalkenyl succinimide is former Son is connected to obtain with the phenyl ring in metoxyphenol by alkylene, and its preparation method is in metoxyphenol and polyamines polyene Aldehyde reaction is added in mixture to obtain amine condensation, form with the reaction of polyolefin-based succinic anhydride again.The preferred C2-C4 of polyolefin The copolymerization of monoolefine or homopolymer, can be polyisobutene, random polypropylene, ethylene-propylene copolymer, its number-average molecular weight is 850- 5000, it is preferably 1000-4000；Metoxyphenol is selected from p methoxy phenol, o-methoxyphenol, the one of meta-methoxy phenol Kind is a variety of；One or more of the aldehyde in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde and benzaldehyde, preferably formaldehyde and/or poly first Aldehyde.The antioxidant polyisobutene succinimide ashless dispersant can be made by the method for patent CN 00107484.9.

Component C accounts for the 0.5%~15% of lubricant oil composite gross mass of the present invention, and preferably 1%~12%.

The mixture of D ＞ alkylsalicylates and alkyl monosulfide phenates, preferably alkyl sodium salicylate and alkyl monosulfide The mixture of phenol calcium, the calcium alkyl salicylate with high base number and be (100- with base number that preferably base number is (200-450) mgKOH/g 200) mixture of the middle base number sulfurized alkylphenol calcium of mgKOH/g, preferred mass ratio therebetween is 0.2：1 to 4：Between 1. Component D can select LZL109B, LZL112 that Lu Borun Lan Lian additives Co., Ltd produces, LZL115A, LZL115B, C9375, C9012, C9391, C9394 of Infineum companies production, the OSCA420 of OSCA companies production, the production of Shell companies SAP007, Lubrizol Corporation production LZ6499, LZ6500, Chevron Oronite Company production OLOA219.

Component D accounts for the 0.5%-8% of lubricant oil composite gross mass, preferably 1%-6%.

Alkyl in E ＞ zinc dialkyl dithiophosphates is the alkyl containing 2 to 12 carbon atoms, preferably contains 2 To the alkyl of 8 carbon atoms, include but not limited to ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, One or more in isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethylhexyls, cyclohexyl and methylcyclopentyl.

The zinc dialkyl dithiophosphate can be selected but be not limited to WUXI SOUTH PETROLEUM ADDITIVE Co., LTD.'s production T202, T203, Jinzhou Petrochemical Company additive factory production T202, T203, brothers alkyl T204, secondary alkyl T205, C9417, C9425, C9426 of LZ1371, LZ1375, Infineum company of Lubrizol companies, Afton companies Hitec7169, Hitec1656 etc..

Additions of the component E in lubricant oil composite is no more than 0.12% in terms of the mass fraction of P elements and is advisable, excellent Select 0.07%-0.12%.

Alkyl in F ＞ dialkyl dithio amino formates is the alkyl containing 2 to 12 carbon atoms, is preferably contained There is the alkyl of 2 to 8 carbon atoms, can be ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, different Amyl group, n-hexyl, isohesyl, n-octyl, 2- ethylhexyls.

The emerging petroleum additive Co., Ltd production in Jinzhou can be selected in the dialkyl dithio amino formate 7723 of T323, Vanderbilt company etc..

Component F accounts for the 0.02%-5% of lubricant oil composite gross mass, preferred amounts 0.05%-2%, preferably 0.1%- 0.5%.

G ＞ auxiliary antioxidants are selected from phenol type antioxidant, amine type antioxidant, phenolic ester type antioxidant and thiophenols ester type antioxidant In one or more.

The phenol type antioxidant can select 2,6- di-t-butyls-alpha, alpha-dimethyl amino paracresol, 2,6- di-t-butyls to first One or more in phenol, 4,4- di-2-ethylhexylphosphine oxides (2,6- di-tert-butylphenols) and 2,6- di-t-butyl -4- alkoxy phenol.

The amine type antioxidant can be alkylated aniline, alkylated diphenylamine and phenyl αnaphthylamine, alkyl carbon therein Number is C2-C12, preferably oil-soluble dialkyl diphenylamine, such as dibutyl diphenylamines, dioctyl diphenylamine, dinonyl hexichol Amine, fourth octyl diphenylamine, nonox, more preferably dinonyldiphenylamine.Alkylated diphenylamine on the market such as moral IRGANOX L-01, the IRGANOX L-57 of BASF AG of state production, the production of Beijing Xing Pu fine chemical technologies development company T534, the LZ5150A of Lanzhou Lu Borun Lan Lian additives Co., Ltd production, the production of R.T.Vanderbilt companies of the U.S. VANLUBE NA, VANLUBE 961, dioctyl diphenylamine VANLUBE 81, pair of German Rhein Chemie companies production, It is right ' N438L etc. of di-iso-octyldiphenylamine RC7001, Chemtura companies production.

The phenolic ester type antioxidant preferred molecular weight is the hydroxy phenyl carboxylate of 200-500, as BASF Corp. of Germany gives birth to The IRGANOX L-135 of production, the T512 of Beijing Xing Pu fine chemical technologies development company production.

The thiophenols ester type antioxidant can select 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) third Acetoacetic ester], for example, the antioxidant 1035 of Sichuan Yong Ye Chemical Co., Ltd.s production, the IRGANOX L115 of BASF AG's production.

The preferred phenolic ester type antioxidant of component G.

Component G accounts for the 0.1%-6% of lubricant oil composite gross mass, preferably 0.2%-4%.

The lube base oil of H ＞ surpluses, one kind in I classes of API, II class, III class, IV class and V class base oil are more Kind, preferably III class base oil of II class base oils of API and/or API.

