CN118047893A - A method for preparing polyolefin elastomer - Google Patents

Abstract

The present invention belongs to the field of chemical industry, and more particularly to a method for preparing a polyolefin elastomer, comprising the following steps: under anhydrous and oxygen-free conditions, ethylene ethane mixed gas, α-olefin comonomer, catalyst and organic solvent are mixed in a reactor to carry out polymerization reaction to obtain a polyolefin elastomer; the temperature of the polymerization reaction is higher than the supercritical temperature of ethane, and lower than the supercritical temperature of the organic solvent; the pressure of the polymerization reaction is higher than the supercritical pressure of the ethane. The preparation method provided by the present invention mixes ethane gas in ethylene gas, and after the mixed gas enters the reactor, the ethane gas does not participate in the reaction, and it is mixed with the organic solvent to form a new mixed solvent, and a supercritical fluid is formed under specific temperature and pressure conditions; under the supercritical fluid state, the viscosity of the polymerization system is reduced, the monomer diffusion rate is increased, the comonomer insertion rate in the polymer segment is increased, and the production efficiency of the polyolefin elastomer is significantly improved.

Description

A method for preparing polyolefin elastomer

Technical Field

The invention belongs to the field of chemical industry, and in particular relates to a method for preparing a polyolefin elastomer.

Background technique

Polyolefin elastomer (POE) is a random copolymer of ethylene/linear α-olefin with a high comonomer content developed by Dow and ExxonMobil in the early 1990s. The industrial production of ethylene/α-olefin copolymers includes gas phase method, slurry method and solution method. Compared with the first two methods, the solution method has the advantages of small polymerization reactor volume, short polymerization time, convenient product brand switching, high ethylene single-pass conversion rate, precise product molecular weight control, and uniform copolymer composition distribution. Therefore, the solution polymerization process is widely used in the production of vinyl polymers, including ethylene/α-olefin copolymers, ethylene-propylene rubber (EPR, EPDM), ethylene/styrene copolymers, ethylene/vinyl acetate copolymers (EVA), etc. Polyolefin elastomer materials have excellent weather resistance, anti-PID effect, and are not easy to yellow. It is an emerging type of photovoltaic encapsulation material.

However, the preparation of polyolefin elastomers by solution polymerization also has some disadvantages. For example, as the concentration of the polymer product increases in the solution polymerization process, the solution viscosity increases, the mass transfer and heat transfer resistance increases, and the production efficiency decreases.

Summary of the invention

In view of this, an object of the present invention is to provide a method for preparing a polyolefin elastomer, which has high production efficiency of the polyolefin elastomer.

The present invention provides a method for preparing a polyolefin elastomer, characterized in that it comprises the following steps:

Under anhydrous and oxygen-free conditions, ethylene-ethane mixed gas, α-olefin comonomer, catalyst and organic solvent are mixed in a reactor to undergo polymerization reaction to obtain a polyolefin elastomer;

The temperature of the polymerization reaction is higher than the supercritical temperature of ethane and lower than the supercritical temperature of the organic solvent; the pressure of the polymerization reaction is higher than the supercritical pressure of ethane; during the polymerization reaction, the polymerization system is in a homogeneous solution state in the reactor.

Preferably, the proportion of ethane in the ethylene-ethane mixed gas is 1 to 50 vol%.

Preferably, the proportion of ethane in the ethylene-ethane mixed gas is 5 to 20 vol%.

Preferably, the α-olefin comonomer is one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Preferably, the molar ratio of ethylene in the ethylene-ethane mixed gas to the α-olefin comonomer is 1:(0.1-10).

Preferably, the catalyst comprises a main catalyst and a co-catalyst;

The main catalyst is dimethylsilyl bridge group-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride and/or dimethylsilyl bridge group-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium;

The cocatalyst is triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenyl boron, triphenylcarbon One or more of tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N,N-dihexadecylanilinium tetrakis(pentafluorophenyl)borate;

The molar ratio of the main catalyst to the co-catalyst is 1:(1.5-10000).

Preferably, the organic solvent is one or more of n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene and xylene.

Preferably, the polymerization reaction temperature is 65-250°C.

Preferably, the polymerization reaction pressure is 1 to 15 MPa.

Preferably, the polymerization reaction is carried out in a continuous polymerization manner.

