阅读说明：本技术 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法 (Contain star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver and preparation method thereof ) 是由 马道林 马浚轩 于 2019-08-14 设计创作，主要内容包括：本发明公开了一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法,它是将马来酸酐接枝的三元乙丙橡胶、催化剂(I)、改性单体(II)、辅助单体(III),经过特定的熔融聚合方法制备而成的的星型聚合物的固体,或溶液聚合方法制备而成的星型聚合物的液体组合物。本发明的在不降低OCP类VII的油品清净性的前提下,能够改善剪切稳定性或低温性能。(Contain star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver and preparation method thereof the invention discloses a kind of, it is by the ethylene propylene diene rubber of maleic anhydride grafting, catalyst (I), modified monomer (II), auxiliary monomer (III), the liquid composition for the star-type polymer that the solid or solution polymerization process for the star-type polymer being prepared by specific melt polymerization process are prepared.It is of the invention under the premise of not reducing the oil product detergency of OCP class VII, shear stability or cryogenic property can be improved.)

1. a kind of be grafted ternary ethylene-propylene copolymer lubricating oil viscosity index improver containing star-like maleic anhydride, it is characterised in that The modifier is by the ethylene propylene diene rubber of maleic anhydride grafting, catalyst (I), modified monomer (II), auxiliary monomer (III), the liquid that the solid or solution polymerization process for the star-type polymer being prepared by melt polymerization process are prepared Body composition.

2. being improved as described in claim 1 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Agent, it is characterised in that according to mass fraction meter, the amount ranges of four kinds of raw material components are as follows: the ternary of maleic anhydride grafting EP rubbers is not less than 98 parts, and catalyst (I) is no more than 1.2 parts, auxiliary monomer (III) no more than 0.1 part, modified monomer (II) No more than 0.7 part.

3. being improved as described in claim 1 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Agent, it is characterised in that the catalyst (I) is the compound containing formula (α) structural unit, wherein R1 and R2 is respectively hydrogen, C1 ~12 alkyl, naphthenic base, aryl, acyl group, ester group, carbonate group, any one or any combination in ketone group；The alkane Base, naphthenic base, aryl, acyl group, ester group, carbonate group, ketone group；The molecular formula of (α) structural unit is as follows:

4. being improved as described in claim 1 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Agent, it is characterised in that the modified monomer (II) be containing there are two the compound of following (β) or (γ) structural unit, (β) and The molecular formula of (γ) structural unit is as follows:

5. being improved as described in claim 1 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Agent, it is characterised in that the auxiliary monomer (III) be styrene, acrylamide, contain formula (δ) structure thiuram derivative In any one, wherein R3 and R4 be the alkyl of C1~7, it is naphthenic base, aryl, benzyl, isobutyl group, any one in piperidyl Kind or any combination；Wherein, the molecular formula of formula (δ) are as follows:

6. a kind of melt polymerization containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver Method, it is characterised in that method includes the following steps:

(11) catalyst (I) is accurately weighed, and is dissolved in solvent, solution (A) is obtained；Solution (A) is equably sprayed into maleic acid Stirring in the terpolymer pellet (B) of acid anhydride grafting, stands, after solvent volatilizees completely, obtains composition (C)；

(12) mixed and modified material (C) is squeezed out on extruder, control extrusion temperature is between 150-300 DEG C, in extruder plus The mixture (D) of modified monomer (II) and auxiliary monomer (III) is added dropwise in hot arc or end, obtains after extrusion described star-like Maleic anhydride be grafted ternary ethylene-propylene copolymer lubricating oil viscosity index improver.

7. being improved as claimed in claim 6 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index The melt polymerization process of agent, it is characterised in that in the melt phase polycondensation, solvent used is energy catalyst-solvent but cannot The solvent for dissolving terpolymer (I), is any one of acetone, ethyl acetate, methanol, ethyl alcohol.

8. a kind of polymerisation in solution containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver Method, it is characterised in that the described method comprises the following steps:

(21) ethylene propylene diene rubber of maleic anhydride grafting is added in the reactor of Xiang Shengyou base oil in batches, control temperature is not More than 100 DEG C, blender is started, dissolves terpolymer, control mass concentration is being no more than 30%.

(22) it is warming up to 120 DEG C~300 DEG C, then injecting catalyst (I) into reaction kettle, is reacted by 1~30min, so that altogether Polymers is degraded, and macromolecular radical is formed；

(23) mixture (D) for reinjecting modified monomer (II) auxiliary monomer (III), persistently stirs 10-30min, cooling discharging, Obtain the composition of the star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver.

