CN108299580B - Method for producing viscosity index improver of ethylene-propylene copolymer lubricating oil - Google Patents
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Abstract
The invention relates to the field of lubricating oil viscosity index improvers and discloses a method for producing an ethylene-propylene copolymer lubricating oil viscosity index improver, wherein the method comprises the steps of dissolving an ethylene-propylene copolymer glue solution in base oil, and then removing a solvent; the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer glue solution is not higher than 120000. The viscosity index improver for the ethylene-propylene copolymer lubricating oil produced by the method provided by the invention omits the processes of coagulation of glue solution, post-treatment drying, shearing hot melting and degradation of dry glue, simplifies the process steps, reduces the production cost, and can be used for preparing a high-performance lubricating oil adhesive.
Description
Technical Field
The invention relates to the field of lubricating oil viscosity index improvers, in particular to a method for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
Background
The viscosity index improver of the lubricating oil, also called tackifier, is mainly used in internal combustion engine oil, hydraulic oil, automatic transmission fluid and gear oil, and has the function of improving the viscosity-temperature performance of oil products to ensure that the oil products have higher viscosity index, so that the engine can be smoothly started at low temperature, and the oil products have enough viscosity at high temperature to ensure good lubricating performance. Lubricating oil viscosity index improvers have evolved from the original Polyisobutylene (PIB), polymethacrylate (PMA) to ethylene-propylene copolymer (OCP) and hydrogenated styrene-conjugated diene copolymer (HSD), where OCP has good thickening power, good shear stability, moderate low temperature performance, and is used more frequently in internal combustion engine oils.
At present, two production modes of the ethylene-propylene copolymer lubricating oil viscosity index improver are mainly provided. Firstly, a direct hot-melt method is adopted, ethylene-propylene dry glue (the number average molecular weight is 50000-80000) with specific relative molecular mass is heated and dissolved in base oil after being sheared to obtain a product with required viscosity, and the method has the defects that the ethylene-propylene dry glue needs to be subjected to technical processes such as rubber cutting hot-melt and the like, and the price of the ethylene-propylene dry glue with specific relative molecular mass is high; the other method is a degradation method, ethylene-propylene dry gum with higher relative molecular mass (the number average molecular weight is higher than 80000) is degraded to specific relative molecular mass (the number average molecular weight is 20000-80000) through thermal oxidation or machinery, and the method usually needs to add degradation catalyst, antioxidant, cosolvent and the like, and the method has the defects of complex process, great control difficulty and long production flow, and also increases the production cost, and the main process flow is as follows: adding base oil and dry ethylene-propylene rubber into a degradation kettle in proportion, heating by using heat conduction oil to raise the temperature, dissolving the dry ethylene-propylene rubber in the base oil, introducing compressed air or oxygen and chemical auxiliaries under specified operating conditions to thermally oxidize and degrade the dry ethylene-propylene rubber, circulating materials in the degradation kettle by using a pump, flowing through a pipeline cutter at a high speed, and controlling the degradation temperature and time to obtain a product with the required viscosity.
Disclosure of Invention
The invention aims to solve the problems of long production flow, high production cost and high quality control difficulty in the production process of the viscosity index improver of the ethylene-propylene copolymer lubricating oil at present, and provides a novel method for producing the viscosity index improver of the ethylene-propylene copolymer lubricating oil.
