CN107663253B - Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition - Google Patents

Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition Download PDF

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CN107663253B
CN107663253B CN201610608192.3A CN201610608192A CN107663253B CN 107663253 B CN107663253 B CN 107663253B CN 201610608192 A CN201610608192 A CN 201610608192A CN 107663253 B CN107663253 B CN 107663253B
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高榕
赖菁菁
李岩
刘东兵
郭子芳
周俊领
廖浩瀚
傅捷
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms

Abstract

The invention provides a catalyst composition for long-chain alpha-olefin polymerization and a method for catalyzing the long-chain alpha-olefin polymerization by using the catalyst composition, wherein the catalyst composition comprises the following components: a main catalyst, a cocatalyst and a chain transfer agent; the main catalyst is a complex with the chemical structure as shown in the specification: wherein R is1‑R10The same or different, each independently selected from hydrogen, saturated or unsaturated alkyl, alkoxy or halogen; x is selected from halogen; the cocatalyst is selected from at least one of alkyl aluminoxane, aryl boron and borate; the chain transfer agent is selected from trialkylaluminums and/or dialkylzinc. The method for catalyzing the polymerization of long-chain alpha-olefin by the catalyst composition comprises the following steps: in the presence of inert gas, the long-chain alpha-olefin, the main catalyst, the cocatalyst and the chain transfer agent are contacted to carry out polymerization reaction. The catalyst composition has high catalytic activity and good thermal stability when catalyzing the chain transfer polymerization of alpha-olefin, and is used for synthesizing poly alpha-olefin with controllable molecular weight.