9. being improved as claimed in claim 8 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index The solution polymerization process of agent, it is characterised in that the base oil is times of mineral base oil, synthetic base oil, vegetalitas base oil It anticipates one kind, 40 DEG C of kinematic viscosity of base oil are 5.0~160.0mm²/ s and/or 100 DEG C of kinematic viscosity is 1.50~34.0mm²/ s。

10. changing as claimed in claim 9 containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Into the solution polymerization process of agent, it is characterised in that the mineral base oil main component includes alkane, cycloalkane, aromatic hydrocarbons, cycloalkanes Base aromatic hydrocarbons and oxygen-containing, nitrogen, sulphur organic compound；Synthetic oil is polyalphaolefin, synthetic ester, polyethers, silicone oil, fluorine-containing oil, phosphate In any one or any combination；Vegetalitas base oil is the natural animal-plant grease in molecular structure containing ester bond.

Technical field

The invention belongs to modifying lubricating oil technical field more particularly to a kind of lubricating oil viscosity index improver composition and Preparation method.

Background technique

Viscosity index improver (VII) is the oil-soluble high-molecular compound under a kind of room temperature in rubber-like or solid-like, Usually the concentrate of 5-10% is diluted to come using a kind of (lubricant oil composite of Li Zhongming with the neutral oil of 150SN or 100SN Viscosity index improver .CN 108048167A).VII is added into lubricating oil, can be obtained that cold cranking capacity is good, high temperature viscosity is suitable Preferably, the multi-grade oil of all-season, long service life.The macromolecular chain of VII is fully extended at high temperature in lubricating oil, plays increase Viscosity effect；Meeting shrinkage crimping, the influence to viscosity are small under low temperature.Thus, compared with the identical single-stage lubricating oil of viscosity, contain The multi-grade oil of VII viscosity index (VI) with higher and smooth viscosity-temperature curve.

The tackifying of ethylene-propylene copolymer viscosity index improver (OCP), shear stability, viscosity temperature characteristic are preferable, and Raw material is easy to get, simple process (Xiang Wencheng dispersion type ethylene-propylene copolymer viscosity index improver lubricating oil .1994,5:36- 42.), but resistance to low temperature is also slightly worse, often needs to be added lipid pour-point depressant.The low temperature properties and oxidation stability of PMA class VII are excellent It is different, but thickening property and oil product detergency are poor.If the advantage of the two is combined together, it can get certain comprehensive performance and mention It rises, such as MA class monomer is grafted or is copolymerized to OCP, but still not significant enough (Chen Dehong, Song Qingwu, Liu Jianxin the dispersion of effect The development petroleum refining of antioxidant ethylene-propylene copolymer viscosity index improver DAOCP and chemical industry .2001,1:34-36.).Malaysia It is a kind of product by ethylene propylene diene rubber after maleic anhydride is grafted that acid anhydrides, which is grafted ethylene propylene diene rubber, is contained on molecular backbone There is anhydride group, cryogenic property is advantageous to improving, with it come to prepare VII be a good selection.

In general, OCP class VII molecular weight is bigger, and molecular entanglement is more significant under low temperature, acts in certain shear Under, flow resistance is bigger.Molecular weight distribution is narrower, and long and short chain molecular ratios are fewer, under certain shearing force, occurs disconnected Chain possibility is smaller, and viscosity retention is stronger.Therefore, molecular weight is smaller and molecular weight distribution is wider, and to improving, cryogenic property is excellent It is different, but to thickening property, unfavorable (Wang Guojin, Zhu Heju, Ye Yuankai, Chen Yuezhu .OCP viscosity index improver molecular structure are to low The influence lubrication of warm nature energy therefore, has both tackifying, shear stability, hot oxygen with sealing .1999,6:26-29.) in order to obtain Change the OCP of stability, oil product detergency, cryogenic property, it can be further from the molecule of maleic anhydride grafting ethylene propylene diene rubber Structure, molecular weight are set about in molecular weight distribution.

