CN108864344B

CN108864344B - Catalyst composition for olefin polymerization and olefin polymerization method

Info

Publication number: CN108864344B
Application number: CN201710334399.0A
Authority: CN
Inventors: 高榕; 周俊领; 李岩; 刘东兵; 赖菁菁; 傅捷
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-05-12
Filing date: 2017-05-12
Publication date: 2020-12-18
Anticipated expiration: 2037-05-12
Also published as: CN108864344A

Abstract

The invention relates to the field of olefin polymerization catalysts, and provides a catalyst composition for olefin polymerization and an olefin polymerization method, wherein the catalyst composition comprises: (1) a first olefin polymerization catalyst (A) selected from the group consisting of metal complexes of the formula I, R¹～R⁵，R⁷～R¹¹The same or different, each independently selected from hydrogen, hydrocarbyl or halogen; m is a group IVA metal, X, which may be the same or different, is selected from the group consisting of halogen, hydrocarbyl, hydrocarbyloxy; l is a group VIA element; (2) a second olefin polymerization catalyst (B) selected from the group consisting of metal complexes of the formula II, R₁‑R₁₀The same or different, each is independently selected from hydrogen, hydrocarbyl, hydrocarbyloxy or halogen; r₂₁、R₂₂The same or different, each is independently selected from hydrogen, hydrocarbyl, hydrocarbyloxy or halogen; m is a group VIII metal, and X is selected from halogens; (3) a chain shuttling agent; (4) a cocatalyst. The catalyst composition still has high activity at high temperature.

Description

Catalyst composition for olefin polymerization and olefin polymerization method

Technical Field

The invention relates to the field of catalysts for olefin polymerization, and more particularly relates to a catalyst composition for olefin polymerization and a method for olefin polymerization.

Background

Polymers of block-type structure have often been superior in properties to random copolymers and blends for a long time. For example, triblock copolymers of Styrene and Butadiene (SBS) and their hydrogenated versions (SEBS) have excellent heat resistance and elasticity. Block copolymers, known as thermoplastic elastomers (TPEs), have "soft" or elastomeric segments in the polymer chain linking "hard" crystallizable moieties. These polymers exhibit the characteristics of elastomeric materials when the temperature reaches the melting point or glass transition temperature of the "hard" segment. At higher temperatures, these polymers become free flowing and exhibit thermoplastic properties. Existing methods for preparing block copolymers include anionic polymerization and controlled radical polymerization. However, these methods for preparing block copolymers require continuous addition of monomers and batch operations, and the kinds of monomers that can be used for polymerization in the above-mentioned methods are relatively small. For example, in the anionic polymerization of styrene and butadiene to form SBS type block copolymers, a stoichiometric amount of initiator is required per polymer chain and the resulting polymer has a very narrow molecular weight distribution Mw/Mn, preferably 1.0 to 1.3. In addition, anionic and radical polymerization are relatively slow, which affects the industrial development thereof.

It would be desirable to be able to achieve better control of the catalytic process for producing block copolymers, i.e., more than one polymer molecule can be formed per catalyst or initiator molecule during the polymerization process. In addition, it would be desirable to be able to produce multi-block copolymers having both highly crystalline and amorphous blocks or segments from a single monomer, such as ethylene.

Previous researchers have indicated that some homogeneous coordination polymerization catalysts can produce polymers with block structures by inhibiting chain transfer during polymerization. For example, block polymers are prepared by minimizing chain transfer agents and lowering the reaction temperature during polymerization, controlling beta-hydrogen transfer or chain transfer. Under the above conditions, it is believed that sequential addition of different monomers will result in the formation of polymers having sequences or segments with different monomer contents. Some examples of such catalyst compositions and methods are described in Coates, Hustad and Reinartz, Angew. chem. int. Ed.,2002,41, 2236-.

