CN108359035B

CN108359035B - Copolymerization method of ethylene and terminal alkenyl silane/siloxane

Info

Publication number: CN108359035B
Application number: CN201710057275.2A
Authority: CN
Inventors: 高榕; 周俊领; 李岩; 刘东兵; 赖菁菁; 傅捷
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-01-26
Filing date: 2017-01-26
Publication date: 2020-07-24
Anticipated expiration: 2037-01-26
Also published as: CN108359035A

Abstract

The invention belongs to the field of olefin copolymerization reaction, and provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene and terminal alkenyl silane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and an optional chain transfer agent, and the main catalyst is selected from at least one of complexes shown as a formula (I), wherein R is¹～R¹⁰Each independently selected from hydrogen, saturated or unsaturated hydrocarbyl, hydrocarbyloxy, and the like; m is selected from group VIII metals and X is a halogen. The catalyst composition adopted by the method has higher polymerization activity in the copolymerization reaction of ethylene and terminal alkenyl silane/siloxane, can improve the content of comonomer and methyl on a polymer molecular chain, and has wide industrial application prospect.

Description

Copolymerization method of ethylene and terminal alkenyl silane/siloxane

Technical Field

The invention belongs to the field of olefin copolymerization, and particularly relates to a copolymerization method of ethylene and terminal alkenyl silane/siloxane.

Background

The olefin copolymers containing vinylsilane or siloxane derivative groups can be used in a variety of applications, for example as various types of cable materials, pipes, adhesives, gaskets and crosslinked foams. Vinyl silane-based groups can be linked to olefin polymers by two methods: one method is to copolymerize olefins and vinylsilanes at high temperature and high pressure under the catalysis of a free radical initiator (e.g., US 3225018), the polymerization process is similar to the high-pressure homopolymerization of ethylene, and the structure of the obtained copolymer is similar to that of low-density polyethylene; another method is to graft an allyl-or vinyl-silane onto an existing polyolefin (e.g.US 3646155), which has the advantage that both low density polyethylene and high density polyethylene can be grafted on, but has the disadvantage that the grafting requires the additional use of free-radical initiators, which also complicates the preparation process. In addition, too little free radical initiator can result in too low a graft; too much free radical initiator may result in excessive crosslinking of the polymer. If the catalyst can catalyze the coordination polymerization of ethylene and the terminal alkenylsilane/siloxane groups, the polymerization process can be simplified, and the content of the terminal alkenylsilane/siloxane groups on a polymer chain can be controlled.

Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins with silicon-containing polar monomers (terminal alkenylsilanes/siloxanes). For example, WO 03/044066A 2 discloses that ethylene and allyl-or vinyl-silane can be copolymerized by using a late transition metal complex of a bidentate or tridentate ligand, however, the method needs to use expensive Modified Methylaluminoxane (MMAO) as a cocatalyst, and the polymerization is carried out under the higher ethylene polymerization pressure of 4.0-6.0 MPa, and the obtained polymer has low molecular weight and branching degree. Dalton reaction, 2015, 44(47):20745-20752 adopts pyridine diimine iron catalyst to catalyze the copolymerization of propylene and polar monomer containing silicon, the method still needs MMAO as cocatalyst, needs 30 ℃ or even lower temperature and 0 ℃ for polymerization reaction for 16 hours, has lower polymerization activity, and cannot carry out copolymerization reaction at higher temperature.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a copolymerization method of ethylene and terminal alkenylsilane/siloxane, wherein a catalyst system in the method has higher polymerization activity, the molecular weight distribution of the obtained polymer is narrow, and the molecular weight and the branching degree of the polymer can be regulated and controlled in a wider range.

The invention provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene and terminated alkenyl silane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and an optional chain transfer agent, and the main catalyst is selected from at least one of complexes shown in a formula (I):

in the formula (I), R¹～R¹⁰The same or different, each independently selected from hydrogen, saturated or unsaturated alkyl, alkoxy or halogen; m is selected from group VIII metals and X is a halogen.