After intensive research, the inventor of the invention finds that when the molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer lubricating oil viscosity index improver is too large and the Mooney viscosity is too high, the ethylene-propylene copolymer needs to be degraded to a small molecular weight in advance, otherwise, the finally obtained viscosity index improver has poor shear stability; the low molecular weight ethylene-propylene copolymer is beneficial to improving the shear stability of the viscosity index improver, but the conventional ethylene-propylene copolymer lubricating oil viscosity index improver is generally prepared by thermally dissolving ethylene-propylene rubber dry glue in base oil, and the process of preparing the low molecular weight ethylene-propylene copolymer glue solution into the dry glue generally needs specific coagulation equipment and has severe requirements on production equipment and production process, so that the low molecular weight ethylene-propylene rubber dry glue is difficult to obtain. The inventor of the invention further finds that in the preparation process of the viscosity index improver of the ethylene-propylene copolymer lubricating oil, if the solvent in the ethylene-propylene copolymer glue solution is not removed to prepare dry glue, the ethylene-propylene copolymer glue solution is directly dissolved in the base oil, and finally the solvent is removed, so that the process can be simplified, and the ethylene-propylene copolymer glue solution with lower molecular weight can be easily obtained only by controlling the polymerization condition without the step of glue solution condensation, thereby being more beneficial to obtaining the high-performance lubricating oil finger-sticking agent. Based on this, the present invention has been completed.
The invention provides a method for producing an ethylene-propylene copolymer lubricating oil viscosity index improver, wherein the method comprises the steps of dissolving an ethylene-propylene copolymer glue solution in base oil, and then removing a solvent; the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer glue solution is not higher than 120000.
The viscosity index improver of the ethylene-propylene copolymer lubricating oil produced by the method provided by the invention omits the processes of coagulation of glue solution, post-treatment drying, shearing thermal dissolution and degradation of dry glue, simplifies the process steps, reduces the production cost, can be used for preparing high-performance lubricating oil adhesive, and has great industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The method for producing the viscosity index improver of the ethylene-propylene copolymer lubricating oil comprises the steps of dissolving an ethylene-propylene copolymer glue solution in base oil, and then removing a solvent; the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer glue solution is not higher than 120000.
According to the present invention, although it is sufficient to control the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer dope to be not higher than 120000, in order to obtain a viscosity index improver having higher shear stability, it is preferable that the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer dope is 20000 to 120000, more preferably 20000 to 80000, still more preferably 20000 to 60000, and most preferably 25000 to 50000.
The concentration of the ethylene-propylene copolymer glue solution is not particularly limited in the invention, but in order to facilitate the preparation of the ethylene-propylene copolymer glue solution and the smooth proceeding of the subsequent dissolving process in the base oil, the concentration of the ethylene-propylene copolymer glue solution is preferably 5-50 wt%, more preferably 6-30 wt%, and most preferably 8-20 wt%.
The mixing ratio of the base oil and the ethylene-propylene copolymer glue solution is not particularly limited in the present invention, and the amount of the ethylene-propylene copolymer glue solution in terms of the ethylene-propylene copolymer is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, and most preferably 60 to 100 parts by weight, relative to 100 parts by weight of the base oil.
The ethylene-propylene copolymer cement may be obtained commercially or prepared by various methods known to those skilled in the art. According to a specific embodiment of the invention, the ethylene-propylene copolymer glue solution is prepared by the following method: ethylene and propylene are solution polymerized in the presence of hydrogen and a catalyst, after which the catalyst is optionally removed.
In the preparation process of the ethylene-propylene copolymer glue solution, the molar ratio of the ethylene to the propylene is preferably 1: 1-15, more preferably 1: 2-10, and most preferably 1: 3-8. Wherein, the hydrogen plays a role in adjusting the molecular weight of the ethylene-propylene copolymer, and the amount of the hydrogen is preferably 0.5-5mol%, more preferably 0.5-4mol%, and most preferably 1-3mol% of the total amount of the ethylene, the propylene and the hydrogen. The ethylene, propylene and hydrogen may be introduced into the polymerization reaction system separately, or may be mixed and then introduced into the polymerization reaction system in the form of a mixed gas or liquid, and the present invention is not particularly limited thereto.