Compared with the prior art, the present invention provides a method for preparing a polyolefin elastomer, comprising the following steps: under anhydrous and oxygen-free conditions, ethylene-ethane mixed gas, α-olefin comonomer, catalyst and organic solvent are mixed in a reactor for polymerization reaction to obtain a polyolefin elastomer; the temperature of the polymerization reaction is higher than the supercritical temperature of ethane and lower than the supercritical temperature of the organic solvent; the pressure of the polymerization reaction is higher than the supercritical pressure of ethane; during the polymerization reaction, the polymerization system is in a homogeneous solution state in the reactor. The preparation method provided by the present invention mixes ethane gas into ethylene gas, and after the mixed gas enters the reactor, the ethane gas does not participate in the reaction, and the ethane gas is mixed with the organic solvent to form a new mixed solvent, and a supercritical fluid is formed under specific temperature and pressure conditions; in the supercritical fluid state, the viscosity of the polymerization system is reduced, the monomer diffusion rate is increased, the comonomer insertion rate in the polymer segment is increased, and the production efficiency of the polyolefin elastomer is significantly improved.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

FIG. 1 is a flow chart of a system for preparing a polyolefin elastomer provided in an embodiment of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

The present invention provides a method for preparing a polyolefin elastomer, comprising the following steps:

Under anhydrous and oxygen-free conditions, ethylene-ethane mixed gas, α-olefin comonomer, catalyst and organic solvent are mixed in a reactor to undergo polymerization reaction to obtain a polyolefin elastomer;

The temperature of the polymerization reaction is higher than the supercritical temperature of ethane and lower than the supercritical temperature of the organic solvent; the pressure of the polymerization reaction is higher than the supercritical pressure of ethane; during the polymerization reaction, the polymerization system (i.e., a mixed system consisting of ethylene-ethane mixed gas, α-olefin comonomer, catalyst, organic solvent and polymerization product) is in a homogeneous solution state in the reactor.

In the preparation method provided by the present invention, the proportion of ethane in the ethylene-ethane mixture is preferably 1-50 vol%, more preferably 5-20 vol%, specifically 1 vol%, 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol% or 50 vol%.

In the preparation method provided by the present invention, the α-olefin comonomer is preferably one or more of straight-chain and branched α-olefins of 3 to 20 carbon atoms, and more preferably one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the preparation method provided by the present invention, the catalyst preferably includes a main catalyst and a co-catalyst; wherein the main catalyst is preferably a restricted geometry catalyst with a single active center, more preferably dimethylsilyl bridge-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride and/or dimethylsilyl bridge-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium; the co-catalyst is preferably triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), perfluorophenylboron, triphenylcarbon One or more of tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate and N,N-di(hexadecyl)aniline tetrakis(pentafluorophenyl)borate; the molar ratio of the main catalyst to the co-catalyst is preferably 1:(1.5-10000), more preferably 1:(50-500), specifically 1:50, 1:80, 1:100, 1:120, 1:150, 1:180, 1:200, 1:230, 1:250, 1:270, 1:300, 1:350, 1:400, 1:450 or 1:500.

In the preparation method provided by the present invention, the organic solvent is preferably one or more of straight-chain alkanes with 6 to 10 carbon atoms, isoalkanes with 6 to 10 carbon atoms, cycloalkanes with 6 to 10 carbon atoms and aromatic alkanes with 6 to 10 carbon atoms, and more preferably one or more of n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoalkane oil (Ispoar), toluene and xylene.

In the preparation method provided by the present invention, the molar ratio of ethylene in the ethylene ethane mixture to the α-olefin comonomer is preferably 1:(0.1-10), specifically 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.5, 1:1.7, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

In the preparation method provided by the present invention, the concentration of the ethylene ethane mixture in the polymerization system is preferably 0.1-20 mol/L, specifically 0.1 mol/L, 0.5 mol/L, 1 mol/L, 1.5 mol/L, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L, 5 mol/L, 6 mol/L, 7 mol/L, 8 mol/L, 9 mol/L, 10 mol/L, 12 mol/L, 15 mol/L, 17 mol/L or 20 mol/L.

In the preparation method provided by the present invention, the concentration of the main catalyst in the catalyst in the polymerization system is preferably 0.1-20 μmol/L, specifically 0.1 μmol/L, 0.5 μmol/L, 0.7 μmol/L, 1 μmol/L, 1.2 μmol/L, 1.5 μmol/L, 2 μmol/L, 2.5 μmol/L, 3 μmol/L, 4 μmol/L, 5 μmol/L, 6 μmol/L, 7 μmol/L, 8 μmol/L, 9 μmol/L, 10 μmol/L, 12 μmol/L, 15 μmol/L, 17 μmol/L or 20 μmol/L.

