CN112920840A - Method for preparing polyolefin synthetic oil - Google Patents

Method for preparing polyolefin synthetic oil Download PDF

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CN112920840A
CN112920840A CN202110034146.8A CN202110034146A CN112920840A CN 112920840 A CN112920840 A CN 112920840A CN 202110034146 A CN202110034146 A CN 202110034146A CN 112920840 A CN112920840 A CN 112920840A
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olefin
reaction
polymerization
alpha
unsaturated
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魏东初
叶健
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Abbott Science And Technology Hangzhou Co ltd
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Abbott Science And Technology Hangzhou Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes

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Abstract

The invention discloses a method for preparing polyolefin synthetic oil, which can prepare synthetic oil products with medium and high viscosity grades. The method comprises the steps of premixing a cocatalyst and a main catalyst or respectively adding the cocatalyst and the main catalyst into a polymerization reactor containing a reaction medium, introducing low-carbon olefin as a main polymerization monomer, controlling proper reaction temperature and reaction pressure, and preparing the polyolefin synthetic oil (mAPO) by homopolymerization of the low-carbon olefin or copolymerization of the low-carbon olefin and alpha-olefin prepared by an ethylene oligomerization method or alpha-olefin prepared by a Fischer-Tropsch method. The invention takes the olefin which is abundant in source and relatively cheap in China as the main raw material, can reduce the cost of the raw material and reduce the dependence on imported high-carbon alpha-olefin. Meanwhile, the invention can prepare a series of synthetic oil products with medium and high viscosity grades at high conversion rate, and has the advantages of excellent product performance, wide viscosity range and flexible adjustment.

Description

Method for preparing polyolefin synthetic oil
Technical Field
The invention relates to a preparation technology of synthetic lubricating oil base oil, relates to a method for preparing polyolefin synthetic oil, and particularly relates to a method for preparing medium-high viscosity polyolefin synthetic oil base oil through low-carbon olefin polymerization.
Background
The fully synthetic base oil is a high-quality lubricating oil raw material, and particularly, the synthetic oil of Poly-Alpha-olefin (PAO) has the best comprehensive performance. PAO mainly composed of C8～C12Compared with mineral oil, the linear alpha-olefin has better low-temperature fluidity, higher viscosity index (generally more than 135), better oxidation resistance and thermal stability, higher shear resistance under heavy-load mechanical shear stress and lower volatility, and has the advantages of environmental protection, energy conservation, safety, no toxicity and comprehensive use costLower, etc.
PAOs can be classified mainly into three grades of low, medium and high viscosity. Generally, the low viscosity PAO has a kinematic viscosity at 100 ℃ of less than 10cSt, the medium viscosity PAO has a kinematic viscosity at 100 ℃ of 10-40cSt, the high viscosity PAO has a kinematic viscosity at 100 ℃ of more than 40cSt, and the high viscosity PAO is called an ultra-high viscosity PAO when the kinematic viscosity at 100 ℃ is more than 100 cSt. Depending on the viscosity, PAOs are widely used in industrial and automotive fields, and play an important role in many fields such as automobile engine oils, gear oils, hydraulic transmission oils, hydraulic oils, aircraft engine oils, aircraft lubricating oils, heat transfer oils, and insulating oils. For example, medium and low viscosity PAOs have important applications in the automotive field, while ultra-high viscosity synthetic lubricating oils have extremely important applications in dynamic and static lubrication of heavy duty, low or ultra-low speed moving parts used in high-speed rail, aircraft carriers, nuclear powered submarines, heavy duty vehicles, heavy armored tanks, and in such fields as the ocean going vessel industry, the steel industry, and the cement industry.
The viscosity and performance of PAOs is closely related to the catalyst and polymerization process employed. The existing mainstream PAO production process mostly adopts BF3Or AlCl3And the like Lewis acid type catalysts, but can only produce medium and low viscosity products with irregular side chains. In 2010, exxon mobil corporation first introduced a new generation of PAO synthetic oils based on metallocene catalyst technology. The Metallocene catalyst is a catalytic system which takes IVB group transition metal elements (such as Ti, Zr, Hf and the like) complexes (ligands contain cyclopentadienyl rings or derivatives thereof) as a main catalyst, has the characteristic of a single active center, has higher activity when catalyzing alpha-olefin polymerization, and can produce mPAO (Metallocene-PAO) with regular comb-shaped structure and uniform polymerization degree. Currently, only five foreign companies, ExxonMobil, snowdrop (Chevron Phillips), infringes (Ineos), langson (Lanxess) and sheen (Idemitsu), are internationally producing high viscosity mPAO products with kinematic viscosities of 40-300 cSt, but none are turning outside the assignee.