The embodiment of instant component A is described in detail below.It is it should be appreciated that described herein Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

Acrylate based copolymer provided by the invention contains as shown in the first monomer shown in formula (1) and formula (2) Two monomers a variety of copolymers that proportionally graded is copolymerized；

Acrylate based copolymer provided by the invention contains as shown in the first monomer shown in formula (1) and formula (2) Two monomers a variety of copolymers that proportionally graded is copolymerized, i.e. it is with gradient molecular structure.The gradient molecule Structure refers to the acrylate based copolymer by P₁、P₂、P₃···P_n-1、P_nComposition, n >=3, wherein, P₁、P₂、P₃··· P_n-1、P_nIt is the copolymer being copolymerized as the first monomer shown in formula (1) and the second comonomer shown in formula (2), P₁It is derived Relative scale from the content and the content of the construction unit derived from second comonomer of the construction unit of the first monomer is X₁:Y₁； P₂-P_nIn P₁On the basis of, the content (X of the derived construction unit from the first monomer of copolymer structure₂-X_n) constantly reduce, and Content (the Y of construction unit derived from second comonomer₂-Y_n) be continuously increased, i.e. X₁:Y₁＞ X₂:Y₂＞ X₃:Y₃＞＞ X_n-1:Y_n-1＞ X_n:Y_n。

The present invention is to containing from the construction unit of the first monomer and second comonomer derived from the acrylate based copolymer Amount is not particularly limited, it is preferable that the content of the construction unit derived from first monomer is 10-90 weight %, derivative Content from the construction unit of the second comonomer is 10-90 weight %；It is highly preferred that the structure derived from first monomer The content of unit is 25-75 weight %, and the content of the construction unit derived from the second comonomer is 25-75 weight %.At this In invention, the content of the construction unit derived from first monomer and second comonomer, which can use, prepares the acrylic ester The dosage of first monomer and second comonomer described in copolymer process is calculated.It is it should be noted that above-mentioned in order to obtain Acrylate based copolymer with gradient molecular structure, first monomer and second comonomer usually require separate charging, because This, although containing partly overlapping monomer in first monomer and second comonomer, is derived from the structure list of the first monomer The content of member and the content of the construction unit derived from second comonomer can be distinguish between according to feed way.

In first monomer, the C₆-C₁₈The example of alkyl include but not limited to：Hexyl, heptyl, octyl group, nonyl Base, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecane Base, nonadecyl or eicosyl.Specifically, first monomer can be selected from Hexyl 2-propenoate, hexyl methacrylate, third Olefin(e) acid heptyl ester, metering system heptyl heptylate, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, acrylic acid nonyl ester, nonyl methacrylate, Decyl acrylate, decyl-octyl methacrylate, acrylic acid hendecane ester, methacrylic acid hendecane ester, dodecylacrylate, Lauryl methacrylate, tridecyl acrylate, Tridecyl methacrylate base ester, acrylic acid tetradecane base ester, Methacrylic acid tetradecane base ester, acrylic acid pentadecane base ester, methacrylic acid pentadecane base ester, aliphatic acrylate, Methacrylic acid cetyl ester, acrylic acid heptadecane base ester, methacrylic acid heptadecane base ester, octadecyl acrylate, One or more mixtures in octadecyl methacrylate.Preferably, first monomer is to contain (methyl) propylene Sour C₆Arrcostab, (methyl) acrylic acid C₈Arrcostab, (methyl) acrylic acid C₁₀Arrcostab, (methyl) acrylic acid C₁₂Arrcostab, (first Base) acrylic acid C₁₄Arrcostab, (methyl) acrylic acid C₁₆Arrcostab, (methyl) acrylic acid C₁₈At least one of Arrcostab.It is preferred that Ground, first monomer contain (methyl) acrylic acid C at the same time₁₂Arrcostab and (methyl) acrylic acid C₁₄Arrcostab.It is highly preferred that First monomer is (methyl) acrylic acid C₁₀Arrcostab, (methyl) acrylic acid C₁₂Arrcostab, (methyl) acrylic acid C₁₄Alkyl Ester, (methyl) acrylic acid C₁₆Arrcostab and (methyl) acrylic acid C₁₈The mixture of Arrcostab；Alternatively, first monomer is (first Base) acrylic acid C₈Arrcostab, (methyl) acrylic acid C₁₀Arrcostab, (methyl) acrylic acid C₁₂Arrcostab and (methyl) acrylic acid C₁₄ The mixture of Arrcostab；Alternatively, first monomer is (methyl) acrylic acid C₁₂Arrcostab, (methyl) acrylic acid C₁₄Arrcostab, (methyl) acrylic acid C₁₆Arrcostab and (methyl) acrylic acid C₁₈The mixture of Arrcostab.

The alkyl side chain average carbon atom number of (methyl) acrylate included by first monomer meetsMore preferably meet