In the preparation method provided by the present invention, the temperature of the polymerization reaction is preferably 65-250°C, more preferably 80-150°C, and even more preferably 120-150°C, and specifically can be 65°C, 70°C, 75°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 170°C, 200°C, 230°C or 250°C.

In the preparation method provided by the present invention, the pressure of the polymerization reaction is preferably 1-15 MPa, more preferably 4-12 MPa, specifically 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa or 15 MPa.

In the preparation method provided by the present invention, the polymerization reaction time is preferably 2 to 120 min, specifically 2 min, 3 min, 5 min, 7 min, 10 min, 12 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min.

In the preparation method provided by the present invention, the reactor is preferably a reactor with a stirring function; the polymerization reaction mode is preferably continuous polymerization, that is, the reactor is continuously fed and discharged during the polymerization reaction. In the present invention, when the polyolefin elastomer is prepared by continuous polymerization, the concentration of the ethylene-ethane mixed gas in the polymerization system described above is the feed concentration of the ethylene-ethane mixed gas in the continuous polymerization process; the polymerization reaction time described above is the residence time of all feeds in the reactor during the continuous polymerization process.

In the preparation method provided by the present invention, when continuous polymerization is used to prepare polyolefin elastomer, the preparation system preferably includes: a raw material refining unit, a gas phase feeding unit, a catalyst configuration unit, a raw material pretreatment unit, a polymerization reaction unit and a post-treatment unit.

In the above-mentioned preparation system provided by the present invention, the raw material refining unit preferably includes a solvent, a storage tank for α-olefins, a diaphragm pump, a refining column, etc.; the refining column preferably includes any one or more of a dehydration tower, a deoxygenation tower, a carbon monoxide removal tower, and a decarbonylation tower. In the present invention, the function of the raw material refining unit is to remove impurities such as water and oxygen in the raw material.

In the above-mentioned preparation system provided by the present invention, the gas phase feeding unit preferably includes gas storage cylinders, pressure reducing valves, refining columns, etc. for ethylene and hydrogen; the refining column preferably includes any one or more of a dehydration tower, a deoxygenation tower, a carbon monoxide removal tower, and a carbon dioxide removal tower. In the present invention, the function of the gas phase feeding unit is to reduce the pressure of ethylene and hydrogen to the use pressure and remove impurities therein by refining.

In the above-mentioned preparation system provided by the present invention, the catalyst preparation unit preferably includes a glove box, a storage tank, an electronic advection pump, etc. for catalysts, additives, antioxidants, and fire extinguishing agents. In the present invention, the catalyst preparation unit is used to prepare catalyst, additives, antioxidants, and fire extinguishing agent solutions, and pressurize them into the next unit through an electronic advection pump.

In the above-mentioned preparation system provided by the present invention, the raw material pretreatment unit preferably includes a mixing kettle and its accessories, and flow meters for each raw material. In the present invention, the raw material pretreatment unit functions to accurately measure the flow of solvent, α-olefin, ethylene, and auxiliary agent added to the mixing kettle, and mix them uniformly in the mixing kettle, while using the auxiliary agent to further remove impurities.

In the above-mentioned preparation system provided by the present invention, the polymerization reaction unit preferably includes two reactors and their accessories, and the polymerization reaction unit is used to perform a polymerization reaction, and the materials uniformly mixed by the mixing kettle enter the reactor, and the catalyst solution is added to the reactor to initiate the reaction. In the present invention, the two reactors can be used separately or in series.

In the above-mentioned preparation system provided by the present invention, the post-processing unit preferably includes a flash kettle, a condenser, a gas-liquid separation tank, a gear pump and other equipment. In the present invention, the post-processing unit functions to remove volatile components such as solvents and unreacted α-olefins in the reaction product.

In the preparation method provided by the present invention, in the process of preparing polyolefin elastomer by the above system, the ratio of the feed flow rate of the organic solvent to the volume of the reactor is preferably (0.5-2) kg/h:1L, more preferably 1 kg/h:1L; the ratio of the feed flow rate of the α-olefin comonomer to the volume of the reactor is preferably (0.4-0.6) kg/h:1L, more preferably (0.54-0.6) kg/h:1L; the ratio of the feed flow rate of the ethylene ethane mixed gas to the volume of the reactor is preferably (0.4-0.6) kg/h:1L, more preferably (0.5-0.55) kg/h:1L; the cocatalyst is fed into the reactor in the form of a cocatalyst solution, and the cocatalyst The volume ratio of the co-catalyst to the solvent in the co-catalyst solution is preferably 50:(900-1000), more preferably 50:950, and the ratio of the feed flow rate of the co-catalyst solution to the volume of the reactor is preferably (1-5) g/min:1L, more preferably 2.5 g/min:1L; the main catalyst is preferably fed into the reactor in the form of a main catalyst solution, and the dosage ratio of the main catalyst to the solvent in the main catalyst solution is preferably (0.1-1) g:800mL, more preferably 0.5 g:800mL, and the ratio of the feed flow rate of the co-catalyst solution to the volume of the reactor is preferably (0.5-2) mL/min:1L, more preferably (0.8-1) mL/min:1L.

The preparation method provided by the present invention mixes ethane gas into ethylene gas. After the mixed gas enters the reactor, the ethane gas does not participate in the reaction, and is mixed with an organic solvent to form a new mixed solvent, and forms a supercritical fluid under specific temperature and pressure conditions. In the supercritical fluid state, the viscosity of the polymerization system is reduced, the monomer diffusion rate is increased, the comonomer insertion rate in the polymer chain segment is increased, and the production efficiency of the polyolefin elastomer is significantly improved.

For the purpose of greater clarity, the invention is described in detail through the following examples.

Example 1

In the system shown in FIG1 , continuous copolymerization is carried out to prepare polyolefin elastomer, and the single reactor volume of the reactor in the system is 1L.

In this embodiment, the main catalyst is dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, the co-catalyst is modified methylaluminoxane, the organic solvent is n-hexane, and the co-monomer is 1-butene; n-hexane and 1-butene are refined in advance, and the ethylene gas enters the subsequent device after refining; the main catalyst and n-hexane are prepared into a solution for use, and the co-catalyst is diluted with n-hexane; before starting the preparation, the pipeline, mixing kettle and reactor are replaced with nitrogen three times, and then the reactor is repeatedly vacuumed and nitrogen-filled at 140°C for 6 hours, and then vacuumed and ethylene-filled twice, the kettle is filled with normal pressure ethylene atmosphere, and the entire pipeline and reactor are sealed and anhydrous and oxygen-free.

The preparation process includes: the reactor is used alone (i.e., only one reactor is operated), connected in series with the mixing reactor, the flow of n-hexane into the mixing reactor is opened, the n-hexane pump is started, and the flow rate of n-hexane is controlled to 1kg/h to supplement n-hexane; when the reactor is full of n-hexane, the pressure of the reactor is set to 4MPa and automatically controlled; the flow of 1-butene into the mixing reactor is opened, the 1-butene pump is started, and the flow rate of 1-butene is controlled to 0.6kg/h to supplement 1-butene; the flow of ethylene into the mixing reactor is opened, and the flow rate of ethylene is controlled to 0.5kg/h to supplement the mixed gas; the flow of the co-catalyst into the mixing reactor is opened, the co-catalyst pump is started, and the flow rate of the co-catalyst is controlled to 2.5g /min auxiliary catalyst; start the oil bath heating of the reactor and set the temperature to 140℃; after the system has been running for 2h, the mixture of each component is stable, start to add the main catalyst, open the process from the main catalyst to the reactor, start the main catalyst pump, and control the main catalyst flow rate at 1mL/min; the temperature in the reactor will rise after the reaction starts, and the reaction temperature is controlled to be stable at 140℃ by changing the oil bath temperature; during the reaction, the polymerization system is maintained in a homogeneous solution state in the reactor; sampling is carried out after the system has reacted stably for 8h, and the sampling time is 15min each time. The samples are filtered, washed with ethanol several times, and then vacuum dried at 60℃ for more than 8 hours.

In this embodiment, the preparation ratio of the main catalyst in the kettle is 0.5g main catalyst + 800mL n-hexane, the preparation ratio of the co-catalyst is 50mL MMAO-7 + 950mL n-hexane, the molar concentration ratio of the co-catalyst to the main catalyst is 180:1; the feed mass ratio of 1-butene to ethylene is 1.2:1; all materials used in this experiment are treated with dehydration and deoxygenation.

The experiment was repeated once, and the experimental results are listed in Table 1 (samples 1-1, 1-2).