It is well known in the art to interrupt chain growth in olefin polymerization by utilizing certain metal alkyl compounds and other compounds, such as hydrogen, as chain transfer agents. In addition, alkylaluminum compounds are often used as scavengers or cocatalysts in olefin polymerization processes. In Macromolecules,2000,33, 9192-. In Macromolecules,2003,3026-3034 by Liu and Rytter, trimethylaluminum chain transfer agents have also been reported to catalyze the copolymerization of ethylene and 1-hexene in combination with similar catalysts.

In USP6,380,341 and 6,169,151, it is reported that by using a "stereogenic" metallocene catalyst, an olefin polymer having a "block-like" structure is formed by converting polymerization characteristics exhibiting different reaction rates and the like between two stereo configurations with each other.

It is well known that nickel and palladium alpha-diimine catalysts can form highly branched (highly branched) polymers by "chain transfer" during polymerization. Examples of such polymerizations are disclosed in chem.rev.,2000,100,1169-1203, macromol.chem.phys.,2004,205,897-906, and the like. Such long chain branched polymers may also be prepared by homopolymerization of ethylene catalyzed by, for example, 1-t-butyldimethylsiloxy-substituted and 2-t-butyldimethylsiloxy-substituted bis (indenyl) zirconium complexes with methylaluminoxane cocatalyst. Examples of such polymerizations are disclosed in j.mol.catal.a: chem.,1995,102, 59-65; macromolecules,1988,21, 617-622; J.mol.Catal.A. chem.,2002,185,57-64, J.am.chem.Soc.,1995,117, 6414-.

There are reports of chain shuttling polymerization using nickel diimine with metallocene catalysts under the action of diethylzinc (Macromolecules 2009,42,1834-1837), but the polymerization temperature is low, only 20 ℃. The existing alpha-nickel diimine catalyst has low ethylene polymerization activity at high temperature, and the molecular weight of the prepared polyethylene is rapidly reduced along with the increase of polymerization temperature. The existing ethylene gas-phase polymerization process requires the polymerization temperature to be more than 85 ℃, the ethylene solution polymerization process requires the polymerization temperature to be 100-250 ℃, and the original late transition metal catalyst can not meet the requirements of the existing gas-phase and solution-method ethylene polymerization device.

Disclosure of Invention

The present invention is directed to a catalyst composition for olefin polymerization and a method for olefin polymerization, which can maintain high ethylene and C at high temperature by using catalyst A and catalyst B₃～C₁₆The obtained polymer has higher molecular weight and narrower molecular weight distribution, can prepare a block polymer under the action of a chain shuttling agent, and can pass through a comonomer C₃～C₁₆The selection and the amount of the alpha-olefin or the cycloolefine are controlled, and the structure and the crystallization property of the obtained polymer are controlled.

In order to achieve the above object, the present invention provides a catalyst composition for olefin polymerization, which is a mixture or a reaction product comprising the following components:

(1) a first olefin polymerization catalyst (A) selected from at least one metal complex represented by the general formula I:

in the general formula I, R¹～R⁵，R⁷～R¹¹Identical or different, each independently selected from hydrogen, hydrocarbyl or halogen, and optionally, R¹And R⁴Are linked to each other to form a ring, and/or R²And R⁵Are connected with each other to form a ring; m is a group IVA metal, X, which may be the same or different, is selected from the group consisting of halogen, hydrocarbyl, hydrocarbyloxy; l is a group VIA element;

(2) a second olefin polymerization catalyst (B) selected from at least one metal complex represented by the general formula II,

in the general formula II, R₁-R₁₀The same or different, each is independently selected from hydrogen, hydrocarbyl, hydrocarbyloxy or halogen; r₂₁、R₂₂The same or different, each is independently selected from hydrogen, hydrocarbyl, hydrocarbyloxy or halogen; m is selected from group VIII metals and X is selected from halogens;

(3) a chain shuttling agent;

(4) a cocatalyst.