In the preparation process of the ethylene-propylene copolymer cement, the catalyst may be any catalyst capable of initiating solution polymerization of ethylene and propylene, for example, a multi-site or single-site catalyst system, specifically, at least one catalyst selected from a vanadium-aluminum catalyst system, a metallocene catalyst system and a non-metallocene catalyst system, and preferably a vanadium-aluminum catalyst system. The vanadium-aluminum catalyst system generally contains, preferably consists of, an alkyl aluminum compound and a vanadium compound. Wherein, the molar ratio of the content of the alkyl aluminum compound to the content of the vanadium compound in the vanadium-aluminum catalyst system can be 10-80: 1, and preferably 10-30: 1. The alkylaluminum compound may be selected from AlR 3 、AlR 2 X、Al 2 R 3 X 3 And AlRX 2 Wherein R is C 1 -C 8 X is halogen. In particular toExamples of the alkyl aluminum compound include, but are not limited to: trimethylaluminum (TMA), triethylaluminum (TEA), tripropylaluminum (TPA), triisopropylaluminum (TIPA), triisobutylaluminum (TIBA), sesquiethylaluminum chloride and Tributylaluminum (TBA). The vanadium compound can be a tetravalent compound or a pentavalent compound of transition metal vanadium, and specifically can be at least one of vanadium halide, oxyhalide, organic acid salt and organic acid ester. The vanadium compound is preferably vanadium acetylacetonate (V (acac) from the viewpoint of availability of raw materials 3 ) Vanadium tetrachloride (VCl) 4 ) Vanadium oxytrichloride (VOCl) 3 ) Trialkoxyvanadyl (VO (OR) 3 ) Monochloroalkoxy vanadyl (VO (OR) 2 Cl), dichloroalkoxyvanadyl (VO (OR) Cl) 2 ) And the like.
The solvent used in the polymerization reaction system of the present invention is not particularly limited in kind, and may be any of various inert liquid substances that can be used as a reaction medium in the prior art, and for example, hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, and the like may be used, and hydrocarbon solvents are preferable. Wherein the hydrocarbon solvent is preferably C 1 -C 10 Alkane, C 5 -C 7 Cycloalkane of (2) 6 -C 10 At least one aromatic hydrocarbon, more preferably C 5 -C 10 Is a saturated alkane. From the viewpoint of availability of raw materials and in order to facilitate removal of the subsequent solvent more, the solvent is particularly preferably at least one of n-hexane, cyclohexane, n-butane, cyclobutane, n-pentane and cyclopentane, and most preferably n-hexane. Among them, these solvents mentioned above may be used alone or in combination. Furthermore, the amount of the solvent may be selected conventionally in the art, preferably such that the concentration of the resulting ethylene-propylene copolymer cement is 5 to 50 wt.%, more preferably 6 to 30 wt.%, most preferably 8 to 20 wt.%.
The conditions of the solution polymerization reaction in the present invention are not particularly limited, and generally include a reaction temperature, a reaction pressure and a reaction time. Wherein, in order to be more beneficial to the solution polymerization reaction, the reaction temperature is preferably-30 ℃ to 150 ℃, and more preferably 0 ℃ to 120 ℃; the reaction pressure is preferably 0.1MPa to 3MPa, more preferably 0.5MPa to 1.5MPa. Generally, the extension of the reaction time is beneficial to improve the molecular weight of the ethylene-propylene copolymer, but in order to obtain the ethylene-propylene copolymer glue solution with the number average molecular weight meeting the requirements of the invention and comprehensively consider the polymerization efficiency and the effect, the reaction time is preferably 10min to 90min, and more preferably 20min to 50min. In the present invention, the pressures are gauge pressures.
According to the invention, the polymerization is generally carried out in an inert atmosphere. The inert atmosphere refers to any gas or gas mixture which does not chemically react with the reactants and products, such as one or more of nitrogen and a gas from group zero of the periodic table of elements. The inert atmosphere may be maintained by introducing any one or a mixture of the above gases which do not chemically react with the reactants and the products into the reaction system.
In the preparation process of the ethylene-propylene copolymer glue solution, the catalyst can be removed or not after the solution polymerization reaction is finished, and the catalyst can be removed or not removed depending on the type and the activity of the catalyst. In the present invention, the mode of removing the catalyst is not particularly limited. According to a specific embodiment of the present invention, the catalyst may be removed by mixing the ethylene-propylene copolymer cement with hot water. Wherein, the amount of the hot water can be 50-400 parts by weight, preferably 100-200 parts by weight, relative to 100 parts by weight of the ethylene-propylene copolymer glue solution. The mixing may be carried out in a mixer or a static mixer.
The base oil is not particularly limited in kind, and may be any of the base oils conventionally used for producing viscosity index improvers of lubricating oils of the ethylene-propylene copolymer type, and is preferably at least one of API group I base oils, group II base oils and group III base oils.
The method for removing the solvent is not particularly limited in the present invention, and can be carried out in various existing apparatuses advantageous for removing the solvent. According to one embodiment of the invention, the solvent removal is performed in a thin film evaporator. Wherein the conditions for removing the solvent in the thin film evaporator generally include a temperature which may be 20 to 100 ℃, preferably 30 to 50 ℃; the flow rate of the material can be selected according to the size of the thin film evaporator so as to remove the solvent fully; the residence time may be from 0.1 to 5min, preferably from 0.5 to 3min. In addition, the specific structure and the working principle of the thin film evaporator are well known to those skilled in the art, and are not described in detail herein.
The viscosity index improver of the ethylene-propylene copolymer lubricating oil obtained by the method can be used for preparing lubricating oil products, such as vehicle oil, industrial oil, agricultural oil, ship oil and the like.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the microstructure of the ethylene-propylene copolymer was measured using a model Bruker AVANCE400 superconducting NMR spectrometer (model: (R)) 1 H-NMR) determination, the solvent is deuterated chloroform CDCl 3 (ii) a The number average molecular weight (Mn) was measured by means of high temperature Gel Permeation Chromatography (GPC) of the type LC-10AT from Shimadzu corporation, in which trichlorobenzene was used as a mobile phase and the measurement temperature was 135 ℃.
In the following examples and comparative examples, the properties of the base oil are shown in table 1:
TABLE 1
Base oil | A | B | C |
Rank of | HVI Ib 150 | API-II6 | API-III6 |
Viscosity at 100 ℃/(mm) 2 ·s -1 ) | 5.31 | 5.67 | 5.54 |
Viscosity index | 93 | 112 | 121 |
Pour point/. Degree.C | -15 | -18 | -15 |
Example 1
This example illustrates the process of the present invention for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
As shown in figure 1, a 2L stainless steel stirred polymerizer is repeatedly replaced with nitrogen for three times, and then 1000mL of n-hexane and 0.3mmol of vanadium oxytrichloride VOCl are added under the protection of nitrogen 3 4mmol of aluminum sesquichloride, starting stirring, controlling the stirring speed at 250rpm, continuously introducing a mixed gas of ethylene, propylene and hydrogen to enable the pressure in a stainless steel stirring polymerization kettle to reach 0.5MPa, wherein the molar ratio of the ethylene to the propylene is 1: 7, the molar content of the hydrogen is 0.75mol%, stirring and reacting at 10 ℃ and 0.5MPa for 30min, introducing the obtained glue solution into a static mixer, mixing the glue solution with hot water at 98 ℃ according to the weight ratio of 100: 150 to remove residual catalyst, and then mixing the glue solution after removing the catalyst (wherein the number average molecular weight of the ethylene-propylene copolymer is 89000, and the concentration is 7.5 wt%) with base oil A (relative to 100 parts by weight of the base oil A, the ethylene-propylene copolymer is calculated by the weight of the base oil A)130 parts by weight of copolymer glue solution) is stirred and mixed evenly in a mixing kettle, and the mixture is continuously introduced into a film evaporator to remove the solvent, in the process, the temperature of the film evaporator is controlled at 45 ℃, and the retention time of the mixture in the film evaporator is controlled at 0.5min, so as to obtain the viscosity index improver of the ethylene-propylene copolymer lubricating oil, which is recorded as Z1.
Example 2
This example illustrates the process of the present invention for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
As shown in FIG. 1, a 2 liter stainless steel stirred polymerizer was repeatedly replaced with nitrogen three times, and then 1000mL of n-hexane, 0.2mmol of vanadium V (acac) acetylacetonate and nitrogen were added thereto under protection of nitrogen 3 3.0mmol of triethyl aluminum, starting stirring, controlling the stirring speed at 250rpm, continuously introducing a mixed gas of ethylene, propylene and hydrogen into the stainless steel stirring polymerization kettle to enable the pressure in the stainless steel stirring polymerization kettle to reach 1.5MPa, wherein the molar ratio of the ethylene to the propylene is 1: 10, the molar content of the hydrogen is 1.2mol%, stirring and reacting at 20 ℃ and 1.5MPa for 20min, introducing the obtained glue solution into a static mixer, and mixing with hot water at the temperature of 98 ℃ according to the ratio of 100:200 weight percent to remove residual catalyst, then evenly stirring and mixing glue solution after removing the catalyst (wherein the number average molecular weight of the ethylene-propylene copolymer is 37000, and the concentration is 9 weight percent) and base oil B (the using amount of the ethylene-propylene copolymer glue solution is 110 weight parts based on the ethylene-propylene copolymer relative to 100 weight parts of the base oil B) in a mixing kettle, and continuously introducing the mixture into a thin film evaporator to remove the solvent, wherein the temperature of the thin film evaporator is controlled at 50 ℃, the retention time of the mixture in the thin film evaporator is controlled at 0.6min, and the viscosity index improver of the ethylene-propylene copolymer lubricating oil, which is recorded as Z2, is obtained.
Example 3
This example illustrates the process of the present invention for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
As shown in FIG. 1, a 2 liter stainless steel stirred polymerizer was repeatedly replaced with nitrogen gas three times, and then, with nitrogen gasUnder the protection of gas, 1000mL of n-hexane and 0.1mmol of vanadium tetrachloride VCl are added 4 And 3mmol of triisobutylaluminum, starting stirring, controlling the stirring speed at 250rpm, continuously introducing a mixed gas of ethylene, propylene and hydrogen so that the pressure in a stainless steel stirring polymerization kettle reaches 0.6MPa, wherein the molar ratio of ethylene to propylene is 1: 6, the molar content of hydrogen is 3mol%, then stirring and reacting at 0 ℃ and 0.6MPa for 50min, introducing the obtained glue solution into a static mixer, mixing the glue solution with hot water at the temperature of 98 ℃ according to the weight ratio of 100:200 so as to remove residual catalyst, uniformly stirring and mixing the glue solution after removing the catalyst (wherein the number average molecular weight of the ethylene-propylene copolymer is 25000 and the concentration is 8 weight percent) and base oil C (relative to 100 weight parts of the base oil C, the using amount of the ethylene-propylene copolymer in terms of the ethylene-propylene copolymer is 125 weight parts) in the mixing kettle, continuously introducing the mixture into a thin film evaporator so as to remove solvent, controlling the temperature of the thin film evaporator to be 55 ℃, controlling the residence time of the mixture in the thin film evaporator to be 0.8min, and obtaining a lubricating oil viscosity index improver Z, wherein the ethylene-propylene copolymer is recorded as 3.
Example 4
This example illustrates the process of the present invention for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
An ethylene-propylene copolymer lubricating oil viscosity index improver was produced in the same manner as in example 1, except that the amount of hydrogen used was adjusted to 4mol% so that the number average molecular weight of the ethylene-propylene copolymer in the obtained ethylene-propylene copolymer gum solution was 15000, to obtain an ethylene-propylene copolymer lubricating oil viscosity index improver, which was designated as Z4.