The industrialization of the Chinese synthetic oil base oil is started late and always in a laggard situation, the structural contradiction of the product is prominent day by day, and the domestic main productivity is concentrated onMiddle and low-end products still have a large gap with the international advanced level in the aspect of mPAO development. Production of PAO generally employs C8～C12Is used as the starting material. However, the domestic shortage of high-quality olefin raw materials for polymerization exists at present, and the domestic prior art can only partially produce hexene-1, C8And above LAOs depend entirely on imports. Since LAO producers are 99% concentrated in Europe and America, C8～C12The supply of olefins has been very short and scarce, with the supply of high purity decene-1 being more limited and very expensive. Before solving the problem of olefin source in China, C is adopted8～C12The PAO synthetic oil prepared by using olefin as a raw material has high production cost and is easily produced by people.
Generally, the reasons why China is in a relatively laggard position in the industrialization of high-performance mPAO synthetic oil are mainly that the synthesis aspect is limited by upstream raw material supply, catalysts and production processes. Therefore, to realize the autonomous development of the high-performance mPAO synthetic oil, domestic research institutions need to further increase research and development investment in the aspects of raw materials, catalysts, polymerization processes and the like.
Disclosure of Invention
In order to reduce the cost of raw materials and reduce the dependence on imported high-carbon alpha-olefin, the invention takes low-carbon olefin such as ethylene, propylene or 1-butene and the like which are abundant and cheap in China and Fischer-Tropsch alpha-olefin as main raw materials, and adopts a Metallocene CGC catalyst system to prepare polyolefin synthetic oil (mAPO, Metallocene Apalene-Poly-Olefins), thereby breaking through the supply limit of market raw materials and greatly reducing the product cost.
The method for preparing the polyolefin synthetic oil is characterized in that a cocatalyst and a main catalyst are premixed or respectively added into a polymerization reactor containing a reaction medium, low-carbon olefin is introduced as a main polymerization monomer, the reaction temperature is controlled to be below 100 ℃, the reaction pressure is controlled to be below 1MPa, and the polyolefin synthetic oil is prepared by homopolymerization of the low-carbon olefin or copolymerization of the low-carbon olefin and Fischer-Tropsch alpha-olefin.
According to a preferred embodiment of the invention, the procatalyst is selected from the group of metallocene CGC catalysts having a defined geometric configuration.
The main catalyst has the following structural general formula:
Figure BDA0002892426160000021
wherein the content of the first and second substances,
i) l is a heteroatom coordinating group such as N, O, P, S, and is used for replacing one Cp ring in the traditional double Cp metal catalyst, L is connected with another Cp through a bridging group E, E can be C, Si, Ge or Sn, and n is an integer more than or equal to 1;
ii)R1and R2Same or different, each independently selected from hydrogen, saturated or unsaturated C1To C20Hydrocarbyl, saturated or unsaturated C1To C20Halogenated hydrocarbon groups, saturated or unsaturated C1To C20Hydrocarbyloxy, saturated or unsaturated C3To C20Cycloalkyl radical, C6To C20Aryl radicals or C6To C20A heterocyclic aromatic hydrocarbon group; r1、R2Can also be reacted with EnTogether form a benzene ring, a heterocycle or other aromatic ring;
iii)R3selected from hydrogen, saturated or unsaturated C1To C20Hydrocarbyl, saturated or unsaturated C1To C20Halogenated hydrocarbon groups, saturated or unsaturated C1To C20Hydrocarbyloxy, saturated or unsaturated C3To C20Cycloalkyl radical, C6To C20Aryl radicals or C6To C20A heterocyclic aromatic hydrocarbon group;
iv)R4、R5、R6and R7The same or different, each independently selected from hydrogen, halogen, saturated or unsaturated C1To C10Hydrocarbyl, saturated or unsaturated C1To C10Halogenated hydrocarbon groups, saturated or unsaturated C1To C10Hydrocarbyloxy, saturated or unsaturated C3To C10Cycloalkyl radical, C6To C10Aryl radicals or C6To C10A heterocyclic aromatic hydrocarbon group;
v) or, R4And R5、R5And R6Or R6And R7Can form a new cyclopentadienyl ring, a benzene ring, a heterocyclic ring or other complex aromatic rings together with the carbon atoms connected with Cp;
vi) M is Ti, Zr or Hf;
vii)X1and X2The same or different, each independently selected from hydrogen, halogen, saturated or unsaturated C1To C20A hydrocarbyl group.