As patent application 99108204.4 discloses a kind of lubricant tackifier and its production method, lubricant tackifier Be made of following composition: A. has 3.98% to 9.96% bibasic ethylene propylene rubber or ethylene propylene diene rubber or their mixing Object；B. there is 0.02% to 0.04% biscyclo pentadienyl iron；C. surplus is machine oil；Or be made of following composition: A. has 3.96% to 9.92% bibasic ethylene propylene rubber or ethylene propylene diene rubber or their mixture: B. has 0.02% to 0.0 4% Biscyclo pentadienyl iron；C. there is 0.02% to 0.04% succimide；D. surplus is machine oil.However, the lubricating oil increases Stick can not improve shear stability under cryogenic, and there is thickening properties, shear stability, oil product detergency, resistance to The problem of cryogenic property etc. cannot be taken into account.

Summary of the invention

Based on this, the primary purpose of the present invention is that providing one under the premise of not reducing the oil product detergency of OCP class VII Kind improves shear stability or the star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity that contains of cryogenic property refers to Number modifier and preparation method thereof.

The purpose of the present invention is to provide one kind take into account tackifying (thickening ability), shear stability, oil product detergency and Cryogenic property contains star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver and its preparation side Method, and reduce the generation of irreversible crosslinking, improve the preparation efficiency and reliability of product.

To achieve the above object, the technical solution of the present invention is as follows:

A kind of to be grafted ternary ethylene-propylene copolymer lubricating oil viscosity index improver containing star-like maleic anhydride, feature exists It is to pass through the ethylene propylene diene rubber of maleic anhydride grafting, catalyst (I), modified monomer (II), auxiliary monomer (III) in it The solid or solution polymerization process for the star-type polymer that specific melt polymerization process is prepared are prepared star-like poly- Close the liquid composition of object.

The solid is paste or block.

According to mass fraction meter, the amount ranges of four kinds of raw material components are as follows: the EPDM of maleic anhydride grafting Rubber be not less than 98 parts, catalyst (I) be no more than 0.1 part, modified monomer (II) be no more than 1.2 parts, auxiliary monomer (III) no More than 0.7 part.

Further, the preferred amount ranges of four kinds of raw material components are as follows: the ethylene-propylene-diene monomer of maleic anhydride grafting 98~99.5 parts of glue, catalyst (I) is 0.05~0.1 part, modified monomer (II) is 0.3~1.2 part, auxiliary monomer (III) is 0.15~0.7 part.

The ethylene propylene diene rubber number-average molecular weight of the maleic anhydride grafting is 2~150,000.

The catalyst (I) is the compound containing formula (α) structural unit.Wherein, R1 and R2 is respectively hydrogen, C1~12 Alkyl, naphthenic base, aryl, acyl group, ester group, carbonate group, any one or any combination in ketone group.Wherein, the alkane Base, naphthenic base, aryl, acyl group, ester group, carbonate group, ketone group, can further 1~6 be independently selected from alkyl, naphthenic base, virtue Replaced the substituent group of base；The molecular formula of (α) structural unit is as follows:

Further, the catalyst (I) can selected from hydrogen peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, Cumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, The peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, any one in di-cyclohexylperoxy di-carbonate.

The modified monomer (II) is containing there are two the compound of following (β) or (γ) structural unit, (β) and (γ) The molecular formula of structural unit is as follows:

Further, the modified monomer (II) is to can be trimethylolpropane trimethacrylate, trimethylolpropane tris Methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxyl group) the third three Alcohol triacrylate, three (2- ethoxy) isocyanuric acid triacrylates, two (trimethylolpropane) tetraacrylates, season penta Tetra-acrylate, 4 (ethyoxyl) pentaerythritol tetraacrylates, any one in double pentaerythritol methacrylate.

The auxiliary monomer (III) is styrene, acrylamide, contains appointing in the thiuram derivative of formula (δ) structure It anticipates one kind, wherein R3 and R4 can be the alkyl of C1~7, naphthenic base, aryl, benzyl, isobutyl group, any one in piperidyl Or any combination；Wherein, the molecular formula of formula (δ) are as follows:

The thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, curing Thiuram, tetra-benzyl thiram disulfide, DMDPTD dimethyl diphenylthiuram disulfide, disulfide diisobutyl autumn are blue Nurse, two rings, penta methylene tetraalkylthiuram disulfide, bis-pentamethylenethiuram tetrasulfide, six vulcanization di-penta methylene thiurams Deng.