In the second comonomer, the C₈-C₂₀The example of alkyl include but not limited to：Octyl group, nonyl, decyl, ten One alkyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecane Base or eicosyl.Specifically, the second comonomer can be selected from 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, acrylic acid nonyl ester, Nonyl methacrylate, decyl acrylate, decyl-octyl methacrylate, acrylic acid hendecane ester, methacrylic acid hendecane ester, third Olefin(e) acid dodecyl ester, lauryl methacrylate, tridecyl acrylate, Tridecyl methacrylate base ester, third Olefin(e) acid tetradecane base ester, methacrylic acid tetradecane base ester, acrylic acid pentadecane base ester, methacrylic acid pentadecane base ester, third Olefin(e) acid cetyl ester, methacrylic acid cetyl ester, acrylic acid heptadecane base ester, methacrylic acid heptadecane base ester, third Olefin(e) acid stearyl, octadecyl methacrylate, acrylic acid nonadecane base ester, methacrylic acid nonadecane base ester, third One or more mixtures in olefin(e) acid eicosane base ester, methacrylic acid eicosane base ester.Preferably, the second comonomer is excellent Elect as with C₈-C₂₀The mixture that alkyl-substituted (methyl) acrylate is formed, further preferably (methyl) acrylic acid C₈ Arrcostab, (methyl) acrylic acid C₁₀Arrcostab, (methyl) acrylic acid C₁₂Arrcostab, (methyl) acrylic acid C₁₄Arrcostab, (methyl) Acrylic acid C₁₆Arrcostab, (methyl) acrylic acid C₁₈Arrcostab, (methyl) acrylic acid C₂₀At least one of Arrcostab.Preferably, The second comonomer contains (methyl) acrylic acid C at the same time₁₄Arrcostab, (methyl) acrylic acid C₁₆Arrcostab, (methyl) acrylic acid C₁₈ Arrcostab and (methyl) acrylic acid C₂₀Arrcostab.It is highly preferred that the second comonomer is (methyl) acrylic acid C₁₄Arrcostab, (first Base) acrylic acid C₁₆Arrcostab, (methyl) acrylic acid C₁₈Arrcostab, (methyl) acrylic acid C₂₀The mixture of Arrcostab；Alternatively, institute It is (methyl) acrylic acid C to state second comonomer₁₀Arrcostab, (methyl) acrylic acid C₁₂Arrcostab, (methyl) acrylic acid C₁₄Arrcostab, (methyl) acrylic acid C₁₆Arrcostab, (methyl) acrylic acid C₁₈Arrcostab and (methyl) acrylic acid C₂₀The mixture of Arrcostab.

The alkyl side chain average carbon atom number of (methyl) acrylate included by the second comonomer meetsMore preferably meet

First monomer and second comonomer can be commercially available, and can also be prepared into using existing various methods Arrive, for example, can react to obtain with alcohol esterification by (methyl) acrylic acid, (methyl) acrylic acid low-carbon ester and alcohol can also be passed through Ester exchange reaction obtains, and is specifically known to the skilled person, and therefore not to repeat here.

The acrylate based copolymer can be prepared using well known to a person skilled in the art various methods, example Such as, any one method in polymerisation in bulk, polymerisation in solution, emulsion polymerization, suspension polymerisation etc. can be used to be prepared, preferably adopted It is prepared with polymerisation in solution.

A preferred embodiment of the invention, the acrylate based copolymer is according to the side comprised the following steps Method is prepared：

(b) while first mixture is added dropwise, second comonomer, initiator and molecular weight shown in formula (2) will be contained Second mixture of conditioning agent is added dropwise in above-mentioned reactor, and the initial drop rate of second mixture is Y₀；Described The drop rate Y of preliminary stage is being added dropwise in two mixtures₁-Y_n/2It is incremented by, the drop rate Y of mid-term stage is being added dropwise_n/2Meet Y₀< Y_n/2<5Y₀, the drop rate Y in stage phase after the drop wise addition_n/2-Y_nRemain constant, be incremented by or successively decrease, the dropwise addition when completion of dropwise addition Speed Y_nMeet 4/5Y_n/2<Y_n<6/5Y_n/2；Total time for adding of second mixture is t2, and t1=t2.

In the present invention, term " dropwise addition preliminary stage " refer to from start be added dropwise material to total time for adding half when Between section；Term " dropwise addition mid-term stage " referred at the time point of half of total time for adding；Term " later stage is added dropwise " refers to always drip The period that half to material dropping between added-time finishes.In other words, for first mixture, the dropwise addition Preliminary stage t is 0 ＜ t ＜ 1/2t1, and mid-term stage t=1/2t1 is added dropwise, and it is 1/2t1 ＜ t ＜ t1 that later stage t, which is added dropwise,；And phase For second mixture, the dropwise addition preliminary stage t is 0 ＜ t ＜ 1/2t2, and mid-term stage t=1/2t2, drop is added dropwise It is 1/2t2 ＜ t ＜ t2 to add later stage t.

When preparing the acrylate based copolymer using the above method, over time, the in polymerization system The relative scale of one monomer gradually decreases, and the relative scale of second comonomer gradually increases, and at this time, polymerisation is by more first Monomer, the gradual gradient of copolymerization of less second comonomer are changed into the copolymer of less first monomer and more second comonomer, so that Obtain containing the copolymer p at the same time₁、P₂、P₃···P_n-1、P_nAcrylate based copolymer, the acrylic ester copolymerization Thing has gradient molecular structure.The copolymer has the monomer mixture that gradient molecular structure refers to form copolymer according to gradually Form into gradient is made of one kind and is changed into another kind and forms, i.e., a part of monomeric building blocks in copolymer molecule structure Content increases with the time and gradually reduces, and the content of another part monomeric building blocks then increases with the time and gradually increases.

In addition, on the basis of total dosage of first monomer and second comonomer, the dosage of first monomer can be 10-90 weight %, be preferably 25-75 weight %, and the dosage of the second comonomer can be 10-90 weight %, be preferably 25-75 Weight %.

In the preparation process of the acrylate based copolymer, the initial temperature of the olefinic polyreaction usually can be with It is preferably 55-165 DEG C for 50-180 DEG C, is most preferably 60-150 DEG C.In addition, total the time for adding t1 and t2 all can be When 1-12 is small, when being preferably 1.5-10 small.

According to the present invention, in order to be more advantageous to the raising of monomer conversion, it is preferable that prepare the acrylic ester copolymerization When the method for thing further includes after first mixture and the second mixture completion of dropwise addition that the reaction was continued 0.5-2 is small, then add Initiator and flux oil, afterwards again by the temperature 0.5-5 that rises at 100-150 DEG C that the reaction was continued it is small when.