In the CGC catalyst, a space multi-membered ring configuration with geometric tension is formed between a cyclopentadienyl ring Cp-bridging group E-coordination heteroatom L-central metal M, the structure limits the free rotation of Cp around a metal center, so that the catalyst structure has rigidity, and the existence of a bridging group enables the metal active center of the CGC catalyst to be opened only in one direction, thereby achieving the purpose of limiting the geometric configuration. In the CGC, the occlusion angle of Cp-M-L is smaller than that of a metallocene bridged complex Cp-M-Cp, so that the space left by an active center for coordination of olefin is larger, and a large-volume alpha-olefin can be more sufficiently close to the active center to facilitate coordination and insertion of the alpha-olefin, thereby endowing the CGC catalyst with extremely strong copolymerization capability.
According to a preferred embodiment of the present invention, the polymerized monomeric lower olefin is selected from ethylene, propylene or butene-1.
According to a preferred embodiment of the present invention, the lower olefin is further preferably ethylene.
According to a preferred embodiment of the present invention, the polyolefin synthetic oil can be prepared by homopolymerization of lower olefins or copolymerization with alpha-olefins prepared by oligomerization of ethylene or with alpha-olefins prepared by a fischer-tropsch process.
According to a preferred embodiment of the invention, the fischer-tropsch alpha-olefins are alpha-olefins or crude products thereof, converted from coal or natural gas by fischer-tropsch synthesis, having an alpha-olefin content of from 10 to 90%, preferably more than 50%, and an oxygenate content of not more than 5%.
The polyolefin synthetic oil can be prepared by homopolymerization of low-carbon olefin or copolymerization of alpha-olefin prepared by an ethylene oligomerization method or alpha-olefin prepared by a Fischer-Tropsch method, and can also utilize crude products obtained by coal or natural gas through Fischer-Tropsch synthesis and conversion, so that the preparation method can fully utilize raw material resources and greatly reduce the production cost.
According to a preferred embodiment of the invention, the fischer-tropsch alpha-olefin preferably has an alpha-olefin content of more than 60% and an oxygenate content of not more than 2%.
According to a preferred embodiment of the invention, the fischer-tropsch alpha-olefins are used for the preparation of polyolefin synthetic oils after removal of oxygenates.
The CGC catalyst is capable of re-coordinating and inserting a long-chain product having a terminal double bond formed in polymerization to obtain a polymerization product having a long side chain, and also can participate in polymerization of α -olefin as a comonomer with a high insertion rate to obtain a long side chain polymerization product.
According to a preferred embodiment of the invention, the cocatalyst is an organoaluminium compound, an organoboron compound or a combination of both.
According to a preferred embodiment of the present invention, the organoaluminum compound is selected from one or more of alkylaluminum, alkylaluminum halide, alkylaluminoxane or modified alkylaluminoxane.
According to a preferred embodiment of the invention, the organoaluminium compound is selected from C1～C10Alkyl aluminium, halogenated C1～C10Alkyl aluminium, C1～C10Alkoxy aluminium, C1～C10Alkylaluminoxane or modified C1～C10 alkyl aluminoxane.
According to a preferred embodiment of the present invention, the organoaluminum compound may be specifically selected from any one or more of aluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, aluminum isopropoxide, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and modified methylaluminoxane and derivatives thereof.
According to a preferred embodiment of the invention, the organoboron compound is selected fromBoroxine, triethylborane, triphenylborane ammonia complex, NaBH4One or more boron compounds such as tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityltetrakis (pentafluorophenyl) borate, tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, diethylphenylammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, ethyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, trioctylammonium tetrakis (pentafluorophenyl) borate, and the like.
According to a preferred embodiment of the invention, the cocatalyst is preferably selected from alkylaluminoxanes, modified alkylaluminoxanes or a combination of alkylaluminums and organic borides.
According to a preferred embodiment of the present invention, in the polymerization reaction system, the molar ratio of aluminum in the cocatalyst to the metal contained in the main catalyst is 20-5000: 1.
