CN113024702B - Ethylene-alpha-olefin copolymer, preparation method thereof and lubricating oil viscosity index improver containing same - Google Patents
Ethylene-alpha-olefin copolymer, preparation method thereof and lubricating oil viscosity index improver containing same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/68—Vanadium, niobium, tantalum or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
Abstract
The invention provides an ethylene-alpha-olefin copolymer, a preparation method thereof and a lubricating oil viscosity index improver containing the same. The preparation method comprises the following steps: in the presence of a solvent, a main catalyst, a cocatalyst and a molecular weight regulator, ethylene and alpha-olefin are taken as polymerization monomers to carry out polymerization reaction to obtain the ethylene-alpha-olefin copolymer, wherein the main catalyst is an alcohol modified vanadium compound with a general formula of VO (OR) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and less than or equal to 2; the cocatalyst is alkylaluminum halide. The ethylene-alpha-olefin copolymer prepared by the preparation method has the advantages of narrow molecular weight distribution, smaller molecular weight and high polymerization activity.
Description
Technical Field
The invention relates to the field of ethylene-propylene rubber manufacturing, in particular to an ethylene-alpha-olefin copolymer, a preparation method thereof and a lubricating oil viscosity index improver containing the same.
Background
The ethylene propylene rubber has become an important rubber in the field of ethylene propylene rubber, and in the world, a plurality of companies have produced the elastomer with the brand number of less than dozens, and because a third monomer is not arranged in the molecular structure, the production cost is relatively low, and the application field is very wide. One of the applications that is not negligible is as a viscosity index improver for lubricating oils.
The ethylene-alpha-olefin copolymer has the advantages of high temperature resistance and aging resistance, so the ethylene-alpha-olefin copolymer is an indispensable viscosity index improver in the field of lubricating oil. When the ethylene-alpha-olefin copolymer is used as a viscosity index improver for a lubricating oil, it is required to be dissolved in a base oil at a high temperature, and therefore the relative molecular mass of the polymer is required not to be too large. If the relative molecular mass is large, it will result in the polymer dissolving in the base oil for too long a time, affecting the yield per unit time, while if it is too small, it will result in the polymer having a reduced thickening ability. In addition, the relative molecular mass distribution of the ethylene- α -olefin copolymer has an effect on shear, and a relatively narrow relative molecular mass distribution can impart shear stability thereto. Therefore, the industry has been devoted to the development of ethylene- α -olefin copolymers having a narrow distribution of relative molecular mass and a low Mooney for use as a viscosity index modifier for lubricating oils.
In the production of ethylene-alpha-olefin copolymers, despite the advent of new catalytic technologies, such as metallocene ethylene-propylene catalysis, the V-alkylaluminum system still plays a dominant role in the synthesis of ethylene-propylene elastomers, and the use of vanadium system Ziegler-Natta catalysts for the copolymerization of ethylene-alpha-olefins to produce rubber elastomers is a well-known process in the industry. Representative procatalysts such as VOCl 3 、VCl 3 、VCl 4 、V(acac) 3 And the other component is an organometallic compound of groups I-III (e.g., an aluminum alkyl).
Disclosure of Invention
The invention mainly aims to provide an ethylene-alpha-olefin copolymer, a preparation method thereof and a lubricating oil viscosity index improver containing the ethylene-alpha-olefin copolymer, so as to solve the problems of wide molecular weight distribution and large molecular weight of the ethylene-alpha-olefin copolymer prepared by the existing method.
In order to achieve the above object, one aspect of the present invention provides a method for preparing an ethylene- α -olefin copolymer, the method comprising: in the presence of a solvent, a main catalyst, a cocatalyst and a molecular weight regulator, ethylene and alpha-olefin are taken as polymerization monomers to carry out polymerization reaction to obtain the ethylene-alpha-olefin copolymer, wherein the main catalyst is an alcohol modified vanadium compound with a general formula of VO (OR) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and more than or equal to m and less than or equal to 2; the cocatalyst is alkylaluminum halide.
Further, the main catalyst is ethanol modified VOCl 3 Of the general formula VO (OEt) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and less than or equal to 2; the cocatalyst is selected from one or more of the group consisting of triethylaluminum trichloride, diethylaluminum monochloride and monoethylaluminum dichloride.
Further, the molar ratio of the Al element in the co-catalyst to the V element in the main catalyst compound is (1 to 100): 1, preferably (5 to 50): 1, and more preferably (6 to 20): 1.