Description

Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition
Technical Field
The invention relates to the technical field of catalysts for olefin polymerization, and in particular relates to a catalyst composition for long-chain alpha-olefin chain transfer polymerization and a method for catalyzing long-chain alpha-olefin polymerization by using the catalyst composition.
Background
Poly-alpha-olefin synthetic oil (PAO) is an oil product with high purity produced by alpha-olefin through oligomerization and hydrogenation saturation under the action of a catalyst. Compared with mineral oil, PAO has the characteristics of high viscosity index, low pour point, high flash point, excellent high and low temperature performance and the like, and can not be replaced in many oil products. A significant challenge in the preparation of alpha-olefin synthetic oils is the search for a method of controlling the viscosity index of the polyalphaolefins, i.e., controlling the molecular weight and distribution of the polyalphaolefins.
The single-site polyolefin catalyst can well control the microstructure of the synthesized polyolefin molecules, particularly can realize the active polymerization of the olefin molecules under certain conditions, and in the active polymerization of the polyolefin, each catalyst can only enable one polymer chain to carry out the polymerization propagation reaction, thereby precisely controlling the chemical structure, the molecular weight and the molecular weight distribution of the polyolefin molecules. In order to significantly reduce the consumption of the more expensive transition metals in the catalyst component, allowing the synthesis of multiple polyolefin molecules per catalyst molecule, researchers have developed coordination chain transfer polymerization of olefins. The coordination chain transfer polymerization of the olefin can realize the controllable/active chain growth process of polyolefin molecules and can realize the design and control of the polyolefin molecular structure. Recent studies at home and abroad find that chain transfer agents (CSA) (generally alkyl metal compounds such as aluminum alkyl, zinc alkyl and the like) are used for catalyzing ethylene polymerization by using a single-active-site catalyst, and have a plurality of advantages.
Patent document CN103288985A provides an alpha-nickel diimine complex (chemical structure is shown as formula (II)) for catalyzing ethylene, propylene and C6-C18By homopolymerization or copolymerization of alpha-olefins, butThe molecular weight of the obtained polymer is higher and is about 200000-400000, so that the wide application of the polymer in PAO is influenced.
Figure BDA0001062488200000021
Disclosure of Invention
The invention aims to overcome the technical defects of poor thermal stability, high molecular weight of long-chain alpha-olefin catalysis and the like of the existing alpha-diimine nickel metal catalyst, and provides a catalyst composition for long-chain alpha-olefin polymerization and a method for catalyzing long-chain alpha-olefin polymerization by using the catalyst composition.
In order to achieve the above objects, the present invention provides a catalyst composition for polymerization of long chain α -olefins, comprising the following components:
a main catalyst, a cocatalyst and a chain transfer agent,
the main catalyst is a complex with a chemical structure shown as a formula (I):
Figure BDA0001062488200000022
wherein R is1-R10The same or different, each independently selected from at least one of hydrogen, saturated or unsaturated hydrocarbon group, hydrocarbyloxy group and halogen; x is selected from halogen;
the cocatalyst is selected from at least one of alkyl aluminoxane, aryl boron and borate;
the chain transfer agent is selected from trialkyl aluminum and/or dialkyl zinc.
In the present invention, the alkyl group includes, but is not limited to, alkyl, alkenyl, alkynyl, aryl, preferably alkyl or alkenyl.
According to the catalyst composition provided by the invention, preferably, in the formula (I), R1-R10Each independently selected from hydrogen and C1-C10Saturated or unsaturated hydrocarbon radicals of (C)1-C10At least one of alkoxy and halogen of (a); preferably selected from hydrogen, C1-C6A saturated or unsaturated hydrocarbon group of C1-C6More preferably at least one of alkoxy and halogen of (2), more preferably selected from hydrogen, C1-C5A saturated or unsaturated hydrocarbon group of C1-C5At least one of alkoxy and halogen. Even more preferably, R1-R10Each independently selected from at least one of hydrogen, methyl, ethyl, vinyl, isopropyl, propenyl, methoxy, ethoxy, propoxy, fluoro, chloro and bromo.
According to a preferred embodiment of the present invention, R is1-R6Each independently selected from hydrogen and C1-C5A saturated or unsaturated hydrocarbon group of C1-C5At least one of alkoxy and halogen of (a); the R is7-R10Are all hydrogen. Further preferably, said R1-R6Each independently selected from at least one of methyl, ethyl, vinyl, isopropyl, propenyl, methoxy, ethoxy, propoxy, fluoro, chloro and bromo; the R is7-R10Are all hydrogen.
According to the catalyst composition provided by the invention, preferably, the complex is selected from at least one of the following complexes, wherein R7-R10Are all hydrogen:
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。
According to the catalyst composition provided by the present invention, preferably, the alkylaluminoxane is methylaluminoxane and/or modified methylaluminoxane.
The aralkyl boron is substituted or unsubstituted phenylboron, and is more preferably trifluorophenylboron.
The borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
According to the catalyst composition provided by the invention, preferably, the chain transfer agent is selected from at least one of trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, dimethyl zinc and diethyl zinc.
According to the catalyst composition provided by the invention, preferably, the molar ratio of the aluminum in the cocatalyst to the nickel in the main catalyst is (10-10000): 1; or the molar ratio of boron in the cocatalyst to nickel in the main catalyst is (1-500): 1.
According to the catalyst composition provided by the invention, preferably, the molar ratio of aluminum in the chain transfer agent to nickel in the main catalyst is (1-1000):1, more preferably (5-500): 1; or the molar ratio of zinc in the chain transfer agent to nickel in the main catalyst is (1-1000):1, more preferably (3-500): 1.
The invention also provides a method for catalyzing the polymerization of long-chain alpha-olefin by the catalyst composition, which comprises the following steps: in the presence of inert gas, the long-chain alpha-olefin, the main catalyst, the cocatalyst and the chain transfer agent are contacted to carry out polymerization reaction.
According to the method provided by the invention, the polymerization reaction temperature is preferably-78-200 ℃, preferably-20-150 ℃, and further preferably 30-120 ℃.
The long-chain alpha-olefin is aliphatic terminal olefin with the carbon number of more than or equal to 5, and the method is particularly suitable for C6-C18Of alpha-olefins.
According to the method provided by the invention, preferably, the amount of the main catalyst in the long-chain alpha-olefin polymerization is 0.0001-10 mmol/L; further preferably 0.001 to 1 mmol/L.
Compared with the prior art, the invention has the following beneficial effects:
when the alpha-olefin chain transfer polymerization reaction is carried out, the catalyst composition can still keep higher catalytic activity at the temperature of more than 90 ℃, and the molecular weight of the obtained polymer can be controlled by selecting and adding the chain transfer agent, so that the molecular weight of the obtained product is reduced, and the quality of the poly alpha-olefin product is improved; more importantly, the catalyst composition is used for carrying out bulk polymerization catalysis reaction, which has very important significance for industrial production of poly alpha-olefin.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples, however, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene), 0.5ml of diethyl zinc (1.0mol/l in toluene) were added in this order and polymerized at 90 ℃ for 2 hoursThen, the reaction system is stopped, and the reaction system is black and sticky. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 3.10g of a polymer in the form of a white solid with a certain elasticity. The catalytic efficiency of the catalytic system is 310kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 25.62 ten thousand, and molecular weight distribution Mw/Mn was 2.41.
Comparative example 1
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, and 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to give 3.88g of a polymer having a certain elasticity and being in the form of a white solid. The weight average molecular weight of the polymer was measured at the end of the reaction and was 34.74 ten thousand, and the molecular weight distribution Mw/Mn was 2.13.
Comparative example 2
A100 ml three-necked reaction flask was evacuated, and replaced with nitrogen three times, and 7.2mg (10. mu. mol) of comparative complex 1 (structural formula (II)), 15ml of 1-decene, and 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 0.52g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 52kg mol-1Ni。
Figure BDA0001062488200000061
Figure BDA0001062488200000071
Comparative example 3:
a100 ml three-necked reaction flask was evacuated, and replaced with nitrogen three times, and 7.2mg (10. mu. mol) of comparative complex 1 (structural formula (II)), 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene), and 0.5ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 0.38g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 38kg mol-1Ni。
Example 2
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethyl zinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 3.64g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system is 364kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 14.24 ten thousand, and molecular weight distribution Mw/Mn was 2.07.
Example 3
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. Terminating the reaction with dilute hydrochloric acid-ethanol solution, dissolving the obtained polymer with tetrahydrofuran, precipitating with methanol, repeating the above steps for three times, and finally placing the sampleDrying in a vacuum drying oven for 24 hours to obtain 1.92g of polymer with certain elasticity. The catalytic efficiency of the catalytic system was 192kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 8.64 ten thousand, and molecular weight distribution Mw/Mn was 2.27.
Example 4
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of trimethylaluminum (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 1.32g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 132kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 3.14 ten thousand, and molecular weight distribution Mw/Mn was 3.44.
Example 5
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.8mg (10. mu. mol) of complex 3, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to give 3.84g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system is 384kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 20.06 ten thousand, and molecular weight distribution Mw/Mn was 1.84.
Example 6
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 6.6mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution), and 1.0ml of diethyl zinc (1.0mol/l toluene solution) were added in this orderLiquid), the polymerization was stopped after 2 hours at 90 ℃ and the reaction system was black and sticky. The reaction was terminated with dilute hydrochloric acid-ethanol solution, the resulting polymer was washed with acetone, and finally the sample was dried in a vacuum oven for 24 hours to give 1.02g of polymer. The catalytic efficiency of the catalytic system was 102kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 0.94 ten thousand, and molecular weight distribution Mw/Mn was 2.07.
Example 7
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.7mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethyl zinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. The reaction was terminated with dilute hydrochloric acid-ethanol solution, the resulting polymer was washed with acetone, and finally the sample was dried in a vacuum oven for 24 hours to give 1.04g of polymer. The catalytic efficiency of the catalytic system is 104kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 0.72 ten thousand, and molecular weight distribution Mw/Mn was 2.04.
Example 8
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-dodecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) and 1.0ml of diethyl zinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 3.91g of a polymer in the form of a white solid with a certain elasticity. The catalytic efficiency of the catalytic system is 391kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 18.27 ten thousand, and molecular weight distribution Mw/Mn was 2.24.
Example 9
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-dodecene and 0.8ml of methyl group were sequentially addedAluminoxane (MAO) (1.53mol/l in toluene), 2.0ml of diethyl zinc (1.0mol/l in toluene), and polymerization was stopped after 2 hours at 90 ℃ and the reaction system was black and sticky. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 2.62g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 262kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 10.17 ten thousand, and molecular weight distribution Mw/Mn was 1.84.
Example 10
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-tetradecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution), and 1.0ml of diethylzinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to give 4.27g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 427kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 20.21 ten thousand, and molecular weight distribution Mw/Mn was 2.16.
Example 11
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-tetradecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution), and 2.0ml of diethylzinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 3.64g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system is 364kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction of 8.86 ten thousand, molecular weightAnd the Mw/Mn of the cloth is 1.93.
Example 12
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-hexadecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 3.87g of a polymer having a certain elasticity and being in a white solid form. The catalytic efficiency of the catalytic system is 387kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 22.61 ten thousand, and molecular weight distribution Mw/Mn was 2.04.
Example 13
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 8.3mg (10. mu. mol) of complex 2, 15ml of 1-hexadecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 2.62g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 262kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 10.41 ten thousand, and molecular weight distribution Mw/Mn was 2.01.
Example 14
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 9.3mg (10. mu. mol) of complex 5, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethyl zinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. And (3) terminating the reaction by using a dilute hydrochloric acid-ethanol solution, washing the obtained polymer by using acetone, and finally putting the sample into a vacuum drying oven to be dried for 24 hours to obtain the product 1.51g of polymer. The catalytic efficiency of the catalytic system was 151kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 1.24 ten thousand, and molecular weight distribution Mw/Mn was 2.07.
Example 15
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 9.3mg (10. mu. mol) of complex 5, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. The reaction was terminated with dilute hydrochloric acid-ethanol solution, the resulting polymer was washed with acetone, and finally the sample was dried in a vacuum oven for 24 hours to give 0.82g of polymer. The catalytic efficiency of the catalytic system was 82kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 0.66 ten thousand, and molecular weight distribution Mw/Mn was 1.84.
Example 16
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.4mg (10. mu. mol) of complex 13, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to give 4.27g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 427kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 20.34 ten thousand, and molecular weight distribution Mw/Mn was 2.07.
Example 17
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.4mg (10. mu. mol) of complex 13, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 90 ℃ with the reaction system being black and sticky. Terminating the reaction by using a dilute hydrochloric acid-ethanol solution to obtain a polymerDissolving with tetrahydrofuran, precipitating with methanol, repeating the above steps for three times, and oven drying the sample in a vacuum oven for 24 hr to obtain 2.16g white solid polymer with certain elasticity. The catalytic efficiency of the catalytic system was 216kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 8.18 ten thousand, and molecular weight distribution Mw/Mn was 1.82.
Compared with the comparative example 1, the chain transfer agent is introduced in the examples 1-4, so that the molecular weight of the polymer can be greatly regulated and controlled; compared with comparative examples 2 and 3, when the metal complex of the invention is used as a main catalyst, the polymerization activity is much higher under the high-temperature polymerization condition, and the nickel metal complex of the invention has better thermal stability.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (11)

1. A catalyst composition for the polymerization of long chain alpha-olefins, the catalyst composition comprising:
a main catalyst, a cocatalyst and a chain transfer agent;
the main catalyst is a complex with a chemical structure shown as a formula (I):
Figure FDA0002629628990000011
the complex is selected from at least one of the following complexes, wherein R7-R10Are all hydrogen:
and (2) the complex: r1＝R3＝R4＝R6＝Et，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 13: r1＝R3＝R4＝R6＝Et，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；
The cocatalyst is selected from at least one of alkyl aluminoxane, aryl boron and borate;
the chain transfer agent is selected from trialkyl aluminum and/or dialkyl zinc.
2. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1, wherein the alkylaluminoxane is methylaluminoxane and/or modified methylaluminoxane; the aryl boron is substituted or unsubstituted phenyl boron; the borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
3. The catalyst composition for the polymerization of long chain alpha olefins according to claim 2 in which the aryl boron is trifluorophenylboron.
4. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1 wherein the chain transfer agent is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc and diethylzinc.
5. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1 wherein the molar ratio of aluminum in the cocatalyst to nickel in the procatalyst is (10-10000): 1; or the molar ratio of boron in the cocatalyst to nickel in the main catalyst is (1-500): 1.
6. The catalyst composition for the polymerization of long chain alpha olefins according to claim 1, wherein the molar ratio of aluminum in the chain transfer agent to nickel in the procatalyst is (1-1000): 1; or the molar ratio of the zinc in the chain transfer agent to the nickel in the main catalyst is (1-1000): 1.
7. A process for the polymerization of long chain alpha olefins catalyzed by the catalyst composition of any of claims 1 to 6, comprising: in the presence of inert gas, the long-chain alpha-olefin, the main catalyst, the cocatalyst and the chain transfer agent are contacted to carry out polymerization reaction.
8. The process of claim 7, wherein the polymerization reaction is at a temperature of-78 ℃ to 200 ℃.
9. The process of claim 8, wherein the polymerization reaction is at a temperature of-20 ℃ to 150 ℃.
10. The method of claim 7, wherein the amount of the procatalyst is 0.0001 to 10 mmol/L.
11. The method of claim 10, wherein the amount of the procatalyst is 0.001-1 mmol/L.
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