Comparative example 1
This comparative example is illustrative of a reference process for producing an ethylene-propylene copolymer lubricating oil viscosity index improver.
An ethylene-propylene copolymer lubricating oil viscosity index improver was produced as in example 1, except that the amount of hydrogen was adjusted to 0.3mol% so that the number average molecular weight of the ethylene-propylene copolymer in the obtained ethylene-propylene copolymer gum solution was 130000, to obtain a reference ethylene-propylene copolymer lubricating oil viscosity index improver, which was designated as DZ1.
Test example
Test examples are used to illustrate the performance of the viscosity index improver for lubricating oils of the ethylene-propylene copolymer type.
(1) Pour point:
the results obtained are shown in Table 2, measured according to the method specified in GB/T3536.
(2) Viscosity at 100 ℃:
the results obtained are shown in Table 2, measured according to the method specified in GB/T265.
(3) Thickening capacity:
the results obtained are shown in Table 2, determined according to the method specified in SH/T0566.
(4) Shear stability index:
the results, determined according to the method specified in SH 0622-appendix A, are given in Table 2.
TABLE 2
From the results, the viscosity index improver of the ethylene-propylene copolymer lubricating oil produced by the method provided by the invention omits the processes of coagulation of glue solution, post-treatment drying, shearing thermal dissolution and degradation of dry glue, simplifies the process steps, reduces the production cost, can be used for preparing high-performance lubricating oil finger-sticking agents, and has great industrial application prospects.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for producing the ethylene-propylene copolymer lubricating oil viscosity index improver is characterized in that the method comprises the steps of dissolving an ethylene-propylene copolymer glue solution in base oil, and then removing a solvent; the number average molecular weight of the ethylene-propylene copolymer in the ethylene-propylene copolymer glue solution is 15000-50000;
the ethylene-propylene copolymer glue solution is obtained by carrying out solution polymerization reaction on ethylene and propylene in the presence of hydrogen and a catalyst;
the molar ratio of ethylene to propylene is 1:3-10, wherein the amount of the hydrogen accounts for 1-4mol% of the total amount of the ethylene, the propylene and the hydrogen;
the catalyst is a vanadium-aluminum catalyst, and the molar ratio of the content of an alkyl aluminum compound to the content of a vanadium compound in the vanadium-aluminum catalyst system is 10-30:1;
the conditions of the solution polymerization reaction include: the reaction temperature is 0-120 ℃, the reaction pressure is 0.5-1.5 MPa, and the reaction time is 20-50 min.
2. The method as claimed in claim 1, wherein the concentration of the ethylene-propylene copolymer gum solution is 5-50 wt%.
3. A method according to claim 1, wherein the ethylene-propylene copolymer gum solution is used in an amount of 20-200 parts by weight, based on the ethylene-propylene copolymer, with respect to 100 parts by weight of the base oil.
4. The process according to claim 1, wherein the alkylaluminum compound is selected from AlR 3 、AlR 2 X、Al 2 R 3 X 3 And AlRX 2 Wherein R is C 1 -C 8 X is halogen.
5. The method of claim 1, wherein the vanadium compound is selected from at least one of a halide, oxyhalide, organic acid salt, and organic acid ester of vanadium.
6. The process according to claim 1, wherein the solvent used in the polymerization system is C 5 -C 10 Is a saturated alkane.
7. The method according to claim 6, wherein the solvent used in the polymerization reaction system is n-hexane.
8. A process according to any one of claims 1 to 3, wherein the base oil is a mineral oil.
9. The method of claim 8, wherein the base oil is at least one of an API group I base oil, a group II base oil, and a group III base oil.
10. The method according to any one of claims 1 to 3, wherein the solvent removal is performed in a thin film evaporator.
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CN105132081B (en) * | 2015-08-19 | 2018-04-06 | 西京学院 | A kind of preparation method of ethylene-propylene copolymer viscosity index improver |
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