Further, the α -olefin is selected from one or more of the group consisting of propylene, 1-butene, 1-hexene, 1-octene and 1-decene; preferably, the molar ratio of alpha-olefin to ethylene is (2-5): 1, more preferably (2.9-3.1): 1.
Further, the temperature of the polymerization reaction is 15-60 ℃, the pressure is 0.01-2 MPa, and the reaction time is 10-180 min; preferably, the temperature of the polymerization reaction is 40-42 ℃, the pressure is 0.5-0.6 MPa, and the reaction time is 20-60 min.
Further, the molecular mass regulator is diethyl zinc and/or hydrogen.
Further, the molecular mass regulator is hydrogen; preferably, the hydrogen is present in a concentration of 5 to 15% by weight, based on the total weight of hydrogen, ethylene and alpha-olefin.
Another aspect of the present application also provides an ethylene- α -olefin copolymer prepared by the preparation method of any one of claims 1 to 7.
Further, the weight average molecular weight of the ethylene-alpha-olefin copolymer is 14-19 ten thousand, and the molecular weight distribution is 1.7-2.2; preferably, the weight average molecular weight of the ethylene- α -olefin copolymer is 16 to 18 ten thousand, and the molecular weight distribution is 1.8 to 2.0.
Still another aspect of the present application provides a lubricating oil viscosity index improver comprising the above ethylene- α -olefin copolymer.
By applying the technical scheme of the invention, in the preparation method, under the existence of a specific main catalyst and a cocatalyst, the polymerization reaction of ethylene and alpha-olefin as polymerization monomers can greatly improve the reaction activity and selectivity of the polymerization reaction, and simultaneously, under the action of the main catalyst and a molecular weight regulator, the ethylene-alpha-olefin copolymer prepared by the polymerization reaction has smaller molecular weight, higher reaction activity and narrower distribution width. The addition of the solvent is beneficial to improving the compatibility of all raw materials in the reaction system, so that the polymerization reaction is carried out in a more uniform environment. On the basis, the ethylene-alpha-olefin copolymer prepared by the preparation method has the advantages of narrow molecular weight distribution, smaller molecular weight and high polymerization activity.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the ethylene-alpha-olefin copolymer produced by the prior art method has problems of broad molecular weight distribution and large molecular weight. In order to solve the above technical problems, the present application provides a method for preparing an ethylene- α -olefin copolymer, the method comprising: in the presence of a solvent, a main catalyst, a cocatalyst and a molecular weight regulator, ethylene and alpha-olefin are taken as polymerization monomers to carry out polymerization reaction to obtain the ethylene-alpha-olefin copolymer, wherein the main catalyst is an alcohol modified vanadium compound with a general formula of VO (OR) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and less than or equal to 2; the cocatalyst is alkylaluminum halide.
In the preparation method, under the existence of a specific main catalyst and a specific cocatalyst, the polymerization reaction of ethylene and alpha-olefin as polymerization monomers can greatly improve the reaction activity and selectivity of the polymerization reaction, and simultaneously, under the action of the main catalyst and a molecular weight regulator, the ethylene-alpha-olefin copolymer prepared by the polymerization reaction has smaller molecular weight, higher reaction activity and narrower distribution width. The addition of the solvent is beneficial to improving the compatibility of all raw materials in the reaction system, so that the polymerization reaction is carried out in a more uniform environment. On the basis, the ethylene-alpha-olefin copolymer prepared by the preparation method has the advantages of narrow molecular weight distribution, smaller molecular weight and high polymerization activity.
In a preferred embodiment, the procatalyst is an ethanol modified VOCl 3 Of the general formula VO (OEt) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and less than or equal to 2; the cocatalyst is selected from one or more of the group consisting of triethylaluminum trichloride, diethylaluminum monochloride and monoethylaluminum dichloride.
In a preferred embodiment, the molar ratio of the Al element in the cocatalyst to the V element in the main catalyst compound is (1-100): 1. The ratio of the Al element in the co-catalyst to the V element in the main catalyst compound includes, but is not limited to, the above range, and it is advantageous to further improve the polymerization activity of the ethylene- α -olefin copolymer while reducing the molecular weight and the width of the molecular weight distribution thereof by limiting it to the above range. Preferably (5-50): 1, and more preferably (6-20): 1.
The α -olefin used in the above polymerization reaction may be selected from those conventionally used in the art according to the objective product. In a preferred embodiment, the alpha-olefins include, but are not limited to, one or more of the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and 1-decene. Preferably, the mole ratio of alpha-olefin to ethylene is (2-5): 1. The mole ratio of the alpha-olefin to ethylene includes, but is not limited to, the above range, and the limitation of the mole ratio to the mole ratio of the alpha-olefin to ethylene in the above range is advantageous for improving the oil solubility of the ethylene-alpha-olefin copolymer, thereby improving the effect of using the ethylene-alpha-olefin copolymer in subsequent applications. More preferably, the ratio of moles of alpha-olefin to moles of ethylene is (2.9-3.1): 1.