Compared with the conventional post-transition metal complex catalytic system adopting a bidentate or tridentate ligand, the catalyst composition adopted by the method has higher polymerization activity in the coordination copolymerization reaction of ethylene and terminal alkenyl silane/siloxane, can improve the content of a comonomer on a polymer molecular chain, can regulate and control the molecular weight and the branching degree of the polymer, and has wide industrial application prospect.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene with a terminal alkenylsilane/siloxane (comonomer) in the presence of a catalyst composition, wherein the catalyst composition comprises a procatalyst, a cocatalyst and optionally a chain transfer agent.

The procatalyst (i.e., single site catalyst) is selected from at least one of the complexes of formula (I):

The halogen is F, Br, Cl or I.

Preferably, R¹～R¹⁰Each independently selected from hydrogen and C₁～C₁₀A saturated or unsaturated hydrocarbon group of C₁～C₁₀Alkoxy or halogen of (a).

C₁～C₁₀The saturated or unsaturated hydrocarbon group of (1) specifically includes C₁～C₁₀Alkyl radical, C₃～C₁₀Cycloalkyl radical, C₂～C₁₀Alkenyl radical, C₂～C₁₀Alkynyl, C₆～C₁₀Aryl radical, C₇～C₁₀Aralkyl groups, and the like.

C₁～C₁₀Alkyl is C₁～C₁₀Straight chain alkyl or C₃～C₁₀Non-limiting examples of branched alkyl groups of (a) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.

C₃～C₁₀Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

C₆～C₁₀Examples of aryl groups may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.

C₂～C₁₀Examples of alkenyl groups may include, but are not limited to: vinyl and allyl.

C₂～C₁₀Examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.

C₇～C₁₀Examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.

C₁～C₁₀Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, and the like.

More preferably, R¹～R¹⁰Each independently selected from hydrogen and C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a).

In the formula (I), M may be, for example, nickel, iron, cobalt, palladium, etc., and preferably nickel.

According to a preferred embodiment of the invention, the procatalyst is selected from at least one of the following complexes,

the complex 1: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝H，X＝Br；

And (2) the complex: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝H，X＝Br；

And (3) complex: r¹＝R³＝R⁴＝R⁶＝iPr，R²＝R⁵＝H，X＝Br；

The complex 4: r¹＝R²＝R³＝R⁴＝R⁵＝R⁶＝Me，X＝Br；

And (3) a complex 5: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Br，X＝Br；

The complex 6: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Et，X＝Br；

The complex 7: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Me，X＝Br；

The complex 8: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Br，X＝Br；

The complex 9: r¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝H，X＝Br；

The complex 10: r¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝H，X＝Br；

The complex 11: r¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝H，X＝Br；

The complex 12: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝H，X＝Cl；

The complex 13: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝H，X＝Cl；

The complex 14: r¹＝R³＝R⁴＝R⁶＝iPr，R²＝R⁵＝H，X＝Cl；

The complex 15: r¹＝R²＝R³＝R⁴＝R⁵＝R⁶＝Me，X＝Cl；

The compound 16: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Br，X＝Cl；

The complex 17: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Et，X＝Cl；

The complex 18: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Me，X＝Cl；

The complex 19: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Br，X＝Cl；

The complex 20: r¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝H，X＝Cl；

The complex 21: r¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝H，X＝Cl；

The complex 22: r¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝H，X＝Cl；

And in the complexes 1-22, R⁷～R¹⁰Are both hydrogen and M is nickel.

In the invention, the complex shown in the formula (I) can be prepared by the following method:

1) refluxing a compound A shown as a formula (I-I) and aniline or substituted aniline in a solvent under the action of a catalyst to prepare a diimine ligand compound shown as a formula (I-II):

2) reacting a diimine ligand compound of formula (I-II) with MX₂Or MX₂Carrying out coordination reaction on the derivative to obtain a complex shown as a formula (I);

wherein, to R¹～R¹⁰And M, X are the same as above and will not be described further herein.