According to the invention, the hydrocarbon radicals mentioned may each be saturated or unsaturated, examples of which include: alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, and alkynyl groups, and the like. The hydrocarbyloxy group is, for example, an alkoxy group, non-limiting examples of which include: methoxy, ethoxy, propoxy, and the like.

Preferably, in the formula (I), R¹～R⁵、R⁷～R¹¹Each independently selected from hydrogen, halogen, C₁～C₂₀The hydrocarbon group (including aliphatic hydrocarbon group and aromatic hydrocarbon group); m is selected from titanium, zirconium or hafnium; the two X are the same or different and are each independently selected from halogen or hydrocarbyl, and L is selected from O or S.

According to the catalyst composition provided by the present invention, preferably, (1) a first olefin polymerization catalyst (a) is at least one selected from the group consisting of metal complexes represented by the general formula III:

general formula (VII)In III, R¹～R⁵，R⁷，R⁹，R¹¹The same or different, each independently selected from hydrogen and C₁～C₂₀Aliphatic hydrocarbon group of (C)₆～C₃₀Aromatic hydrocarbon groups of (a) or halogen; and optionally, R¹And R⁴Are linked to each other to form a ring, and/or R²And R⁵Are connected with each other to form a ring; m is titanium, zirconium or hafnium, and X is halogen.

In the invention C₁～C₂₀The aliphatic hydrocarbon group of (A) means C₁～C₂₀Alkane or C₁～C₂₀Cycloalkane of (a); c₁～C₂₀The alkane is C₁～C₂₀Straight chain alkyl or C₃-C₂₀A branched alkyl group of (a); c₁～C₁₀The alkane 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.

In the present invention, the first olefin polymerization catalyst (A) can be prepared by a conventional method, for example, the references Organometallics,1998,17, 2152-; macromolecules,1998, 31, 7588-; J.mol.Catal.A 2009,303, 102-. The disclosures of the foregoing documents are incorporated herein by reference in their entirety and are not described in detail herein.

According to the catalyst composition provided by the present invention, the polymerization activity of the second olefin polymerization catalyst (B) is lower than that of the first olefin polymerization catalyst (A). Preferably, in formula II, R₁-R₁₀The same or different, each independently selected from hydrogen and C₁～C₂₀Saturated hydrocarbon group of (C)₂～C₂₀Unsaturated hydrocarbon group of (C)₁～C₂₀Hydrocarbyloxy or halogen of (a); preferably selected from hydrogen, C₁～C₁₀Saturated hydrocarbon group of (C)₂-C₁₀Unsaturated hydrocarbon group of (C)₁～C₁₀Alkoxy or halogen of (a); further preferably selected from hydrogen and C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a); r₂₁、R₂₂The same or different, each independently selected from hydrogen and C₁～C₂₀Saturated hydrocarbon group of (C)₂～C₂₀Unsaturated hydrocarbon group of (C)₁～C₂₀Hydrocarbyloxy or halogen of (a); preferably selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Alkoxy or halogen of (a); further preferably selected from hydrogen and C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a); m is nickel or palladium, and X is selected from halogen.

The polymerization activity of the second olefin polymerization catalyst (B) is lower than that of the first olefin polymerization catalyst (A).

According to the catalyst composition provided by the present invention, preferably, the second olefin polymerization catalyst (B) is selected from at least one of the following metal complexes; in the general formula II, R₇-R₁₀Are both hydrogen, M is nickel:

the complex 1: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝H，X＝Br；

And (2) the complex: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝H，X＝Br；

And (3) complex: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝iPr，R₂＝R₅＝H，X＝Br；

The complex 4: r₂₁＝R₂₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆＝Me，X＝Br；

And (3) a complex 5: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Br，X＝Br；

The complex 6: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Et，X＝Br；

The complex 7: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Me，X＝Br；

The complex 8: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Br，X＝Br；

The complex 9: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝F，R₂＝R₅＝H，X＝Br；

The complex 10: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Cl，R₂＝R₅＝H，X＝Br；