In a preferred embodiment, the polymerization temperature is 15 to 60 ℃, the pressure is 0.01 to 2MPa, and the reaction time is 10 to 180min. It is advantageous to further improve the polymerization activity of the ethylene- α -olefin copolymer by limiting the polymerization temperature, pressure and reaction time to the above ranges. More preferably, the temperature of the polymerization reaction is 40 to 42 ℃, the pressure is 0.5 to 0.6MPa, and the reaction time is 20 to 60min.
The molecular mass regulator used in the polymerization reaction may be any one commonly used in the art. In a preferred embodiment, the molecular mass regulator includes, but is not limited to, diethyl zinc and/or hydrogen. The raw materials are selected as molecular mass regulators, so that the molecular weight of the ethylene-alpha-olefin copolymer is further reduced, and the distribution width of the molecular weight is narrowed. More preferably, the molecular mass regulator is hydrogen. The use of hydrogen as a molecular weight regulator is advantageous for further reducing the molecular weight of the ethylene-alpha-olefin copolymer and narrowing the molecular weight distribution width as compared with other molecular weight regulators. In a preferred embodiment, the hydrogen concentration is from 5 to 15%, more preferably from 5 to 15%, based on the total weight of hydrogen, ethylene and alpha-olefin.
In another aspect of the present application, there is provided an ethylene- α -olefin copolymer, which is prepared by the above-mentioned preparation method.
In the preparation method, in the presence of a specific main catalyst and a cocatalyst, the reaction activity and selectivity of the polymerization reaction can be greatly improved by using ethylene and alpha-olefin as polymerization monomers for polymerization reaction, and simultaneously, under the action of the main catalyst and a molecular weight regulator, the ethylene-alpha-olefin copolymer prepared by the polymerization reaction has smaller molecular weight and narrower distribution width. The addition of the solvent is beneficial to improving the compatibility of all raw materials in the reaction system, so that the polymerization reaction is carried out in a more uniform environment. On the basis, the ethylene-alpha-olefin copolymer prepared by the preparation method has the advantages of narrow molecular weight distribution, smaller molecular weight and high polymerization activity.
In a preferred embodiment, the ethylene- α -olefin copolymer has a weight average molecular weight of 14 to 19 ten thousand and a molecular weight distribution of 1.7 to 2.2. The ethylene-alpha-olefin copolymer having the above weight average molecular weight and molecular weight distribution range is selected to contribute to further reduction in the Mooney viscosity, shortening of the dissolution time and reduction in the thickening ability. More preferably, the weight average molecular weight of the ethylene- α -olefin copolymer is 16 to 18 ten thousand, and the molecular weight distribution is 1.8 to 2.0.
Still another aspect of the present application provides a lubricating oil viscosity index improver comprising the above ethylene- α -olefin copolymer.
The ethylene-alpha-olefin copolymer prepared by the preparation method has the advantages of narrow molecular weight distribution, smaller molecular weight and high polymerization activity. Therefore, the lubricating oil viscosity index improver prepared by the lubricating oil viscosity index improver can have the advantages of better solubility, lower viscosity, higher shear stability and the like in base oil.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
And (3) performance testing:
(1) The ethylene content was analyzed by infrared spectroscopy.
(2) Mooney viscosity analysis the Mooney viscosity machine was preheated at 100 ℃ for 1 minute and tested for 4 minutes.
(3) The analysis of the relative molecular mass distribution adopts normal temperature gel permeation chromatography, takes tetrahydrofuran or toluene as a solvent, and analyzes at normal temperature.
(4) Shear stability: SSI is shear stability, measured using a shear manufactured by BOSCH, using ASTM D3945/6278-98.
(5) Thickening capacity: 1% of the polymer was dissolved in 150N of a base oil and then measured by an Ubbelohde viscometer.
Example 1
Polymerization test
Ethylene (E) and propylene (P) were prepared in a mixing apparatus at a (mol) ratio of P/E =3:1, with a hydrogen content of 7.5% in the mixed monomers.