In step 1), the catalyst may be at least one selected from the group consisting of p-toluenesulfonic acid, acetic acid and formic acid. The solvent may be selected from at least one of toluene, methanol, ethanol and acetonitrile. The molar ratio of the compound A to aniline or substituted aniline is 1: 2 to 1: 10, preferably 1: 2 to 1: 3. The reflux temperature is 40-120 ℃, and preferably 65-110 ℃; the refluxing time is 0.5-7 days, preferably 1-2 days. Preferably, the amount of the catalyst is 0.01-20 mol% of the amount of the compound A.

The substituents on said substituted anilines are as defined for R¹～R¹⁰However, R¹～R¹⁰Not both being hydrogen, for example, the substituted aniline may be one or more of 2, 6-methylaniline, 2, 6-diethylaniline, 2, 6-diisopropylaniline, 2, 6-dimethyl-4-bromo-aniline and 2, 6-difluoroaniline.

In step 2), the diimine ligand compound is reacted with MX₂Or MX₂The molar ratio of the derivative (such as nickel halide or nickel halide derivative) may be 1: 1 to 1: 1.2. The nickel halide or nickel halide derivative may be selected from NiBr₂、NiCl₂、(DME)NiBr₂Or (DME) NiCl₂Wherein DME is an abbreviation for dimethyl ether. The temperature of the coordination reaction can be 0-60 ℃, and the reaction time is 0.5-12 h. The coordination reaction is carried out in an anhydrous and oxygen-free atmosphere, for example, under an inert atmosphere (usually nitrogen).

According to a particular embodiment, the synthesis of the complex may comprise the steps of:

a) refluxing compound A and substituted aniline in ethanol with acetic acid as catalyst for 1 day, filtering, removing solvent, dissolving the residue with dichloromethane, passing through alkaline alumina column, eluting with petroleum ether/ethyl acetate (20: 1), collecting the second eluate, and removing solvent to obtain yellow solid; or

b) Refluxing compound A and substituted aniline in toluene with p-toluenesulfonic acid as catalyst for 1 day, evaporating reaction solution to dryness, dissolving residue with dichloromethane, passing through alkaline alumina column, eluting with petroleum ether/ethyl acetate (20: 1), collecting second stream, and removing solvent to obtain yellow solid;

the yellow solid is determined as the diimine ligand compound through nuclear magnetism, infrared and element analysis characterization;

c) under the protection of inert gas, (DME) NiCl₂Or (DME) NiBr₂The dichloromethane solution is added dropwise to the solution of the diimine ligand compound at a molar ratio of 1: 1 to 1: 1.2, and the mixture is stirred at room temperatureAnd separating out a precipitate, filtering, washing with diethyl ether, drying in vacuum, and determining the obtained product as the complex shown in the formula (I) by elemental analysis and infrared characterization.

In addition, the complexes related to the following examples are prepared by using corresponding raw materials according to the synthesis method, and the details are not repeated.

In the present invention, the cocatalyst may be a conventional choice in coordination polymerization of olefins. Preferably, the cocatalyst is selected from at least one of alkylaluminoxane, arylboronium and borate.

The alkylaluminoxane is for example selected from Methylaluminoxane (MAO) and/or Modified Methylaluminoxane (MMAO).

More preferably, the cocatalyst is methylaluminoxane, so that the catalyst composition has higher copolymerization activity and the raw material cost can be reduced.

The aralkyl boron is substituted or unsubstituted phenyl boron, preferably, trifluorophenyl boron.

The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.

In the catalyst composition, the molar ratio of aluminum in the cocatalyst to M (such as nickel) in the main catalyst may be (10-100000): 1, preferably (10-10000): 1, and more preferably (100-5000): 1; or the molar ratio of boron in the cocatalyst to M in the main catalyst can be (0.01-1000): 1, preferably (0.1-100): 1.

According to the invention, the selection and the addition amount of the chain transfer agent can control the molecular weight of the obtained polymer, and the molecular weight of the polymer can be regulated and controlled in a wide range. In the present invention, the type of the chain transfer agent is not particularly limited, and may be selected according to the type of the transition metal M.

According to one embodiment, the chain transfer agent is selected from trialkylaluminums and/or dialkylzinc.

Preferably, the chain transfer agent is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, and diethylzinc.

In this embodiment, the molar ratio of aluminum in the chain transfer agent to M in the main catalyst may be (1 to 10000): 1, preferably (1 to 1000): 1; or the molar ratio of zinc in the chain transfer agent to M in the main catalyst is (1-1000): 1.

The copolymerization process of the present invention can be carried out in the following manner: contacting the catalyst composition with ethylene, a terminal alkenylsilane/siloxane, in the presence of an organic solvent, under anhydrous and oxygen-free conditions. The main catalyst, the cocatalyst and other catalyst components can be added into the reactor respectively, or all the components can be added into the reactor after being mixed in advance, and the adding sequence or the mixing condition is not particularly limited.

The organic solvent may be selected from C₃～C₂₀Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, toluene, xylene, etc. Preferably, the organic solvent is toluene and/or hexane.

In the present invention, "terminal alkenyl" includes vinyl groups, α -alkenyl groups, and the double bond of the group is located at one end of the molecular chain.

Specifically, the terminal alkenylsilane is selected from at least one of compounds shown in a formula (II):

wherein m and n are 0 or positive integers, and are preferably integers of 0-20.

Non-limiting examples of the terminal alkenylsilanes include: vinyltrimethylsilane, vinyltriethylsilane, allyltriethylsilane, allyltri-n-butylsilane, 7-octenyltrimethylsilane, and the like.

The terminal alkenyl siloxane is selected from at least one of the compounds shown in the formula (III):

wherein p and q are each 0 or a positive integer, and each is preferably an integer of 0 to 20.

Non-limiting examples of the terminal alkenylsiloxanes include: vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 7-octenyltrimethoxysilane and the like.

According to the copolymerization method of the invention, the dosage of the terminal alkenyl silane/siloxane is 0.01-3000 mmol/L, preferably 0.1-1000 mmol/L, and more preferably 1-500 mmol/L.

According to the invention, the amount of the main catalyst can be 0.00001-10 mmol/L, preferably 0.0001-1 mmol/L, and more preferably 0.001-0.5 mmol/L.

In the present invention, "mmol/L" means the concentration of the material in the reactor.

According to the invention, the temperature of the copolymerization reaction can be selected within a wide range, for example from-20 ℃ to 200 ℃, preferably from 40 ℃ to 120 ℃, more preferably from 60 ℃ to 110 ℃.

The pressure of the copolymerization reaction in the present invention is not particularly limited as long as the monomer can be subjected to coordination copolymerization. From the viewpoint of cost reduction and simplification of the polymerization process, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50 atm.

The catalyst composition in the method can catalyze the monomer to carry out copolymerization reaction with high activity, so that the reaction can be completed in a short time, and the time of the copolymerization reaction can be 10-120 min, preferably 20-50 min.

In addition, after the time for the copolymerization reaction is reached, the method of the invention further comprises terminating the reaction by using a terminating agent, wherein the terminating agent can be a compound containing active hydrogen, such as water, alcohol, acid, amine and the like which are conventionally selected for coordination polymerization. In one embodiment, the terminator may be a 5-20 vol% acidified methanol or ethanol solution of hydrochloric acid, i.e., alcohol/concentrated hydrochloric acid (95/5-80/20 (vol/vol)).

The complex adopted by the method can be combined with a cocatalyst to realize the copolymerization reaction of ethylene and terminal alkenyl silane/siloxane under lower pressure, and the catalyst composition can still maintain higher catalytic activity even at high temperature (for example, above 90 ℃), namely, comonomer is successfully introduced into a polymer molecular chain; the method can realize the regulation and control of the molecular weight and the branching degree of the polymer, and the molecular weight distribution of the polymer is narrow, so that the method can be used for preparing the copolymer of ethylene and terminal alkenyl silane/siloxane with different physical properties.

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

In the following examples and comparative examples,

analyzing the relative content of Si element in the polymer by adopting X-ray fluorescence spectrum of PANALYTICAL company Axios-Advanced type, wherein the higher the content of Si is, the higher the content of comonomer is;

the methyl content of the polymer was tested using 13C NMR spectroscopy: on a 400MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, a 10mm PASEX 13 probe is utilized, a polymer sample is dissolved by 1,2, 4-trichlorobenzene at 120 ℃ for analysis and test, wherein the higher the methyl content is, the higher the branching degree of the polymer is;

the molecular weight and molecular weight distribution of the polymer, PDI (PDI. Mw/Mn), were determined by P L-GPC 220 using trichlorobenzene as solvent at 150 deg.C (standard: PS, flow rate: 1.0M L/min, column: 3 × Plgel 10um M1 × ED-B300 × 7.5.5 nm).

Example 1

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.

Example 2

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 100 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.

Example 3

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 10m L of allyltrimethoxysilane (57.4mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.

Example 4

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.2m L of diethylzinc (1 mol/L in hexane), Zn/Ni 20, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 5

A1L stainless steel polymerizer equipped with mechanical agitation was continuously operated at 130 ℃Drying for 6hrs, vacuum-pumping while hot and applying N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 6

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.3mg (10. mu. mol) of complex 2, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 7

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.3mg (10. mu. mol) of complex 2, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 8

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Pneumatic deviceChanging 3 times, adding 10.7mg (10. mu. mol) of complex 1, then evacuating and replacing 3 times with ethylene, injecting 500m L of toluene, adding 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), making Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintaining 10atm of ethylene pressure at 70 ℃, stirring for 30min, finally neutralizing with 5 vol% of hydrochloric acid acidified ethanol solution, obtaining the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 9

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 12.8mg (10. mu. mol) of complex 8, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 10

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.0mg (10. mu. mol) of complex 14, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 11

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Air-substituted 3 times, 11.9mg (10. mu. mol) of complex 3 are added, which is then again evacuated and substituted 3 times with ethylene, 500m L of toluene are injected and 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene) are added to the solution and Al is/is presentNi 1000, 5m L7-octenyltrimethoxysilane (17.8mmol), ethylene pressure of 10atm was maintained at 70 ℃, and the reaction was stirred for 30 min.

Example 12

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.2m L of diethylzinc (1 mol/L in hexane), Zn/Ni 20, 5m L7-octenyltrimethoxysilane (17.8mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 13

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L7-octenyltrimethoxysilane (17.8mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 14

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂3 times replacement by gas, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and replacement by ethylene 3 times, injection of 500m of toluene L and addition of 6.5m of L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to convert Al/Ni to 1000, 5m of L vinyltrimethoxysilane(31.6 mmol). The reaction was carried out at 70 ℃ under an ethylene pressure of 10atm with stirring for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 15

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethylsilane (22.1mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and finally neutralization with 5 vol% of acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 16

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), setting Al/Ni to 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), setting Zn/Ni to 50, 5m L of allyltrimethylsilane (22.1mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.

Example 17

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂3 times replacement by gas, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and replacement by ethylene 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), setting Al/Ni to 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 40 ℃ and stirring for 30min, finally acidification with 5% by volume of hydrochloric acid in ethanolAnd neutralizing to obtain the polymer. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 18

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 120 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.

Example 19

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂3 times by gas displacement, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and 3 times by ethylene displacement, injection of 500m of L toluene, addition of 5m of L N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene (2 mmol/L in toluene), Ni/B ═ 1, 5m of L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30min, and finally termination of the reaction with 5% by volume of hydrochloric acid in ethanol, the polymerization activity and the performance parameters of the polymer being shown in Table 1.