A kind of melting containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver is poly- Conjunction method, it is characterised in that method includes the following steps:

(11) catalyst (I) is accurately weighed, and is dissolved in solvent, solution (A) is obtained；Solution (A) is equably sprayed into horse Stirring in maleic anhydride grafted terpolymer pellet (B), stands, after solvent volatilizees completely, obtains composition (C)；

(12) mixed and modified material (C) is squeezed out on extruder, control extrusion temperature is to squeeze out between 150-300 DEG C The mixture (D) of modified monomer (II) and auxiliary monomer (III) is added dropwise in machine bringing-up section or end, obtains after extrusion described Star-like maleic anhydride is grafted ternary ethylene-propylene copolymer lubricating oil viscosity index improver.

In the melt phase polycondensation, solvent used is energy catalyst-solvent but cannot dissolve terpolymer (I) Solvent can be acetone, ethyl acetate, methanol, ethyl alcohol and other solvents for being easy to volatilize.

A kind of solution containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver is poly- Conjunction method, it is characterised in that the described method comprises the following steps:

(21) ethylene propylene diene rubber of maleic anhydride grafting, control temperature is added in the reactor of Xiang Shengyou base oil in batches Degree is no more than 100 DEG C, starts blender, dissolves terpolymer, and control mass concentration is being no more than 30%.

(22) it is warming up to 120 DEG C~300 DEG C, then injecting catalyst (I) into reaction kettle, reacts, makes by 1~30min It obtains copolymer to degrade, forms macromolecular radical；

(23) mixture (D) of modified monomer (II) auxiliary monomer (III) is reinjected, 10-30 min is persistently stirred, it is cooling It discharges to get the composition of ternary ethylene-propylene copolymer lubricating oil viscosity index improver is grafted to the star-like maleic anhydride.

The base oil be mineral base oil, synthetic base oil, vegetalitas base oil any one, 40 DEG C of base oil Kinematic viscosity is 5.0~160.0mm²/ s and/or 100 DEG C of kinematic viscosity is 1.50~34.0mm²/s。

Further, the mineral base oil main component include alkane, cycloalkane, aromatic hydrocarbons, naphthenic base aromatic hydrocarbons and it is oxygen-containing, Nitrogen, sulphur organic compound；Synthetic oil can be polyalphaolefin, synthetic ester, polyethers, silicone oil, fluorine-containing oil, any one in phosphate Kind or any combination；Vegetalitas base oil is the natural animal-plant grease in molecular structure containing ester bond.

The present invention is by being added catalyst (II), so that the upper propyl moiety of maleic anhydride grafting ternary ethylene-propylene copolymer Unit is degraded, and propyl unit ratio is reduced, and the molecular weight distribution of strand broadens；In conjunction with control catalyst (I) and The addition sequence and dosage of modified monomer (II) make macromolecular radical react with modified monomer (II), form long-chain branch Star copolymer；The use of auxiliary monomer (III), reduces the generation of irreversible crosslinking, it is low to be formed by star-type polymer The lower strand of temperature is shunk, but does not occur seriously to tangle, and the influence to viscosity is smaller；Under high temperature, strand is unfolded, and is increased to lubricating oil Glutinous effect is significant.

More importantly structural unit (β) ratio is reduced and the molecular weight distribution of strand broadens, gained lubricating oil VII's Cryogenic property is significant.The modifier and preparation method thereof overcomes the crosslinking problem in polymerization process, to make preparation Lubricating oil VII has the characteristics that thickening capabilities are strong, shear stability is good, cryogenic property and high-temperature oxydation detergency are excellent.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.

What the present invention was realized improves containing star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index Agent is by the ethylene propylene diene rubber of maleic anhydride grafting, catalyst (I), modified monomer (II), auxiliary monomer (III), by spy The solid for the star-type polymer that fixed melt polymerization process is prepared, such as paste or block or solution polymerization process The liquid composition being prepared.

According to mass fraction meter, the amount ranges of four kinds of raw material components are as follows: the EPDM of maleic anhydride grafting Rubber be not less than 98 parts, catalyst (I) be no more than 0.1 part, modified monomer (II) be no more than 1.2 parts, auxiliary monomer (III) no More than 0.7 part.The preferred amount ranges of four kinds of above-mentioned raw material components are as follows: the ethylene propylene diene rubber 98 of maleic anhydride grafting~ 99.5 parts, catalyst (I) is 0.05~0.1 part, modified monomer (II) is 0.3~1.2 part, auxiliary monomer (III) be 0.15~ 0.7 part.

The ethylene propylene diene rubber number-average molecular weight of the maleic anhydride grafting is 2~150,000.