Example 2

Referring to Example 1, the difference is that a mixed gas of 5 vol% ethane + 95 vol% ethylene is used instead of the ethylene gas in Example 1, and the main catalyst flow rate is changed to 0.8 mL/min. A repeated experiment is conducted, and the experimental results are listed in Table 1 (samples 2-1, 2-2).

Example 3

Referring to Example 1, the difference is that the flow rate of 1-butene is changed to 0.54 kg/h, a mixed gas of 5 vol% ethane + 95 vol% ethylene is used instead of the ethylene gas in Example 1, and the mixed gas flow rate is set to 0.55 kg/h, and the main catalyst flow rate is changed to 0.8 mL/min. A repeated experiment is conducted, and the experimental results are listed in Table 1 (samples 3-1, 3-2).

Example 4

Referring to Example 2, the difference is that the ratio of ethane to ethylene in the mixed gas is adjusted to 10 vol% ethane + 90 vol% ethylene. A repeated experiment was conducted, and the experimental results are listed in Table 1 (samples 4-1, 4-2).

Example 5

Referring to Example 3, the difference is that the ratio of ethane to ethylene in the mixed gas is adjusted to 10 vol% ethane + 90 vol% ethylene. A repeated experiment was conducted, and the experimental results are listed in Table 1 (samples 5-1, 5-2).

Example 6

Referring to Example 2, the difference is that the ratio of ethane to ethylene in the mixed gas is adjusted to 20 vol% ethane + 80 vol% ethylene. A repeated experiment was conducted, and the experimental results are listed in Table 1 (samples 6-1, 6-2).

Example 7

Referring to Example 3, the difference is that the ratio of ethane to ethylene in the mixed gas is adjusted to 20 vol% ethane + 80 vol% ethylene. A repeated experiment was conducted, and the experimental results are listed in Table 1 (samples 7-1, 7-2).

Table 1 Experimental results of continuous polymerization to prepare polyolefin elastomers

As can be seen from Table 1, under the condition of similar output, that is, under the condition of similar concentration of copolymerization product in the reaction system, with the increase of ethane ratio, the stirring torque gradually decreases, indicating that the viscosity of the polymerization system can be reduced in the supercritical state of the mixed solvent composed of ethane and n-hexane. The activity of the catalysts of Examples 2 to 7 is higher than that of the catalyst of the control group Example 1, indicating that polymerization in the supercritical state of ethane can improve production efficiency.

The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims (10)

1. A process for the preparation of a polyolefin elastomer comprising the steps of:

Under the anhydrous and anaerobic condition, ethylene-ethane mixed gas, alpha-olefin comonomer, catalyst and organic solvent are mixed in a reaction kettle to carry out polymerization reaction, thus obtaining polyolefin elastomer;

The temperature of the polymerization reaction is higher than the supercritical temperature of ethane and lower than the supercritical temperature of the organic solvent; the pressure of the polymerization reaction is higher than the supercritical pressure of the ethane; in the polymerization reaction process, the polymerization system is in a homogeneous solution state in the reaction kettle.

2. The method according to claim 1, wherein the ratio of ethane in the ethylene-ethane mixture is 1 to 50vol%.

3. The method according to claim 2, wherein the ratio of ethane in the ethylene-ethane mixture is 5 to 20vol%.

4. The method of claim 1, wherein the alpha-olefin comonomer is one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

5. The method according to claim 1, wherein the molar ratio of ethylene to the alpha-olefin comonomer in the ethylene-ethane mixture is 1 (0.1 to 10).

6. The method of preparation of claim 1, wherein the catalyst comprises a procatalyst and a cocatalyst;

The main catalyst is dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-titanium dichloride and/or dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-dimethyl titanium;

the cocatalyst is triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenylboron and triphenylcarbon One or more of tetrakis (pentafluorophenyl) boron salt, N-dimethylanilinium tetrakis (pentafluorophenyl) boron salt, and N, N-di (hexadecyl) anilinium tetrakis (pentafluorophenyl) boron salt;

The mol ratio of the main catalyst to the cocatalyst is 1 (1.5-10000).

7. The method according to claim 1, wherein the organic solvent is one or more of n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, and xylene.

8. The process according to claim 1, wherein the polymerization reaction temperature is 65 to 250 ℃.

9. The process according to claim 1, wherein the polymerization is carried out at a pressure of 1 to 15MPa.

10. The process according to any one of claims 1 to 9, wherein the polymerization is carried out continuously.