Comparative example 1

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂The gas exchange was carried out 3 times, 6.6mg (10. mu. mol) of comparative catalyst A (complex A, structure formula (IV)) was added, followed by evacuation and 3 times replacement with ethylene, 500m L of toluene was injected, 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L of toluene solution) was added to make Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), ethylene pressure of 10atm was maintained at 70 ℃, the reaction was stirred for 30min, and finally neutralized with 5 vol% of ethanol acidified with hydrochloric acid, and only a small amount of polymer was formed, polymerization activity and polymer properties were as shown in Table 1.

Comparative example 2

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂The gas exchange was carried out 3 times, 6.6mg (10. mu. mol) of comparative catalyst A was added, followed by further vacuum evacuation and 3 times replacement with ethylene, 500m L of toluene was injected, 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene) was added to make Al/Ni 1000, 5m L of vinyltrimethoxysilane (28.7mmol), ethylene pressure was maintained at 70 ℃ at 10atm, the reaction was stirred for 30min, and finally neutralized with 5 vol% hydrochloric acid acidified ethanol solution, no polymer was formed.

Comparative example 3

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂Air replacement 3 times, addition of 6.3mg (10. mu. mol) of comparative catalyst B (complex B, structure shown in formula (V)), followed by evacuation and replacement with ethylene 3 times, injection of 500m L toluene, addition of 6.5m L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to make Al/Ni 1000, 5m L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% HCl-acidified ethanol solution, no polymer formation.

Comparative example 4

The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N₂The reaction was carried out by gas displacement 3 times, addition of 6.0mg (10. mu. mol) of comparative catalyst C (complex C, structure formula (VI)), further evacuation and displacement with ethylene 3 times, injection of 500m L toluene, addition of 6.5m L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to make Al/Ni 1000, 5m L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol solution, and no polymer was formed.

TABLE 1

As can be seen from Table 1, the catalyst compositions of the examples have a copolymerization activity of up to 14.30 × 10⁶g·mol^-1(Ni)·h^-1. Compared with the complexes of comparative examples 1 to 4, the complexes adopted in examples 1 to 19 have significantly improved copolymerization activity when used as a main catalyst, the obtained polymer has a molecular weight significantly higher than that of the comparative example, the contents of the comonomer and methyl are also significantly improved, the molecular weight distribution of the polymer is lower than that of the comparative example, and the branching degree and the molecular weight of the polymer can be regulated and controlled in a wider range.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims

1. A method of copolymerizing ethylene with a terminal alkenylsilane/siloxane, the method comprising: copolymerizing ethylene and a terminal alkenylsilane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and optionally a chain transfer agent, wherein the main catalyst is at least one selected from complexes represented by the formula (I):

in the formula (I), R¹～R¹⁰Are the same or different, wherein R²、R⁵And R⁷～R¹⁰Each independently selected from hydrogen, saturated or unsaturated hydrocarbyl, hydrocarbyloxy or halogen; r¹、R³、R⁴And R⁶Each independently selected from saturated or unsaturated hydrocarbyl, hydrocarbyloxy or halogen; m is nickel and X is halogen.

2. The copolymerization process according to claim 1, wherein in the formula (I), R is²、R⁵And R⁷～R¹⁰Each independently selected from hydrogen and C₁～C₁₀A saturated or unsaturated hydrocarbon group of C₁～C₁₀Alkoxy or halogen of (a); r¹、R³、R⁴And R⁶Each independently selected from C₁～C₁₀A saturated or unsaturated hydrocarbon group of C₁～C₁₀Alkoxy or halogen of (a).

3. The copolymerization process according to claim 2, wherein R²、R⁵And R⁷～R¹⁰Each independently selected from hydrogen and C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a); r¹、R³、R⁴And R⁶Each independently selected from C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a).

4. The copolymerization process according to claim 1, wherein the procatalyst is selected from at least one of the following complexes,

the complex 1: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝H，X＝Br；

And (2) the complex: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝H，X＝Br；

And (3) complex: r¹＝R³＝R⁴＝R⁶＝iPr，R²＝R⁵＝H，X＝Br；

The complex 4: r¹＝R²＝R³＝R⁴＝R⁵＝R⁶＝Me，X＝Br；

And (3) a complex 5: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Br，X＝Br；

The complex 6: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Et，X＝Br；

The complex 7: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Me，X＝Br；

The complex 8: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Br，X＝Br；

The complex 9: r¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝H，X＝Br；

The complex 10: r¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝H，X＝Br；

The complex 11: r¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝H，X＝Br；

The complex 12: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝H，X＝Cl；

The complex 13: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝H，X＝Cl；

The complex 14: r¹＝R³＝R⁴＝R⁶＝iPr，R²＝R⁵＝H，X＝Cl；

The complex 15: r¹＝R²＝R³＝R⁴＝R⁵＝R⁶＝Me，X＝Cl；

The compound 16: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Br，X＝Cl；

The complex 17: r¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝Et，X＝Cl；

The complex 18: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Me，X＝Cl；

The complex 19: r¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝Br，X＝Cl；

The complex 20: r¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝H，X＝Cl；

The complex 21: r¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝H，X＝Cl；

The complex 22: r¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝H，X＝Cl；

And in the complexes 1-22, R⁷～R¹⁰Are both hydrogen and M is nickel.

5. The copolymerization process of claim 1, wherein the cocatalyst is selected from at least one of alkylaluminoxanes, arylborohydrides and borates.

6. The copolymerization process according to claim 1, wherein the chain transfer agent is selected from trialkylaluminums and/or dialkylzinc.

7. The copolymerization method of claim 5, wherein the molar ratio of aluminum in the cocatalyst to M in the main catalyst is (10-100000): 1; or the molar ratio of boron in the cocatalyst to M in the main catalyst is (0.01-1000): 1.

8. The copolymerization method of claim 6, wherein the molar ratio of aluminum in the chain transfer agent to M in the main catalyst is (1-10000): 1; or the molar ratio of zinc in the chain transfer agent to M in the main catalyst is (1-1000): 1.

9. The copolymerization process according to claim 1, wherein the terminal alkenylsilane is selected from at least one compound of formula (II) and the terminal alkenylsiloxane is selected from at least one compound of formula (III):

in the formula (II), m and n are respectively 0 or a positive integer;

in the formula (III), p and q are each 0 or a positive integer.

10. The copolymerization process according to claim 9, wherein in the formula (II), m and n are each an integer of 0 to 20;

in the formula (III), p and q are each an integer of 0 to 20.

11. The copolymerization process according to claim 1, wherein the temperature of the copolymerization reaction is from-20 ℃ to 200 ℃;

the pressure of ethylene is 1 to 1000 atm.

12. The copolymerization process according to claim 11, wherein the temperature of the copolymerization reaction is 40 to 120 ℃.

13. The copolymerization process according to claim 12, wherein the temperature of the copolymerization reaction is 60 to 110 ℃.

14. The copolymerization process according to claim 11, wherein the pressure of ethylene is 1 to 200 atm.

15. The copolymerization process according to claim 1, 9, 10, 11, 12, 13 or 14, wherein the terminal alkenylsilane/siloxane is used in an amount of 0.01 to 3000 mmol/L.

16. The copolymerization process according to claim 15, wherein the terminal alkenylsilane/siloxane is used in an amount of 0.1 to 1000 mmol/L.

17. The copolymerization method according to claim 1, wherein the amount of the main catalyst is 0.00001 to 100 mmol/L.

18. The copolymerization process according to claim 17, wherein the amount of the procatalyst used is from 0.001 to 1 mmol/L.