According to a preferred embodiment of the present invention, in the polymerization reaction system, the molar ratio of aluminum in the cocatalyst to the metal contained in the main catalyst is more preferably 50 to 3000: 1.
According to a preferred embodiment of the present invention, in the polymerization reaction system, the molar ratio of boron in the organic boride to the metal contained in the main catalyst is 1-5: 1.
According to a preferred embodiment of the present invention, in the polymerization reaction system, the molar ratio of boron in the organic boron compound to the metal contained in the main catalyst is more preferably 1 to 2: 1.
According to a preferred embodiment of the present invention, the concentration of the main catalyst in the polymerization system is 1X 10 based on the central metal-7～1×10-3mol/L。
According to a preferred embodiment of the present invention, the concentration of the main catalyst in the polymerization reaction system is more preferably 1X 10 in terms of the central metal-6～5×10-4mol/L。
According to a preferred embodiment of the present invention, the cocatalyst and the main catalyst may be pre-mixed and then added into the reactor, or may be added directly into the reactor to form the catalytic active sites in situ.
According to a preferred embodiment of the present invention, the polymerization reactor is selected from one or more of a microchannel reactor, a tubular reactor, a tank reactor, a tower reactor, a packed reactor, a bubble reactor, a falling film reactor, a hypergravity reactor, an applied sound field reactor, an applied electric field reactor and an applied magnetic field reactor.
The reactors may be multiple reactors combined in series and/or parallel.
According to a preferred embodiment of the present invention, the reaction medium is selected from one or more of aromatic hydrocarbon, halogenated aromatic hydrocarbon, aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, cycloaliphatic hydrocarbon or olefin.
According to a preferred embodiment of the invention, C is chosen as the reaction medium6～C18Aromatic hydrocarbons, halogenated C6～C18Aromatic hydrocarbon, C1～C18Aliphatic hydrocarbons, halogenated C1～C18Aliphatic hydrocarbons, C5～C18Cycloaliphatic hydrocarbon, C5～C18Linear alpha-olefins, C5～C18One or more of cycloolefins.
According to a preferred embodiment of the present invention, the reaction medium may be one or more selected from benzene, toluene, xylene, chlorobenzene, ethylbenzene, chlorotoluene, cumene, pentane, isopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, chloromethane, chloroethane, 1-hexene, 1-octene, and cyclohexene.
According to a preferred embodiment of the present invention, the reaction medium is further selected from one or more of n-hexane, cyclohexane, methylcyclohexane, n-heptane, toluene, xylene.
According to a preferred embodiment of the present invention, the polymerization temperature is 0 to 100 ℃.
According to a preferred embodiment of the present invention, the polymerization temperature is more preferably 30 to 100 ℃.
According to a preferred embodiment of the present invention, the polymerization pressure is 0.05 to 1 MPa.
According to a preferred embodiment of the present invention, the polymerization pressure is further preferably 0.1 to 1 MPa.
In the preparation method of the polyolefin synthetic oil provided by the invention, the viscosity of the oil product is very sensitive to the change of the reaction temperature and the reaction pressure, and the viscosity of the oil product can be flexibly adjusted through different temperature and pressure combinations.
According to a preferred embodiment of the present invention, the resulting polymerization product is quenched, the catalyst residue is removed by adsorption, and the solvent and unreacted monomers are distilled off to obtain a polyolefin synthetic oil. According to the method provided by the invention, a series of medium-high viscosity synthetic oil base oil products can be produced by adopting different catalysts and/or different polymerization process conditions.
In a preferred embodiment of the present invention, the method for preparing the polyolefin synthetic oil comprises the steps of:
a) heating and baking the polymerization reaction kettle, vacuumizing and drying, and replacing with high-purity nitrogen for many times to remove water/oxygen impurities in the reaction system;
b) adjusting the temperature of the reaction kettle to the set reaction temperature below 100 ℃, adding a certain amount of reaction medium and comonomer, and starting stirring;
c) sequentially adding a cocatalyst and a main catalyst, opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is below 1MPa, and starting to react;
d) and adding acidified ethanol to terminate the reaction after the reaction is finished, adding a certain amount of activated clay into the obtained product to adsorb and remove catalyst residues, then performing pressure filtration to obtain filtrate, and performing reduced pressure distillation on the filtrate to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil.
Compared with the prior art, the invention has the following advantages:
rich raw material sources, low production cost, high catalyst activity, strong regulation and control capability on the chain structure of a product, adjustable viscosity of a polymerization product, high viscosity index and narrow molecular weight distribution.
