CN108359097B - Copolymerization method of ethylene and terminal alkenyl silane/siloxane - Google Patents

Copolymerization method of ethylene and terminal alkenyl silane/siloxane Download PDF

Info

Publication number
CN108359097B
CN108359097B CN201710057292.6A CN201710057292A CN108359097B CN 108359097 B CN108359097 B CN 108359097B CN 201710057292 A CN201710057292 A CN 201710057292A CN 108359097 B CN108359097 B CN 108359097B
Authority
CN
China
Prior art keywords
complex
ethylene
copolymerization
added
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710057292.6A
Other languages
Chinese (zh)
Other versions
CN108359097A (en
Inventor
高榕
周俊领
李岩
刘东兵
赖菁菁
傅捷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201710057292.6A priority Critical patent/CN108359097B/en
Publication of CN108359097A publication Critical patent/CN108359097A/en
Application granted granted Critical
Publication of CN108359097B publication Critical patent/CN108359097B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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 a comonomer 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):
Figure BDA0001219609190000021
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, 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):
Figure BDA0001219609190000031
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.
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 synthesized 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):
Figure BDA0001219609190000051
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, the reaction may be carried out 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 dripped into the solution of the diimine ligand compound according to the mol ratio of (1: 1 to 1: 1.2), the mixture is stirred at room temperature, precipitates are separated out, filtered, washed by diethyl ether and dried in vacuum, and the obtained product is identified as the ligand shown in the formula (I) by infrared and elemental analysis 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 arylborole is a substituted or unsubstituted phenylborone, more preferably a trifluorophenylborole.
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, the "terminal alkenyl group" includes a vinyl group and an α -alkenyl group, and the double bond in the group is located at one end of the molecular chain. "terminal alkenylsilane/siloxane" refers to "terminal alkenylsilane" and/or "terminal alkenylsiloxane".
Specifically, the terminal alkenylsilane is selected from at least one of compounds shown in a formula (II):
Figure BDA0001219609190000081
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.
According to the invention, the terminal alkenylsiloxane is selected from at least one compound of formula (III):
Figure BDA0001219609190000091
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 PDI (PDI. Mw/Mn) of the polymer were determined by PL-GPC220 using trichlorobenzene as a solvent at 150 ℃ (standard: PS, flow: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
Example 1
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was injected and then added6.5mL of Methylaluminoxane (MAO) (1.53mol/L in toluene), and 5mL of allyltrimethoxysilane (28.7mmol) were reacted at 70 ℃ under 10atm of ethylene pressure with stirring for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 100 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 10mL of allyltrimethoxysilane (57.4mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 4
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L in toluene) was added to make Al/Ni 1000, 0.2mL of diethyl zinc (1mol/L in hexane) was added to make Zn/Ni 20, 5mL of allyltrimethoxysilane (28.7mmol),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% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 5
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added to make Al/Ni 1000, 0.5mL of diethyl zinc (1mol/L hexane solution) was added to make Zn/Ni 50, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the mixture was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 6
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 11.8mg (10. mu. mol) of complex 2 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 7
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 11.8mg (10. mu. mol) of complex 2 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was charged, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added to make Al/Ni 1000, 0.5mL of diethyl zinc (1mol/L hexane solution) was added to make Zn/Ni 50, 5mL of allyltrimethoxysilane (28.7mmol) was added, and ethylene pressure of 10atm was maintained at 70 ℃, and the mixture was stirredIt should be 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 8
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 11.2mg (10. mu. mol) of complex 1 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 9
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 13.3mg (10. mu. mol) of complex 8 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 10
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 11.4mg (10. mu. mol) of complex 14 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 11