The preparation method comprises the steps of fully and uniformly mixing by a circulating compressor, carrying out anhydrous and anaerobic treatment on a 5L polymerization kettle in a vacuum state, using high-purity nitrogen as inert gas, continuously adding dry hexane (the water content is less than or equal to 5 ppm) into the polymerization kettle by a metering pump, introducing mixed gas into the polymerization kettle by the circulating compressor, enabling the mixed gas dissolved in the hexane to reach saturation by the flow of the mixed gas to be 130L/h, sequentially adding 72ml/h (the concentration is 0.0175mmol/ml hexane) of dichloroethoxy vanadyl hexane solution by the metering pump, adding triethyl aluminum into the polymerization kettle by the metering pump to enable the Al/V ratio to be 10, controlling the polymerization temperature to be 42 ℃, the polymerization pressure to be 0.5MPa and the polymerization reaction time to be 0.75 hour, continuously discharging the obtained polymerization glue solution, stopping by using ethanol, and adding an anti-aging agent (2,6-di-tert-butyl p-methyl phenol).
And (3) recovering hexane from the obtained glue solution by a steam distillation method, and drying the obtained ethylene-propylene copolymer for 24 hours at 80 ℃ in a vacuum state after glue solution separation. By gel permeation chromatography analysis, the weight average relative molecular mass is 17.5 ten thousand, the relative molecular mass distribution is 1.94, the Mooney viscosity (ML 1+4100 ℃) is 10.5, and by infrared spectrophotometer analysis, the ethylene content is 46.1%.
Performance test
Weighing 20g of ethylene-propylene copolymer obtained in a polymerization test, adding the ethylene-propylene copolymer into 180g of base oil (150N), stirring and dissolving at 120 ℃, enabling the complete dissolution time to be 2.2 hours visually, diluting the ethylene-propylene copolymer to 1% by using the base oil, and testing the thickening capacity to be 4.4mm 2 The resulting product was sheared with a shear stability tester (BOSCH, germany) to give an SSI of 23.1. The results are shown in tables 1 and 2.
Example 2
The differences from example 1 are:
the molar ratio of propylene to ethylene was 3.02 to 1, and the hydrogen content in the mixed monomer was 8.1%, as in example 1.
Example 3
The differences from example 1 are:
the molar ratio of propylene to ethylene was 3.05.
Example 4
The differences from example 1 are:
the molar ratio of propylene to ethylene was 3.06.
Example 5
The differences from example 1 are:
the ratio of the number of moles of propylene to the number of moles of ethylene was 2:1, and the hydrogen content of the mixed monomer was 15%, the same as in example 1.
Example 6
The differences from example 1 are:
the ratio of the number of moles of propylene to the number of moles of ethylene was 5:1, and the hydrogen content of the mixed monomer was 5%, the same as in example 1.
Example 7
The differences from example 1 are:
the ratio of the number of moles of propylene to the number of moles of ethylene was 1:1, and the hydrogen content of the mixed monomer was 5%, the same as in example 1.
Example 8
The differences from example 1 are:
the main catalyst is dichloropropoxy vanadyl and VOCH 3 CH 2 CH 2 OCl 2 Otherwise, the same as in example 1.
Example 9
The differences from example 1 are:
the main catalyst is dichloro methoxy vanadyl and VOCH 3 OCl 2 The rest is the same as in example 1.
Example 10
The differences from example 1 are:
the main catalyst is diethoxy vanadyl chloride and is VO (CH) 3 CH 2 O) 2 Cl, otherwise the same as in example 1.
Example 11
The differences from example 1 are:
the main catalyst is triethoxy vanadyl and is VO (CH) 3 CH 2 O) 3 The rest is the same as in example 1.
Example 12
The differences from example 5 are: the molecular weight regulator was diethyl zinc, and the rest was the same as in example 1.
Example 13
The differences from example 5 are: the molecular weight regulator is a mixed gas of diethyl zinc and hydrogen, the mole ratio is 1:1, and the rest is the same as the example 1.
Example 14
The differences from example 1 are: the temperature of the polymerization reaction is 15 ℃, the pressure is 2MPa, and the reaction time is 60min.
Example 15
The differences from example 1 are: the temperature of the polymerization reaction is 60 ℃, the pressure is 0.01MPa, and the reaction time is 60min.
Comparative example 1
The polymerization process was the same as in example 1, with triethylaluminum trichloride as cocatalyst and VOCl as procatalyst 3 The amount of the catalyst was 1.35mmol, the Al/V ratio was 10, P/E =2.3, the hydrogen content was 3%, the other reaction conditions were the same as in example 1, and the weight average relative molecular mass was 22 ten thousand, the relative molecular mass distribution was 2.3, the Mooney viscosity (ML 1+4100 ℃ C.) was 16, and the ethylene content was 39% as determined by infrared spectrophotometer analysis.