Detailed Description
The following examples are provided to further illustrate the preparation method and the technical scheme of the polyolefin synthetic oil of the present invention, but the scope of the present invention should not be limited thereby. All changes and modifications that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
The analysis method applied in the present embodiment is as follows:
the kinematic viscosity of the polyolefin synthetic oil is measured according to GB265 petroleum product kinematic viscosity measurement method and dynamic viscometer algorithm;
the viscosity index is calculated according to a GB2541 petroleum product viscosity index calculation table;
pour point was measured according to GB3535 petroleum products pour point determination.
Example 1
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 30 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalysts used are as follows.
Figure BDA0002892426160000061
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 2
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 50 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 1.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 3
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 70 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 1.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 4
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 90 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 1.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 5
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. Then the temperature of the reaction kettle is adjusted to 70 ℃ through jacket cooling water circulation, 180mL of methylcyclohexane is added as a reaction medium, and 20mL of Fischer-Tropsch coal prepared olefin is added as a comonomer. The content of alpha-olefin in the coal-made olefin is 69.6 percent, the content of alkane is 30 percent, the content of oxygen-containing compound is less than 0.4 percent, and 97 percent of the alpha-olefin is C5-C9 olefin. The main catalyst and cocatalyst used were the same as in example 1.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 6
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The reactor temperature was then adjusted to 70 ℃ by jacket cooling water circulation, 160mL of methylcyclohexane was added as the reaction medium, and 40mL of coal-to-olefin was added as the comonomer. The composition of the coal-to-olefin was the same as in example 5, and the main catalyst and the cocatalyst used were the same as in example 1.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 7
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 30 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst used is as follows,
Figure BDA0002892426160000081
the adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 8
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 50 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 7.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 9
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 70 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 7.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 10
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 90 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and cocatalyst used were the same as in example 7.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 11
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. Then the temperature of the reaction kettle is adjusted to 70 ℃ through jacket cooling water circulation, 180mL of methylcyclohexane is added as a reaction medium, and 20mL of coal olefin is added as a comonomer. The composition of the coal-to-olefin was the same as in example 5, and the main catalyst and the cocatalyst used were the same as in example 7.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 12
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The reactor temperature was then adjusted to 70 ℃ by jacket cooling water circulation, 160mL of methylcyclohexane was added as the reaction medium, and 40mL of coal-to-olefin was added as the comonomer. The composition of the coal-to-olefin was the same as in example 5, and the main catalyst and the cocatalyst used were the same as in example 7.
The adopted cocatalyst is modified methylaluminoxane MMAO-7, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding MMAO-7 into the [ Zr ] ═ 500 mol ratio, adding the main catalyst, and stirring to react. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 13
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 40 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalysts used are as follows.
Figure BDA0002892426160000101
The adopted cocatalysts are triisobutylaluminum and tri (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, the dosage of the main catalyst is set to be 20 mu mol, and according to the set dosage, the [ Al ]: adding a certain amount of triisobutylaluminum in a molar ratio of [ Zr ] ═ 150, adding the main catalyst and tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, and stirring for reaction, wherein [ B ]: [ Zr ] ═ 1.2. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 14
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 60 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and the cocatalyst used were the same as in example 13.
The amount of the main catalyst used was set to 20. mu. mol, and according to the set amount, [ Al ]: adding a certain amount of triisobutylaluminum in a molar ratio of [ Zr ] ═ 150, adding the main catalyst and tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, and stirring for reaction, wherein [ B ]: [ Zr ] ═ 1.2. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 15
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 80 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and the cocatalyst used were the same as in example 13.
The amount of the main catalyst used was set to 20. mu. mol, and according to the set amount, [ Al ]: adding a certain amount of triisobutylaluminum in a molar ratio of [ Zr ] ═ 150, adding the main catalyst and tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, and stirring for reaction, wherein [ B ]: [ Zr ] ═ 1.2. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 16
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. Then the temperature of the reaction kettle is adjusted to 60 ℃ through jacket cooling water circulation, 180mL of methylcyclohexane is added as a reaction medium, and 20mL of coal olefin is added as a comonomer. The composition of the coal-to-olefin was the same as in example 5, and the main catalyst and the cocatalyst used were the same as in example 13.
The amount of the main catalyst used was set to 20. mu. mol, and according to the set amount, [ Al ]: adding a certain amount of triisobutylaluminum in a molar ratio of [ Zr ] ═ 150, adding the main catalyst and tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, and stirring for reaction, wherein [ B ]: [ Zr ] ═ 1.2. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 0.5MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 17
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 60 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalysts used are as follows.
Figure BDA0002892426160000121
The cocatalyst used is methylaluminoxane MAO (10 wt% toluene solution), the amount of the main catalyst is set to 20 μmol, and according to the set amount, [ Al ]: adding a certain amount of MAO into the mixture with the molar ratio of [ Ti ] - [ 500 ], adding the main catalyst, and stirring for reaction. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 1.0MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
Example 18
The polymerization was carried out in a 500mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The temperature of the reactor was then adjusted to 80 ℃ by circulation of jacket cooling water, and 200mL of methylcyclohexane was added as the reaction medium. The main catalyst and the cocatalyst used were the same as in example 17.
The amount of the main catalyst used was set to 20. mu. mol, and according to the set amount, [ Al ]: adding a certain amount of MAO into the mixture with the molar ratio of [ Ti ] - [ 500 ], adding the main catalyst, and stirring for reaction. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and ensuring that the reaction pressure is 1.0MPa and the polymerization reaction time is 60 min.
After the reaction is finished, 1mL of acidified ethanol is added to terminate the reaction, 2-5 wt% of activated clay is added to the obtained product to adsorb and remove catalyst residues, then pressure filtration is carried out to obtain filtrate, the filtrate is subjected to reduced pressure distillation to remove the solvent and unreacted monomers to obtain the polyolefin synthetic oil, and the polymerization result is shown in Table 1.
TABLE 1 summary of the results of the examples
Figure BDA0002892426160000131
As can be seen from the above examples and comparative examples, the preparation method of the polyolefin synthetic oil provided by the invention can prepare a series of medium and high viscosity polyolefin synthetic oil base oil products (mAPO, Metallocene Apalene-Poly-Olefins), and the key indexes of the products are close to those of the PAO products with similar viscosity grades of Mofu, and the performances are excellent.

Claims (10)

1. A method of preparing a polyolefin synthetic oil comprising: premixing a cocatalyst and a main catalyst or respectively adding the cocatalyst and the main catalyst into a polymerization reactor containing a reaction medium, introducing low-carbon olefin as a main polymerization monomer, controlling the reaction temperature below 100 ℃ and the reaction pressure below 1MPa, and preparing the medium-high viscosity polyolefin synthetic oil by homopolymerization of the low-carbon olefin or copolymerization of the low-carbon olefin and alpha-olefin prepared by an ethylene oligomerization method or alpha-olefin prepared by a Fischer-Tropsch method; alpha-olefin or crude product thereof in the Fischer-Tropsch alpha-olefin, wherein the content of the alpha-olefin is 10-90 percent; the raw material conditions enable the preparation method to fully utilize raw material resources and obviously reduce the production cost;
the procatalyst is selected from the group consisting of metallocene CGC catalysts having a defined geometry and having the general structural formula:
Figure FDA0002892426150000011
wherein the content of the first and second substances,
i) l is N, O, P, S heteroatom coordinating group to replace one Cp ring in the traditional double Cp metal catalyst, L is connected with another Cp by a bridging group E, E is C, Si, Ge or Sn, n is an integer more than or equal to 1;
ii)R1and R2Same or different, each independently selected from hydrogen, saturated or unsaturated C1To C20Hydrocarbyl, saturated or unsaturated C1To C20Halogenated hydrocarbon groups, saturated or unsaturated C1To C20Hydrocarbyloxy, saturated or unsaturated C3To C20Cycloalkyl radical, C6To C20Aryl radicals or C6To C20A heterocyclic aromatic hydrocarbon group; r1、R2Can also be reacted with EnTogether form a benzene ring, a heterocycle or other aromatic ring;
iii)R3selected from hydrogen, saturated or unsaturated C1To C20Hydrocarbyl, saturated or unsaturated C1To C20Halogenated hydrocarbon groups, saturated or unsaturated C1To C20Hydrocarbyloxy, saturated or unsaturated C3To C20Cycloalkyl radical, C6To C20Aryl radicals or C6To C20A heterocyclic aromatic hydrocarbon group;
iv)R4、R5、R6and R7The same or different, each independently selected from hydrogen, halogen, saturated or unsaturated C1To C10Hydrocarbyl, saturated or unsaturated C1To C10Halogenated hydrocarbon groups, saturated or unsaturated C1To C10Hydrocarbyloxy, saturated or unsaturated C3To C10Cycloalkyl radical, C6To C10Aryl radicals or C6To C10A heterocyclic aromatic hydrocarbon group;
v) or, R4And R5、R5And R6Or R6And R7Can be combined with carbon atoms connected with Cp to form a novel cyclopentadienyl ring, a benzene ring, a heterocyclic ring or the likeA complex aromatic ring of He;
vi) M is Ti, Zr or Hf;
viii)X1and X2The same or different, each independently selected from hydrogen, halogen, saturated or unsaturated C1To C20A hydrocarbyl group.
2. The process of claim 1 wherein said polymerized monomeric lower olefin is selected from the group consisting of ethylene, propylene, and butene-1; the polyolefin synthetic oil can be prepared by homopolymerization of low-carbon olefin or copolymerization of the low-carbon olefin and alpha-olefin prepared by an ethylene oligomerization method or alpha-olefin prepared by a Fischer-Tropsch method; the Fischer-Tropsch alpha-olefin is alpha-olefin or crude product thereof converted from coal or natural gas through Fischer-Tropsch synthesis, wherein the content of the alpha-olefin is 10-90%, and the content of oxygen-containing compounds is not more than 5%.
3. The process of claim 1 wherein the cocatalyst is an organoaluminum compound, an organoboron compound, or a combination of both.
4. The process of claim 3, wherein the organoaluminum compound is selected from one or more of the following groups: one or more of alkylaluminum, alkylaluminum halide, alkylaluminum alkoxide, alkylaluminoxane or modified alkylaluminoxane, and specifically can be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, aluminum isopropoxide, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and modified methylaluminoxane and derivatives thereof.
5. A process as claimed in claim 3, wherein the organoboron compound is selected from one or more of the group consisting of: boroxine, triethylborane, triphenylborane ammonia complex, NaBH4Tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityltetrakis (pentafluorophenyl) borate, tris (p-n-octylphenyl) methyltetrakis (pentafluorophenyl) borate, dimethylbenzeneAminotetrakispentafluorophenyl borate, diethylphenylammoniumtetrakis (pentafluorophenyl) borate, methyldiphenylammoniumtetrakis (pentafluorophenyl) borate, ethyldiphenylammoniumtetrakis (pentafluorophenyl) borate, methyldioctadecylammoniumtetrakis (pentafluorophenyl) borate, trioctylammonium tetrakis (pentafluorophenyl) borate.
6. The process of claim 3 wherein the cocatalyst is selected from the group consisting of combinations of organoaluminum compounds and organic borides, wherein the organoaluminum compounds are alkylaluminoxanes, modified alkylaluminoxanes or alkylaluminums.
7. The process according to claim 3, wherein the concentration of the main catalyst in the polymerization system is 1X 10 based on the central metal-7～1×10-3mol/L; the molar ratio of aluminum in the organic aluminum compound to metal in the main catalyst is 20-5000: 1; the molar ratio of boron in the organic boride to metal contained in the main catalyst is 1-5: 1.
8. The process of claim 1, wherein the polymerization reactor is selected from one or more of the group consisting of: microchannel reactors, tubular reactors, tank reactors, tower reactors, packed reactors, bubble reactors, falling film reactors, hypergravity reactors, applied sound field reactors, applied electric field reactors and applied magnetic field reactors, and the polymerization reactors may be multiple reactors combined in series and/or in parallel.
9. The method of claim 1, wherein the reaction medium is selected from one or more of the group consisting of: aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, cycloaliphatic hydrocarbons or olefins.
10. The process according to claim 1, wherein the polymerization temperature is from 0 to 100 ℃, preferably from 30 to 100 ℃; the reaction pressure is 0.05-1 MPa, preferably 0.1-1 MPa; and carrying out quenching and purification treatment on the polymerization product to obtain the polyolefin synthetic oil.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN108752509A (en) * 2018-06-08 2018-11-06 北京化工大学 Metallocene catalyst and preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752509A (en) * 2018-06-08 2018-11-06 北京化工大学 Metallocene catalyst and preparation method and application

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Title
艾则孜▪麦麦提明: "制备全系列聚烯烃材料的高性能单活性中心催化剂研究进展", 《化工进展》 *
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