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and 5mL of 7-octenyltrimethoxysilane (17.8mmol) was added to make Al/Ni 1000, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 12
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added to the mixture so that Al/Ni becomes 1000, 0.2mL of diethyl zinc (1mol/L hexane solution) was added to the mixture so that Zn/Ni becomes 20, 5mL of 7-octenyltrimethoxysilane (17.8mmol) was added, and the mixture was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 13
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added to the mixture so that Al/Ni becomes 1000, 0.5mL of diethyl zinc (1mol/L hexane solution) was added to the mixture so that Zn/Ni becomes 50, 5mL of 7-octenyltrimethoxysilane (17.8mmol) was added, and the reaction mixture was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 14
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and 5mL of vinyltrimethoxysilane (31.6mmol) was added to make Al/Ni 1000, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 15
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethylsilane (22.1mmol) was reacted at 70 ℃ under a pressure of ethylene of 10atm, and the reaction mixture was stirred for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 16
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added to make Al/Ni 1000, 0.5mL of diethyl zinc (1mol/L hexane solution) was added to make Zn/Ni 50, 5mL of allyltrimethylsilane (22.1mmol) was added, and the mixture was stirred at 70 ℃ under a pressure of ethylene of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 17
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Air replacement3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 40 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 18
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 120 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% hydrochloric acid acidified ethanol solution, and the polymerization activity and the polymer property parameters are shown in Table 1.
Example 19
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; 12.3mg (10. mu. mol) of complex 3 are added, followed by evacuation and 3 replacements with ethylene; 500mL of toluene was charged, 5mL of a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (2mmol/L toluene solution) was added thereto, and Ni/B was changed to 1, 5mL of allyltrimethoxysilane (28.7mmol), and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the reaction was terminated with 5 vol% hydrochloric acid in ethanol to obtain a polymer, and the polymerization activity and the polymer properties were as shown in Table 1.
Comparative example 1
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; adding 6.6mg (10 mu mol) of a comparative catalyst A (a complex A, the structure of which is shown in a formula (IV)), vacuumizing and replacing for 3 times by using ethylene; 500mL of toluene was injected into the reactor,then, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L in toluene) was added thereto, and 5mL of allyltrimethoxysilane (28.7mmol) was added thereto, and the mixture was stirred at 70 ℃ under 10atm of ethylene pressure for 30 min. Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol, only a small amount of polymer was formed, and the polymerization activity and the polymer performance parameters were as shown in Table 1.
Figure BDA0001219609190000171
Comparative example 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 6.6mg (10. mu. mol) of comparative catalyst A were added, followed by evacuation and replacement with ethylene 3 times; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and 5mL of vinyltrimethoxysilane (28.7mmol) was added to make Al/Ni 1000, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol solution, and no polymer was formed.
Comparative example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Gas replacement for 3 times; adding 6.3mg (10 μmol) of comparative catalyst B (complex B, structure shown in formula (V)), vacuumizing and replacing with ethylene for 3 times; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol solution, and no polymer was formed.
Figure BDA0001219609190000181
Comparative example 4
Continuously drying in a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, evacuation while hot and application of N2Gas replacement for 3 times; adding 6.0mg (10 mu mol) of a comparative catalyst C (complex C, the structure is shown in a formula (VI)), vacuumizing and replacing for 3 times by using ethylene; 500mL of toluene was added, 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added thereto, and Al/Ni was 1000, 5mL of allyltrimethoxysilane (28.7mmol) was added, and the reaction was stirred at 70 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol solution, and no polymer was formed.
Figure BDA0001219609190000191
TABLE 1
Figure BDA0001219609190000192
Figure BDA0001219609190000201
As can be seen from Table 1, the catalyst compositions of the examples have a copolymerization activity of up to 13.20X 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 (18)