The present invention is not particularly limited the dosage of the initiator, for example, the first monomer relative to 100 parts by weight With total dosage of second comonomer, the dosage of initiator can be 0.01-2.5 parts by weight in whole polymerization process, be preferably 0.05-2 parts by weight, more preferably 0.1-1.5 parts by weight.Total dosage of initiator in first mixture and the second mixture Weight ratio with the dosage for the initiator added can be 1-20:1, it is preferably 2-10:1, more preferably 2.5-7.5:1.In addition, The species of the initiator of initiator used with adding can be identical in first mixture and the second mixture, can not also Together, and existing various radical initiators can be each independently, as azo-initiator, peroxide type initiators and At least one of redox type initiators.

Wherein, the azo-initiator can be selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, idol Nitrogen diformamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo One kind in dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile It is or a variety of.

The peroxide type initiators can be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, peroxide Change lauroyl, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, benzoyl peroxide first In the acyl tert-butyl ester, the peroxidating trimethylacetic acid tert-butyl ester, cyclohexanone peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate One or more.

The redox type initiators can be selected from sulfate-sulphite, persulfate-thiocarbamide, persulfate-has One or more in machine salt and ammonium persulfate-fatty amine.Wherein, the sulfate-sulphite can be selected from sodium sulphate-Asia One or more in sodium sulphate, potassium sulfate-potassium sulfite, ammonium sulfate-ammonium sulfite；Persulfate-thiocarbamide can be selected from One or more in sodium sulphate-thiocarbamide, potassium peroxydisulfate-thiocarbamide, ammonium persulfate-thiocarbamide；Persulfate-organic salt can be selected from One or more in sodium peroxydisulfate-potassium acetate, potassium peroxydisulfate-potassium acetate, ammonium persulfate-ammonium acetate；Ammonium persulfate-fatty amine The one or more that can be selected from ammonium persulfate-N, N- tetramethylethylenediamine and ammonium persulfate-diethylamine.

The present invention is not particularly limited the dosage of the flux oil, for example, the first monomer relative to 100 parts by weight With total dosage of second comonomer, the dosage of flux oil can be 10-150 parts by weight in whole polymerization process, be preferably 50- 100 parts by weight, more preferably 60-80 parts by weight.The dosage of the dosage of the flux oil of initial polymerization stage and the flux oil added Weight ratio can be 0.5-1.5:1, it is preferably 0.8-1.2:1.In addition, the flux oil of initial polymerization stage and the dilution added The species of oil may be the same or different, and can be each independently and existing various can dilute the acrylate The viscosity of based copolymer is simultaneously conducive to its material for adding and disperseing in subsequent applications, for example, the flux oil can be bavin At least one of oil, kerosene, solvent naphtha, aromatic solvent, white oil, mineral oil base oil, artificial oil etc., are preferably white oil, ore deposit At least one of thing oil base oil, artificial oil, are most preferably mineral base oil.The flux oil can be commercially available, For example, can be 100N purchased from the Shuan Long companies trade mark flux oil.The flux oil can be the same as third after polymerisation Olefin(e) acid ester based copolymer separates, and can not also separate.

The species of first mixture and the molecular weight regulator in the second mixture may be the same or different, And all can be this area conventional selection, for example, lauryl mercaptan and/or 2- sulfydryl second can be each independently Alcohol.In addition, the dosage of molecular weight regulator contained in first mixture and the second mixture all can be this area Conventional selection, therefore not to repeat here.

In order to overcome oxygen inhibition, the copolymerization product with larger molecular weight is obtained, it is preferable that the olefinic polyreaction exists Carried out in inert atmosphere.The inert atmosphere refers to any one gas or gas not chemically reacted with reactant and product Mixture, such as the one or more in nitrogen, helium and periodic table of elements zero group gas.Keeping the method for inert atmosphere can be Above-mentioned any one gas or admixture of gas not chemically reacted with reactant and product is passed through into reaction system.

The present invention is not particularly limited the molecular size range of the acrylate based copolymer, for example, the propylene The number-average molecular weight of acid esters based copolymer can be 10,000-100 ten thousand, be preferably 10,000-50 ten thousand, more preferably 10,000-10 ten thousand.At this In invention, the number-average molecular weight is measured using gel permeation chromatography (GPC), wherein, using polybutyl methacrylate as standard specimen, Sample solution concentration is 0.05mmol/L, and solvent is tetrahydrofuran.

Typically 50-180 DEG C of the initial temperature of the olefinic polyreaction, is preferably 55-165 DEG C, is most preferably 60-150℃.In addition, total the time for adding t1 and t2 all can be 1-12 it is small when, when being preferably 1.5-10 small.

Preferably, the preparation method further includes after first mixture and the second mixture completion of dropwise addition that the reaction was continued When 0.5-2 is small, initiator and flux oil are then added, temperature risen at 100-150 DEG C the reaction was continued again afterwards, and 0.5-5 is small When.

First monomer, second comonomer, flux oil, initiator, molecular weight regulator specific species and dosage and Other conditions have been described herein above, and therefore not to repeat here.

Pour-point depressant of the acrylate based copolymer provided by the invention be especially suitable for separate sources base oil, including I class mineral base oils of API, II/III class hydrogenated base oils of API and the lubrication containing II/III class base oil of I classes of API and API Oil.Wherein, except containing I classes of API/API, II classes basis in the lubricating oil containing II/III class base oil of I classes of API and API Outside oil, also containing other base oils, in such as IV class artificial oils of API, V class artificial oils of API, GTL synthetic base oils at least It is a kind of.

Acrylate based copolymer provided by the invention has excellent depression effeCt, particularly to the complicated basis of composition Oil, the distribution of aforesaid propylene acid esters based copolymer and side-chain structure can realize quantitative matching with base oil paraffin, so that So that pour point depression efficiency significantly improves.

Acrylate based copolymer provided by the invention can be used alone or make with the mixing of other pour depressant for lubricating oil To improve the cryogenic property of base oil.During specifically used, the addition of pour-point depressant typically constitutes from basic weight of oil 0.01-2%, preferably accounts for the 0.05-1.5% of basic weight of oil, more preferably accounts for the 0.1-1% of basic weight of oil.

The acrylate based copolymer provided and other additives and base oil are used in combination the present invention, can make lubrication Fluid composition has excellent cryogenic property, is particular enable to make the low-temperature pumpability of the lubricating oil containing soot after aging to be changed It is kind.

The lubricant oil composite of the present invention can use following methods to prepare：Above-mentioned each additive is added separately to lubricating oil Concentrate is mixed and made into base oil or by each component is then added in lube base oil be mixed, the temperature of mixing Degree is between 40 DEG C -90 DEG C, and the time is between 1h-6h.

The lubricant oil composite of the present invention has the low-temperature pumpability of the oil containing soot after excellent cryogenic property and aging. Calculated with mass fraction, the present composition has the phosphorus content no more than 0.12%, and the sulfur content no more than 0.4%, does not surpass 1% sulfate ash content is crossed, disclosure satisfy that the requirement of the high-performance diesel engine lubricant of CJ-4 ranks.

Embodiment

The present invention will be described in detail by way of examples below.

In following embodiments and comparative example, the content of each construction unit in the content and copolymer of copolymer and flux oil It is calculated according to inventory.

Embodiment 1

The embodiment is used to illustrate acrylate based copolymer pour-point depressant provided by the invention and preparation method thereof.

Under nitrogen protection, (Shuan Long companies, board are purchased to equipped with addition 113kg flux oils in churned mechanically reaction kettle Number it is 100N, similarly hereinafter), 83-91 DEG C is heated to, in A feed inlets, with stabilized speeies of 50kg/ when small by the first monomers of 270kg [decyl-octyl methacrylate/lauryl methacrylate/methacrylic acid tetradecane base ester/methacrylic acid cetyl Ester/octadecyl methacrylate (C₁₀=28 weight %, C₁₂=32 weight %, C₁₄=28 weight %, C₁₆=8 weight %, C₁₈=4 weight %),The mixture of 1.35kg benzoyl peroxides and 1.08kg lauryl mercaptans is added dropwise Into reaction kettle, when stabilization charging 3 is small, subsequent drop rate linearly reduces so that when the combined feed time was to 6 hours, flow Be reduced to 30kg/ it is small when.150kg second comonomer [metering systems are added dropwise in the initial velocity when B feed inlets are small with 10kg/ at the same time Sour tetradecane base ester/methacrylic acid cetyl ester/octadecyl methacrylate/methacrylic acid eicosane base ester (C₁₄=38 weight %, C₁₆=20 weight %, C₁₈=25 weight %, C₂₀=17 weight %,0.75kg peroxides The mixture for changing benzoyl and 0.6kg lauryl mercaptans is added dropwise in reaction kettle, and it is linear to set the flow pumped at feed inlet B Increase so that when the combined feed time was to 3 hours, flow increase to 30kg/ it is small when, then keep the flow charging 3 it is small when.A、 During the equal completion of dropwise addition of B feed inlets, reaction kettle continue to keep at 95 DEG C 1 it is small when, then add 0.3kg benzoyl peroxides and 113kg flux oils, reaction was completed after being warming up to when holding 2 is small at 103 DEG C, obtains pour-point depressant J1, wherein, monomer in pour-point depressant J1 Conversion ratio is 99.1%, number-average molecular weight 40120.In addition, contain 64.3 weights in copolymer contained by the pour-point depressant J1 Measure the structure derived from monomer shown in formula (2) derived from the construction unit of monomer shown in formula (1) and 35.7 weight % of % Unit.

Embodiment 2

Under nitrogen protection, to equipped with 113kg flux oils are added in churned mechanically reaction kettle, 83-91 DEG C is heated to, A feed inlets, with initial velocities of 40kg/ when small by the first monomers of 171kg [methacrylic acid octyl group ester/methacrylic acid decane Base ester/lauryl methacrylate/methacrylic acid tetradecane base ester (C₈=12 weight %, C₁₀=15 weight %, C₁₂= 48 weight %, C₁₄=25 weight %),0.9kg benzoyl peroxides and 0.7kg lauryl mercaptans it is mixed Compound is added dropwise in reaction kettle, then linear slowly to reduce so that when the combined feed time was to 3 hours, flow-reduction to 32kg/ Hour, it is then linear quick to reduce so that when the combined feed time was to 6 hours, flow-reduction to 10kg/ it is small when.At the same time B into 255kg second comonomer [methacrylic acid tetradecane base esters/methacrylic acid ten are added dropwise with initial velocities of 20kg/ when small in material mouth Six Arrcostabs/octadecyl methacrylate/methacrylic acid eicosane base ester (C14=38 weight %, C₁₆=20 weights Measure %, C₁₈=25 weight %, C₂₀=17 weight %,0.9kg benzoyl peroxides and 0.7kg dodecyls The mixture of mercaptan is added dropwise in reaction kettle, set at feed inlet B pump flow to be linearly increasing so that when the combined feed time extremely At 3 hours, flow increase to 50kg/ it is small when, then keep the flow charging 3 it is small when.A, during the equal completion of dropwise addition of B feed inlets, instead Answer kettle continue to keep at 95 DEG C 1 it is small when, then add 0.3kg benzoyl peroxides and 113kg flux oils, be warming up to 103 DEG C It is lower keep 2 it is small when after reaction was completed, obtain pour-point depressant J2, wherein, monomer conversion is 99.4% in pour-point depressant J2, the equal molecules of number Measure as 41702.In addition, formula (1) institute is derived from containing 40.0 weight % in copolymer contained by the copolymer pour-point depressant J2 Show the construction unit of monomer and the construction unit derived from monomer shown in formula (2) of 60.0 weight %.

Comparative example 1

Method according to embodiment 1 prepares pour-point depressant, unlike, after the first monomer and second comonomer are uniformly mixed It is added dropwise to again with constant rate of speed in reaction system, specifically：

Under nitrogen protection, to equipped with 113kg flux oils are added in churned mechanically reaction kettle, 83-91 DEG C is heated to, will The first monomers of 270kg [decyl-octyl methacrylate/lauryl methacrylate/methacrylic acid tetradecane base ester/methyl-prop Olefin(e) acid cetyl ester/octadecyl methacrylate (C₁₀=28 weight %, C₁₂=32 weight %, C₁₄=28 weight %, C₁₆=8 weight %, C18=4 weight %),150kg second comonomers [methacrylic acid tetradecane base ester/first Base aliphatic acrylate/octadecyl methacrylate/methacrylic acid eicosane base ester (C₁₄=38 weight %, C₁₆ =20 weight %, C₁₈=25 weight %, C₂₀=17 weight %,2.1kg benzoyl peroxides and 1.68kg The mixture of lauryl mercaptan is added dropwise in reaction kettle with constant rate of speed of 70kg/ when small, when time for adding is 6 small, is added dropwise At the end of, reaction kettle continue to keep at 95 DEG C 1 it is small when, then add 0.3kg benzoyl peroxides and 113kg flux oils, rise Reaction was completed after when holding 2 is small at warm to 103 DEG C, obtains pour-point depressant DJ1, wherein, monomer conversion is in pour-point depressant DJ1 99.3%, number-average molecular weight 41768.In addition, the derivative containing 64.3 weight % in copolymer contained by the pour-point depressant DJ1 From the construction unit of monomer shown in formula (1) and the construction unit derived from monomer shown in formula (2) of 35.7 weight %.

Embodiment 3

Under nitrogen protection, to equipped with 100kg flux oils are added in churned mechanically reaction kettle, 83-91 DEG C is heated to, A feed inlets, with speed of 48kg/ when small by 166kg the first monomer [lauryl methacrylate/methacrylic acids 14 Arrcostab/methacrylic acid cetyl ester/octadecyl methacrylate (C₁₂=50 weight %, C₁₄=18 weight %, C₁₆=20 weight %, C₁₈=12 weight %),0.4kg benzoyl peroxides and 0.5kg lauryl mercaptans Mixture be added dropwise in reaction kettle, be then linearly slowly increased so that when the combined feed time to 2h constantly, flow velocity increases to It is then linear quick to reduce when 56kg/ is small so that when the combined feed time was to 4 hours, flow-reduction to 6kg/ it is small when.At the same time 303kg second comonomer [decyl-octyl methacrylate/methacrylic acids 12 are added dropwise in initial velocity when B feed inlets are small with 30kg/ Arrcostab/methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/octadecyl methacrylate/methyl-prop Olefin(e) acid eicosane base ester (C₁₀=12 weight %, C₁₂=27 weight %, C₁₄=19 weight %, C₁₆=18 weight %, C₁₈=14 weights Measure %, C₂₀=10 weight %),The mixture of 0.75kg benzoyl peroxides and 0.9kg lauryl mercaptans It is added dropwise in reaction kettle, sets the flow pumped at feed inlet B to be linearly increasing so that when the combined feed time was to 2 hours, flow Increase to 100kg/ it is small when, then keep the flow charging 2 it is small when.A, during the equal completion of dropwise addition of B feed inlets, reaction kettle is at 95 DEG C Continue to keep 2 it is small when, then add 0.2kg benzoyl peroxides and 142kg flux oils, be warming up at 103 DEG C keep 2 it is small when after Reaction was completed, obtains pour-point depressant J3, wherein, monomer conversion is 98.9% in pour-point depressant J3, number-average molecular weight 43196.This Outside, in the copolymer contained by the pour-point depressant J3 construction unit derived from monomer shown in formula (1) containing 35.4 weight % with And 64.6 weight % the construction unit derived from monomer shown in formula (2).

Embodiment 4

Under nitrogen protection, to equipped with 100kg flux oils are added in churned mechanically reaction kettle, 83-91 DEG C is heated to, A feed inlets, with speed of 40kg/ when small by 255kg the first monomer [lauryl methacrylate/methacrylic acids 14 Arrcostab/methacrylic acid cetyl ester/octadecyl methacrylate (C₁₂=50 weight %, C₁₄=18 weight %, C₁₆=20 weight %, C₁₈=12 weight %),1.2kg benzoyl peroxides and 1.0kg lauryl mercaptans Mixture be added dropwise in reaction kettle, be then linearly slowly increased so that when the combined feed time to 3h constantly, flow velocity increases to It is then linear quick to reduce when 50kg/ is small so that when the combined feed time was to 6 hours, flow-reduction to 30kg/ it is small when.At the same time 150kg second comonomer [methacrylic acid tetradecane base esters/metering system are added dropwise in initial velocity when B feed inlets are small with 10kg/ Sour cetyl ester/octadecyl methacrylate/methacrylic acid eicosane base ester (C14=38 weight %, C₁₆=20 weights Measure %, C₁₈=25 weight %, C₂₀=17 weight %,0.70kg benzoyl peroxides and 0.60kg dodecanes The mixture of base mercaptan is added dropwise in reaction kettle, sets the flow pumped at feed inlet B to be linearly increasing so that when the combined feed time During to 3 hours, flow increase to 30kg/ it is small when, then keep the flow feed 3h.A, during the equal completion of dropwise addition of B feed inlets, reaction Kettle continue to keep at 95 DEG C 2 it is small when, then add 0.2kg benzoyl peroxides and 66kg flux oils, be warming up at 103 DEG C and protect Hold 2 it is small when after reaction was completed, obtain pour-point depressant J4, wherein, monomer conversion is 99.7% in pour-point depressant J4, and number-average molecular weight is 42637.In addition, the knot derived from monomer shown in formula (1) containing 63.0 weight % in copolymer contained by the pour-point depressant J4 The construction unit derived from monomer shown in formula (2) of structure unit and 27.0 weight %.

Test case

Test case is used to test pour point depression performance of the pour-point depressant in base oil.The property of base oil is as shown in table 1：

Table 1

Base oil	A	B	C	D	E	F
							Rank	API-Ⅱ6	API-Ⅲ6	150SN	500SN	API-Ⅱ4	150BS
100 DEG C of viscosity/(mm²·s^-1)	5.67	5.54	5.46	11.22	3.97	29.6
							Viscosity Index	112	121	90	95	114	98
Pour point/DEG C	-18	-15	-15	-12	-15	-9

Pour-point depressant J1-J4 and reference pour-point depressant DJ1 is added in base oil respectively, wherein, the dosage of pour-point depressant, basis The results are shown in Table 2 for the species and gained of oil.

It can be seen that third with gradient molecular structure for being obtained using this method from the contrast of result obtained as above Olefin(e) acid ester based copolymer pour-point depressant, is respectively provided with excellent depression effeCt, particularly in few addition in a variety of base oils When, the pour point of base oil is still decreased obviously, and pour point depression efficiency significantly improves.

Table 2

Note：In table 2, the addition of pour-point depressant is on the basis of the gross weight of base oil.

The embodiment 5-9 and comparative example 2-5 of diesel engine lubricating oil composite

The formula composition of the embodiment 5-9 and comparative example 2-5 of diesel engine lubricating oil composite are shown in Table 3.By each group Point be proportionally added into and to reconcile in container, 45 DEG C -80 DEG C are heated under normal pressure, when stirring 1 is small -2 it is small when, viscosity rank is prepared For the CJ-4 diesel engine lubricating oil composites of 15W-40.

These lubricant oil composites and CJ-4 15W-40 markets oil are carried out plus the degradation of carbon black is to obtain simulation Containing soot oil after aging.Analogies using carbon black as soot, are stirred black dispersion to lubricant oil composite by high speed machine Fresh oil in, formed carbon black and oil dispersion liquid, carbon black content 3%, then carries out degradation.Degradation condition is： The iron naphthenate for adding 15ppm in the dispersion liquid of 100g carbon blacks and oil does catalyst, 165 DEG C of test temperature, oxygen flow 150mL/min, ageing time 40h.The MRV low temperature pumpmg qualities survey of carbon containing dirty oil after aging is carried out using ASTM D6896 methods Fixed, the MRV low temperature pumpmg qualities that fluid composition fresh oil is lubricated using ASTM D4684 methods are measured, including yield stress and low Temperature pumping viscosity.In API CJ-4 diesel engine oil specifications, the Mack T-11A engine tests 180h of oil is tested containing soot oil MRV low temperature pumpmg qualities test temperature be -20 DEG C, be yield stress ＜ 35Pa by standard, temperature pumping viscosity is not more than 25000mPa·s.Bar of the MRV low temperature pumpmg qualities test of carbon containing dirty oil at -20 DEG C after the lubricant oil composite aging of the present invention Carried out under part, result of the test is shown in Table 4.

From the results shown in Table 4, using embodiment pour-point depressant J1-J4 and comparative example pour-point depressant DJ1 and suitably The glutinous lubricant oil composite for referring to agent, base oil and the allotment of other functional additives, the MRV low temperature pumpmg qualities of its fresh oil are all qualified, Not plus pour-point depressant, the yield stress of carbon containing dirty oil and MRV temperature pumping viscositys be not all unqualified after its fresh oil and aging for comparative example 5. Carbon containing dirty oil MRV low temperature pumpmg qualities and CJ-4 15W-40 markets after aging using the lubricant oil composite of embodiment pour-point depressant Oil phase ratio, yield stress is qualified, and MRV temperature pumpings viscosity is less than CJ-4 markets oil, and uses the lubricating oil of comparative example pour-point depressant Carbon containing dirty oil MRV temperature pumpings viscosity is more than CJ-4 markets oil after the aging of composition, the unqualified phenomenon of yield stress also occurs. Illustrate that acrylate based copolymer pour-point depressant provided by the invention has significantly the low-temperature pumpability of the oil containing soot after aging Improvement result.

Table 4

The embodiment 10-12 and comparative example 6-8 of diesel engine lubricating oil composite.

The formula composition of the embodiment 10-12 and comparative example 6-8 of diesel engine lubricating oil composite are shown in Table 5.Will be each Component be proportionally added into reconcile container in, under normal pressure heat 45 DEG C -80 DEG C, stirring 1 it is small when -2 it is small when, viscosity level is prepared Not Wei 15W-40 CJ-4 diesel engine lubricating oil composites.Using foregoing same method to these lubricant oil composites into The degradation of row plus carbon black, and the MRV low temperature pumpmg qualities measure of carbon containing dirty oil and fresh oil after aging is carried out, result of the test is shown in Table 6。

From the results shown in Table 6, pour-point depressant is subject to the improvement result of the low-temperature pumpability of lubricating oil after aging The glutinous influence for referring to the additives such as agent, antioxidant.The present invention by by a kind of acrylate based copolymer pour-point depressant provided with The functional additives such as suitable viscosity index improver, base oil and oxidation and corrosion inhibitor, detergent-dispersant additive rationally compound, and make lubrication Fluid composition has excellent cryogenic property, and the lubricating oil containing soot has excellent low-temperature pumpability after especially making aging. It disclosure satisfy that the requirement of CJ-4 rank top grade diesel engine lubricants.

Table 6

The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of diesel engine lubricating oil composite, including following components：

A ＞ acrylate based copolymer pour-point depressants, containing as the first monomer shown in formula (1) and the second comonomer shown in formula (2) A variety of copolymers that proportionally graded is copolymerized；

Wherein, R₁For C₆-C₁₈Alkyl, R₂For C₈-C₂₀Alkyl, R in first monomer₁Average valueLess than described R in second comonomer₂Average valueAnd R₃And R₄It is each independently hydrogen Or methyl；

B ＞ viscosity index improvers；

C ＞ dispersants；

The mixture of D ＞ alkylsalicylates and alkyl monosulfide phenates；

E ＞ zinc dialkyl dithiophosphates；

F ＞ dialkyl dithio amino formates；

G ＞ auxiliary antioxidants；

The lube base oil of H ＞ surpluses.

2. composition according to claim 1, it is characterised in that ∑ R₁=12.2-13.5, ∑ R₂=14.0-15.6.

3. composition according to claim 1, it is characterised in that in the acrylate based copolymer, derived from institute The content for stating the construction unit of the first monomer is 10-90 weight %, and the content of the construction unit derived from the second comonomer is 10-90 weight %.

4. according to the composition described in any one in claim 1-3, it is characterised in that the acrylate based copolymer is pressed It is prepared according to method comprising the following steps：

(a) under the conditions of olefinic polyreaction, the first monomer shown in formula (1), initiator and molecular weight regulator will be contained First mixture is added dropwise in the reactor equipped with flux oil, and the initial drop rate of first mixture is X₀；Described The drop rate X of preliminary stage is being added dropwise in one mixture₁-X_n/2Remain constant, be incremented by or successively decrease, mid-term stage is being added dropwise Drop rate X_n/2Meet 4/5X₀<X_n/2<5/4X₀, the drop rate X in stage phase after the drop wise addition_n/2-X_nSuccessively decrease, when completion of dropwise addition Drop rate X_nMeet 1/10X_n/2<X_n<4/5X_n/2；Total time for adding of first mixture is t1；

(b) while first mixture is added dropwise, second comonomer, initiator and molecular-weight adjusting shown in formula (2) will be contained Second mixture of agent is added dropwise in above-mentioned reactor, and the initial drop rate of second mixture is Y₀；Described second is mixed The drop rate Y of preliminary stage is being added dropwise in compound₁-Y_n/2It is incremented by, the drop rate Y of mid-term stage is being added dropwise_n/2Meet Y₀<Y_n/2< 5Y₀, the drop rate Y in stage phase after the drop wise addition_n/2-Y_nRemain constant, be incremented by or successively decrease, the drop rate when completion of dropwise addition Y_nMeet 4/5Y_n/2<Y_n<6/5Y_n/2；Total time for adding of second mixture is t2, and t1=t2.

5. composition according to claim 4, it is characterised in that the initial temperature of the olefinic polyreaction is 50-180 ℃；When total the time for adding t1 and t2 are 1-12 small.

6. composition according to claim 4, it is characterised in that the method for preparing the acrylate based copolymer is also wrapped When the 0.5-2 that includes after first mixture and the second mixture completion of dropwise addition that the reaction was continued is small, initiator and dilution are then added Oil, afterwards again by the temperature 0.5-5 that rises at 100-150 DEG C that the reaction was continued it is small when.

7. composition described in accordance with the claim 1, it is characterised in that the component A accounts for the lubricant oil composite gross mass 0.01%-2%.

8. composition described in accordance with the claim 1, it is characterised in that the component B be selected from amorphous ethylene propylene copolymer, The copolymerization of polymethacrylates, poly- alkylmethacrylate, methacrylate copolymer, styrene and acrylate Thing, styrene/isoprene, phenylethylene/butadiene, the partially hydrogenated copolymer of isoprene/butadiene, and butadiene With isoprene, the partially hydrogenated homopolymer of isoprene/divinylbenzene；The component B accounts for the lubricant oil composite The 0.1%-25% of gross mass.

9. composition described in accordance with the claim 1, it is characterised in that the component C be selected from polyisobutene succinimide without Grey dispersant and/or antioxidant polyisobutene succinimide ashless dispersant；It is total that the component C accounts for the lubricant oil composite The 0.5%-15% of quality.

10. composition described in accordance with the claim 1, it is characterised in that the component D is alkyl sodium salicylate and alkyl monosulfide The mixture of phenol calcium；The component D accounts for the 0.5%-8% of the lubricant oil composite gross mass.

11. composition described in accordance with the claim 1, it is characterised in that the alkyl in the zinc dialkyl dithiophosphate is Alkyl containing 2 to 12 carbon atoms；Additions of the component E in the lubricant oil composite is with the quality of P elements point Number meter is no more than 0.12%.

12. composition described in accordance with the claim 1, it is characterised in that the alkyl of the dialkyl dithio amino formate It is the alkyl containing 2 to 12 carbon atoms；The component F accounts for the 0.02%-5% of the lubricant oil composite gross mass.

13. composition described in accordance with the claim 1, it is characterised in that the component G be phenol type antioxidant, amine type antioxidant, One or more in phenolic ester type antioxidant and thiophenols ester type antioxidant；The component F accounts for the total matter of the lubricant oil composite The 0.1%-6% of amount.

14. the preparation method of the composition described in one of claim 1-13, it is characterised in that add each lube oil additive Into lube base oil, heating is uniformly mixed.