Comparative examples 2 and 3
The polymerization process was the same as in example 1, the hydrogen, ethylene and propylene were adjusted, the main catalyst was VOCl 3 The reaction conditions were the same as in example 1 except that the amount was 1.35mmol and the Al/V ratio was 10.
TABLE 1
TABLE 2
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 7 and comparative examples 1 to 3, it is understood that limiting the ratio of the number of moles of propylene to the number of moles of ethylene and the hydrogen content in the mixed monomer to the preferable range in the present application is advantageous for further reducing the molecular weight of the ethylene- α -olefin copolymer, narrowing the width of the molecular weight distribution thereof, and improving the polymerization activity thereof.
Comparing examples 1, 8 to 11 and comparative example 1, it can be seen that the use of the preferred procatalyst of the present application is advantageous in further reducing the molecular weight of the ethylene- α -olefin copolymer, narrowing the width of the molecular weight distribution thereof, and improving the polymerization activity thereof.
As can be seen from comparison of examples 1, 12 to 13 and comparative example 1, the use of the preferred molecular weight regulator of the present application is advantageous in further reducing the molecular weight of the ethylene- α -olefin copolymer, narrowing the width of the molecular weight distribution thereof, and improving the polymerization activity thereof.
Comparing examples 1, 14 to 15, it can be seen that the preferred polymerization process parameters are selected to further reduce the molecular weight of the ethylene- α -olefin copolymer, to narrow the molecular weight distribution width, and to improve the polymerization activity.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A method for producing an ethylene- α -olefin copolymer, the method comprising:
in the presence of a solvent, a main catalyst, a cocatalyst and a molecular weight regulator, ethylene and alpha-olefin are used as polymerization monomers to carry out polymerization reaction to obtain the ethylene-alpha-olefin copolymer, wherein the main catalyst is ethanol modified VOCl 3 Of the general formula VO (OEt) n Cl m N is more than or equal to 1 and less than or equal to 3,0 and less than or equal to 2; the cocatalyst is alkyl aluminum halide; the alpha-olefin is propylene, and the mole ratio of the propylene to the ethylene is (2.9-3.1): 1; the temperature of the polymerization reaction is 40-42 ℃; the molecular weight regulator is selected from a mixture of diethyl zinc and hydrogen, or hydrogen, and the concentration of the hydrogen is 5-15% by weight of the total weight of the hydrogen, the ethylene and the alpha-olefin.
2. The method of claim 1, wherein the cocatalyst is one or more selected from the group consisting of triethylaluminum trichloride, diethylaluminum monochloride and monoethylaluminum dichloride.
3. The production method according to claim 1 or 2, wherein the molar ratio of the Al element in the co-catalyst to the V element in the main catalyst compound is (1 to 100): 1.
4. The process according to claim 3, wherein the molar ratio of the Al element in the co-catalyst to the V element in the main catalyst compound is (5-50): 1.
5. The method according to claim 4, wherein the molar ratio of the Al element in the co-catalyst to the V element in the main catalyst compound is (6-20): 1.
6. The method according to claim 1, wherein the pressure of the polymerization reaction is 0.01 to 2MPa, and the reaction time is 10 to 180min.
7. The method according to claim 6, wherein the polymerization pressure is 0.5 to 0.6MPa and the reaction time is 20 to 60min.
8. An ethylene- α -olefin copolymer produced by the production method according to any one of claims 1 to 7.
9. The ethylene- α -olefin copolymer according to claim 8, wherein the weight average molecular weight of the ethylene- α -olefin copolymer is from 14 to 19 ten thousand, and the molecular weight distribution is from 1.7 to 2.2.
10. The ethylene- α -olefin copolymer according to claim 9, wherein the weight average molecular weight of the ethylene- α -olefin copolymer is 16 to 18 ten thousand, and the molecular weight distribution is 1.8 to 2.0.
11. A lubricating oil viscosity index improver comprising the ethylene- α -olefin copolymer defined in any one of claims 8 to 10.
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| CN1329656A (en) * | 1998-12-09 | 2002-01-02 | 三井化学株式会社 | Viscosity modifier for lubricating oil and lubricating oil composition |
| CN106916243A (en) * | 2015-12-25 | 2017-07-04 | 中国石油天然气股份有限公司 | The fit preparation method of ethene system random copolymerization |
| CN109836523A (en) * | 2017-11-27 | 2019-06-04 | 中国石油天然气股份有限公司 | Carbon monoxide-olefin polymeric, ethylene-alpha-olefin polymers and preparation method thereof |
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