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):
Figure FDA0002638880810000011
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), R2、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；
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 all hydrogen.
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):
Figure FDA0002638880810000031
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 0.001 to 1 mmol/L.
CN201710057292.6A 2017-01-26 2017-01-26 Copolymerization method of ethylene and terminal alkenyl silane/siloxane Active CN108359097B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710057292.6A CN108359097B (en) 2017-01-26 2017-01-26 Copolymerization method of ethylene and terminal alkenyl silane/siloxane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710057292.6A CN108359097B (en) 2017-01-26 2017-01-26 Copolymerization method of ethylene and terminal alkenyl silane/siloxane

Publications (2)

Publication Number Publication Date
CN108359097A CN108359097A (en) 2018-08-03
CN108359097B true CN108359097B (en) 2020-11-10

Family

ID=63011399

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710057292.6A Active CN108359097B (en) 2017-01-26 2017-01-26 Copolymerization method of ethylene and terminal alkenyl silane/siloxane

Country Status (1)

Country Link
CN (1) CN108359097B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260344B (en) * 2021-04-29 2023-08-15 中国石油化工股份有限公司 Application of metal complex in catalyzing olefin polymerization

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087382A (en) * 1976-11-24 1978-05-02 Halcon International, Inc. Catalyst
CN1215733A (en) * 1996-05-17 1999-05-05 台湾合成橡胶股份有限公司 Process for selective hydrogenation of conjugated diolefine polymer
CN1392890A (en) * 2000-07-25 2003-01-22 三井化学株式会社 Curable composition and uses thereof
CN101248099A (en) * 2005-07-11 2008-08-20 陶氏环球技术公司 Silane-grafted olefin polymers, compositions and articles prepared therefrom, and methods for making the same
CN102050904A (en) * 2001-11-16 2011-05-11 纳幕尔杜邦公司 Copolymers of olefins and vinyl- and allylsilanes
CN102399361A (en) * 2010-08-02 2012-04-04 赢创高施米特有限公司 Modified alkoxylation products with at least one non-terminal alkoxysilyl group and use of same in hardenable masses
CN103154062A (en) * 2010-06-14 2013-06-12 朗盛德国有限责任公司 Blends of partially hydrogenated nitrile rubber and silicone rubber, vulcanizable mixtures and vulcanizates based thereon
CN104277145A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof
CN104277148A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof
DE102014209408A1 (en) * 2014-05-19 2015-11-19 Evonik Degussa Gmbh Ethoxylate preparation using highly active double metal cyanide catalysts
CN105916917A (en) * 2013-12-13 2016-08-31 莫门蒂夫性能材料股份有限公司 Process for the production of silane-crosslinked polyolefin in the presence of non-tin catalyst and the resulting crosslinked polyolefin
CN105916871A (en) * 2013-11-19 2016-08-31 莫门蒂夫性能材料股份有限公司 Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087382A (en) * 1976-11-24 1978-05-02 Halcon International, Inc. Catalyst
CN1215733A (en) * 1996-05-17 1999-05-05 台湾合成橡胶股份有限公司 Process for selective hydrogenation of conjugated diolefine polymer
CN1392890A (en) * 2000-07-25 2003-01-22 三井化学株式会社 Curable composition and uses thereof
CN102050904A (en) * 2001-11-16 2011-05-11 纳幕尔杜邦公司 Copolymers of olefins and vinyl- and allylsilanes
CN101248099A (en) * 2005-07-11 2008-08-20 陶氏环球技术公司 Silane-grafted olefin polymers, compositions and articles prepared therefrom, and methods for making the same
CN103154062A (en) * 2010-06-14 2013-06-12 朗盛德国有限责任公司 Blends of partially hydrogenated nitrile rubber and silicone rubber, vulcanizable mixtures and vulcanizates based thereon
CN102399361A (en) * 2010-08-02 2012-04-04 赢创高施米特有限公司 Modified alkoxylation products with at least one non-terminal alkoxysilyl group and use of same in hardenable masses
CN104277145A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof
CN104277148A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof
CN105916871A (en) * 2013-11-19 2016-08-31 莫门蒂夫性能材料股份有限公司 Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
CN105916917A (en) * 2013-12-13 2016-08-31 莫门蒂夫性能材料股份有限公司 Process for the production of silane-crosslinked polyolefin in the presence of non-tin catalyst and the resulting crosslinked polyolefin
DE102014209408A1 (en) * 2014-05-19 2015-11-19 Evonik Degussa Gmbh Ethoxylate preparation using highly active double metal cyanide catalysts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
New highly ordered hydrophobic siloxane-based coordination polymers;CarmenRacles等;《Polymer》;20131018;第54卷(第22期);第6096-6104页 *
Photochemical formation of substituted pentacenes;Yuewei Zhao等;《The Journal of Organic Chemistry》;20080614;第73卷(第14期);第5506-5513页 *
氧化石墨负载铂配合物的制备及其催化烯烃硅氢加成反应的性能研究;饶福原;《中国优秀硕士学位论文全文库工程科技Ι辑》;20150215(第2期);第B014-268页 *

Also Published As

Publication number Publication date
CN108359097A (en) 2018-08-03

Similar Documents

Publication Publication Date Title
US8022152B2 (en) Copolymers of vinyl- and allylsilanes
CN111116806B (en) Preparation method of olefin-unsaturated carboxylic acid copolymer
CN108383739A (en) A kind of aromatic amine and its alpha-diimine complex with hydroxyl and application in olefin polymerization
EP3246343A1 (en) Method for preparing polyolefin
CN111116802B (en) Preparation method of olefin-unsaturated carboxylic acid copolymer
CN108359030B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN108359036B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN111116801B (en) Preparation method of olefin-unsaturated carboxylic acid copolymer
CN108359097B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN108359037B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN108864346A (en) A kind of ethylene and end alkenyl silanes/siloxanes copolymerization process
CN108359039B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN108359038B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN108359035B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane
CN103804551A (en) Preparation method of ethylene copolymer
CN115260368B (en) Polymerization method of ethylene-internal olefin-diene copolymer and copolymer obtained by polymerization method
CN112745358A (en) Diimine metal complex and preparation method and application thereof
CN111116790A (en) Propylene polymer and preparation method and application thereof
CN111116787B (en) Diamine ligand, diamine complex, and catalyst comprising diamine complex
EP3255069A1 (en) Supported metallocene catalyst, and method for preparing polyolefin by using same
CN115260360B (en) Copolymerization method of ethylene and terminal alkenyl silane/siloxane, copolymer and application thereof
CN112745361A (en) Diimine complex and preparation method and application thereof
CN114478866B (en) Catalyst for olefin polymerization, preparation method and application thereof
CN110964049B (en) Transition metal compound, olefin polymerization catalyst composition containing same, preparation method and application
CN113233994B (en) Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant