CN107663251B - Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition - Google Patents

Abstract

The invention provides a catalyst composition for long-chain α -olefin polymerization and a method for catalyzing long-chain α -olefin polymerization by using the catalyst composition¹‑R¹⁰The catalyst composition is used for catalyzing α -olefin chain transfer polymerization, has higher catalytic activity and good thermal stability, and is used for synthesizing poly α -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 a α -diimine nickel metal complex (chemical structure is shown as formula (II)) for catalyzing ethylene, propylene and C₆-C₁₈The α -olefin homopolymerization or copolymerization reaction is carried out, but the 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.

Disclosure of Invention

The invention aims to provide a catalyst composition capable of catalyzing long-chain alpha-olefin chain polymerization at a higher temperature and a method for catalyzing long-chain alpha-olefin polymerization by using the catalyst composition, aiming at 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; 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.

In order to achieve the above object, the present invention provides a catalyst composition for long chain α -olefin polymerization, characterized in that the catalyst composition comprises 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):

wherein X is halogen; r¹-R¹⁰The same or different, each independently selected from at least one of hydrogen, saturated or unsaturated hydrocarbon group, hydrocarbyloxy group and 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-C₁₀A saturated or unsaturated hydrocarbon group of C₁-C₁₀At least one of alkoxy and halogen of (a); further preferably selected from hydrogen and C₁-C₆A saturated or unsaturated hydrocarbon group of C₁-C₆At least one of alkoxy and halogen. Even more preferably, R¹-R¹⁰Each independently selected from hydrogen, methyl, ethyl, vinyl, isopropyl, propenyl, methoxyAt least one of alkyl, 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 compounds, wherein R is⁷-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 aryl boron is phenyl boron, and is further 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 α -olefin is aliphatic terminal olefin with the carbon number of more than or equal to 5, and the method is particularly suitable for C₆-C₁₈α -olefin of (1).

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 invention is used for carrying out alpha-olefin chain transfer polymerization reaction, the catalyst composition still maintains higher catalytic activity at 100 ℃; 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 11.3mg (10. mu. mol) of complex 2, 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 added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system 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 4.07g of a white solid polymer with a certain elasticity. The catalytic efficiency of the catalytic system was 407kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 30.27 ten thousand, and molecular weight distribution Mw/Mn was 2.04.

Comparative example 1:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ 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 4.86g of a polymer having a certain elasticity and being in the form of a white solid. The weight average molecular weight of the polymer at the end of the reaction was measured to be 45.27 ten thousand, and the molecular weight distribution Mw/Mn was measured to be 2.11.

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。

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 11.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system 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 4.04g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 404kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 18.68 ten thousand, and molecular weight distribution Mw/Mn was 1.92.

Example 3

A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ to make the reaction system 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 3.41g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 341kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 12.16 ten thousand, and molecular weight distribution Mw/Mn was 2.02.

Example 4

A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (10. mu. mol) of complex 2, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 0.5ml of trimethylaluminum (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. 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 oven drying the sample in a vacuum drying oven for 24 hr to obtain 1.12g white solid polymer with certain elasticityA compound (I) is provided. The catalytic efficiency of the catalytic system was 112kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 8.62 ten thousand, and molecular weight distribution Mw/Mn was 2.27.

Example 5:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.9mg (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 added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system 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 3.82g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 382kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 24.17 ten thousand, and molecular weight distribution Mw/Mn was 1.98.

Example 6:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, 10.7mg (10. mu. mol) of complex 1, 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 100 ℃ 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 3.22g of polymer. The catalytic efficiency of the catalytic system was 322kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 4.04 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, 10.7mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ with the reaction system being black and sticky. Terminating the reaction with dilute hydrochloric acid-ethanol solution, thereby obtainingThe resulting polymer was washed with acetone and finally the sample was dried in a vacuum oven for 24 hours to give 1.97g of polymer. The catalytic efficiency of the catalytic system is 197kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 2.04 ten thousand, and molecular weight distribution Mw/Mn was 1.88.

Example 8:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ 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 4.65g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system is 465kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 27.27 ten thousand, and molecular weight distribution Mw/Mn was 2.10.

Example 9:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (10. mu. mol) of complex 2, 15ml of 1-dodecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) and 2.0ml of diethyl zinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ 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 3.34g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 334kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 15.33 ten thousand, and molecular weight distribution Mw/Mn was 1.86.

Example 10:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, 11.3mg (10. mu. mol) of complex 2, 15ml of 1-tetradecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) were successively added,1.0ml of diethyl zinc (1.0mol/l in toluene) was polymerized at 100 ℃ for 2 hours and then the polymerization was stopped, and the reaction system was 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 4.16g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 416kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 24.17 ten thousand, and molecular weight distribution Mw/Mn was 2.04.

Example 11:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ 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 2.87g of a polymer having a certain elasticity and being a white solid. The catalytic efficiency of the catalytic system is 287kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 14.16 ten thousand, and molecular weight distribution Mw/Mn was 1.91.

Example 12:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ 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 3.83g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system is 383kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 24.67 ten thousand, molecular weight distribution Mw/Mn＝2.12。

Example 13:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 11.3mg (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 100 ℃ 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 2.02g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 202kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 16.21 ten thousand, and molecular weight distribution Mw/Mn was 1.94.

Example 14:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 12.3mg (10. mu. mol) of complex 5, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system 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 2.31g of polymer. The catalytic efficiency of the catalytic system was 231kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 3.42 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 12.3mg (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 100 ℃ to make the reaction system black and sticky. The reaction was terminated with a 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 1.42g of polymer. The catalytic efficiency of the catalytic system was 142kg mol^-1NiThe weight average molecular weight of the polymer at the end of the reaction was 1.47 ten thousand, and the molecular weight distribution Mw/Mn was 1.82.

Example 16:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, 10.4mg (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 100 ℃ 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 5.27g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 527kg mol^-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 34.82 ten thousand, and molecular weight distribution Mw/Mn was 2.08.

Example 17:

a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, 10.4mg (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 100 ℃ 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 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 14.72 ten thousand, and molecular weight distribution Mw/Mn was 1.98.

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 (15)

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):

wherein X is halogen; r¹-R¹⁰The same or different, each independently selected from at least one of hydrogen, saturated or unsaturated hydrocarbon group, hydrocarbyloxy group and 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.

2. The catalyst composition for the polymerization of long chain α -olefins according to claim 1, wherein in formula (I), R is¹-R¹⁰Each independently selected from hydrogen and C₁-C₁₀A saturated or unsaturated hydrocarbon group of C₁-C₁₀At least one of alkoxy and halogen.

3. The catalyst composition for polymerization of long chain α -olefins according to claim 2, wherein in formula (I), R is¹-R¹⁰Each independently selected from hydrogen and C₁-C₆A saturated or unsaturated hydrocarbon group of C₁-C₆At least one of alkoxy and halogen.

4. The catalyst composition for polymerization of long chain α -olefins according to claim 3, wherein in formula (I), R is¹-R¹⁰Each independently selected from at least one of hydrogen, methyl, ethyl, vinyl, isopropyl, propenyl, methoxy, ethoxy, propoxy, fluoro, chloro and bromo.

5. The catalyst composition for the polymerization of long chain α -olefins according to claim 1, wherein the complex is selected from at least one of the following compounds, 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。

6. 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 phenyl boron; the borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

7. The catalyst composition for the polymerization of long chain alpha olefins according to claim 6 wherein the aryl boron is trifluorophenylboron.

8. 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.

9. 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.

10. 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.

11. A process for the polymerization of long chain alpha olefins catalysed by the catalyst composition according to any one of claims 1 to 10, characterized in that the process comprises: 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.

12. The process of claim 11, wherein the polymerization reaction is at a temperature of-78 ℃ to 200 ℃.

13. The process of claim 12, wherein the temperature of the polymerization reaction is from-20 ℃ to 150 ℃.

14. The method of claim 11, wherein the amount of the procatalyst is 0.0001 to 10 mmol/L.

15. The method of claim 14, wherein the amount of the procatalyst is 0.001-1 mmol/L.