The catalyst (I) is the compound containing formula (α) structural unit.Wherein, R1 and R2 is respectively hydrogen, C1~12 Alkyl, naphthenic base, aryl, acyl group, ester group, carbonate group, any one or any combination in ketone group.Wherein, the alkane Base, naphthenic base, aryl, acyl group, ester group, carbonate group, ketone group, can further 1~6 be independently selected from alkyl, naphthenic base, virtue Replaced the substituent group of base；The molecular formula of (α) structural unit is as follows:

Wherein, the catalyst (I) can be selected from hydrogen peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, mistake Aoxidize diisopropylbenzene (DIPB), di-t-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, mistake Aoxidize the trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, any one in di-cyclohexylperoxy di-carbonate.

The modified monomer (II) is containing there are two the compound of following (β) or (γ) structural unit, (β) and (γ) The molecular formula of structural unit is as follows:

Wherein, the modified monomer (II) is to can be trimethylolpropane trimethacrylate, trimethylolpropane tris first Base acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxyl group) glycerine Triacrylate, three (2- ethoxy) isocyanuric acid triacrylates, two (trimethylolpropane) tetraacrylates, pentaerythrite Tetraacrylate, 4 (ethyoxyl) pentaerythritol tetraacrylates, any one in double pentaerythritol methacrylate.

The auxiliary monomer (III) is styrene, acrylamide, contains appointing in the thiuram derivative of formula (δ) structure It anticipates one kind, wherein R3 and R4 can be the alkyl of C1~7, naphthenic base, aryl, benzyl, isobutyl group, any one in piperidyl Or any combination；Wherein, the molecular formula of formula (δ) are as follows:

The thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, curing Thiuram, tetra-benzyl thiram disulfide, DMDPTD dimethyl diphenylthiuram disulfide, disulfide diisobutyl autumn are blue Nurse, two rings, penta methylene tetraalkylthiuram disulfide, bis-pentamethylenethiuram tetrasulfide, six vulcanization di-penta methylene thiurams Deng.

The present invention realizes the molten of star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver Melt polymerization, comprising the following steps:

(11) catalyst (I) is accurately weighed, and is dissolved in solvent, solution (A) is obtained；Solution (A) is equably sprayed into horse Stirring in maleic anhydride grafted terpolymer pellet (B), stands, after solvent volatilizees completely, obtains composition (C)；

(12) mixed and modified material (C) is squeezed out on extruder, control extrusion temperature is to squeeze out between 150-300 DEG C The mixture (D) of modified monomer (II) and auxiliary monomer (III) is added dropwise in machine bringing-up section or end, obtains after extrusion described Star-like maleic anhydride be grafted ternary ethylene-propylene copolymer lubricating oil viscosity index improver.

In the melt phase polycondensation, solvent used is energy catalyst-solvent but cannot dissolve terpolymer (I) Solvent can be acetone, ethyl acetate, methanol, ethyl alcohol and other solvents for being easy to volatilize.

The present invention realizes the molten of star-like maleic anhydride grafting ternary ethylene-propylene copolymer lubricating oil viscosity index improver Liquid polymerization, comprising the following steps:

(21) ethylene propylene diene rubber of maleic anhydride grafting, control temperature is added in the reactor of Xiang Shengyou base oil in batches Degree is no more than 100 DEG C, starts blender, dissolves terpolymer, and control mass concentration is being no more than 30%.

(22) it is warming up to 120 DEG C~300 DEG C, then injecting catalyst (I) into reaction kettle, reacts, makes by 1~30min It obtains copolymer to degrade, forms macromolecular radical；

(23) mixture (D) of modified monomer (II) auxiliary monomer (III) is reinjected, 10-30 min is persistently stirred, it is cooling It discharges to get the combination of ternary ethylene-propylene copolymer lubricating oil viscosity index improver is grafted to the star-like maleic anhydride Object.

The base oil be mineral base oil, synthetic base oil, vegetalitas base oil any one, 40 DEG C of base oil Kinematic viscosity is 5.0~160.0mm²/ s and/or 100 DEG C of kinematic viscosity is 1.50~34.0mm²/s。

Wherein, the mineral base oil main component include alkane, cycloalkane, aromatic hydrocarbons, naphthenic base aromatic hydrocarbons and it is oxygen-containing, Nitrogen, sulphur organic compound；Synthetic oil can be polyalphaolefin, synthetic ester, polyethers, silicone oil, fluorine-containing oil, any one in phosphate Kind or any combination；Vegetalitas base oil is the natural animal-plant grease in molecular structure containing ester bond.