The complex 11: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Br，R₂＝R₅＝H，X＝Br；

The complex 12: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝H，X＝Cl；

The complex 13: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝H，X＝Cl；

The complex 14: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝iPr，R₂＝R₅＝H，X＝Cl；

The complex 15: r₂₁＝R₂₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆＝Me，X＝Cl；

The compound 16: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Br，X＝Cl；

The complex 17: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Et，X＝Cl；

The complex 18: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Me，X＝Cl；

The complex 19: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Br，X＝Cl；

The complex 20: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝F，R₂＝R₅＝H，X＝Cl；

The complex 21: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Cl，R₂＝R₅＝H，X＝Cl；

The complex 22: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Br，R₂＝R₅＝H，X＝Cl。

The complex 23: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝H，X＝Br；

The complex 24: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝H，X＝Br；

The complex 25: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝iPr，R₂＝R₅＝H，X＝Br；

The complex 26: r₂₁＝tBu，R₂₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆＝Me，X＝Br；

The complex 27: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Br，X＝Br；

The complex 28: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Et，X＝Br；

The complex 29: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Me，X＝Br；

The complex 30: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Br，X＝Br；

The complex 31: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝F，R₂＝R₅＝H，X＝Br；

The complex 32: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Cl，R₂＝R₅＝H，X＝Br；

The complex 33: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Br，R₂＝R₅＝H，X＝Br；

The complex 34: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝H，X＝Cl；

The complex 35: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝H，X＝Cl；

The complex 36: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝iPr，R₂＝R₅＝H，X＝Cl；

The complex 37: r₂₁＝tBu，R₂₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆＝Me，X＝Cl；

The complex 38: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Br，X＝Cl；

The complex 39: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Me，R₂＝R₅＝Et，X＝Cl；

The complex 40: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Me，X＝Cl；

The complex 41: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Et，R₂＝R₅＝Br，X＝Cl；

The complex 42: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝F，R₂＝R₅＝H，X＝Cl；

Complex 43: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Cl，R₂＝R₅＝H，X＝Cl；

The complex 44: r₂₁＝tBu，R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Br，R₂＝R₅＝H，X＝Cl。

In the present invention, the second olefin catalyst B can be obtained by referring to the preparation method of the complex disclosed in Organometallics,2013,32, 2291-.

According to the catalyst composition provided by the invention, the molar ratio of the first olefin polymerization catalyst (a) to the second olefin polymerization catalyst (B) is preferably 1:100 to 100:1, and preferably 10:90 to 90: 10.

According to the catalyst composition provided by the invention, the chain shuttling agent can be selected by referring to the existing chain shuttling polymerization reaction; preferably, the chain shuttling agent is selected from the group consisting of at least one C₁-C₂₀Hydrocarbyl group IA, II A, IB, IIB metal compounds or complexes, more preferably selected from the group consisting of C-containing compounds₁-C₁₂Aluminum compound of hydrocarbon group, C₁-C₁₂Gallium compounds containing hydrocarbon radicals or containing C₁-C₁₂A zinc compound of a hydrocarbon group; the hydrocarbyl group is preferably an alkyl group.

Further preferably, the chain shuttling agent is selected from at least one of trialkylaluminum, dialkylzinc and trialkylgallium, more preferably from at least one of triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, diethylzinc and trimethylgallium.

According to the catalyst composition provided by the invention, the olefin polymerization catalyst is combined with a cocatalyst, so that the olefin polymerization catalyst has higher activity. The co-catalyst may be selected from Lewis acids, for example, preferably the co-catalyst is selected from C₁-C₃₀A hydrocarbyl-substituted group IIIA compound, more preferably at least one selected from the group consisting of alkylaluminoxanes, arylboranes and arylborates; further preferably at least one selected from the group consisting of methylaluminoxane, modified methylaluminoxane, triarylborane, and tetraarylborate.

According to the catalyst composition provided by the present invention, preferably, the molar ratio of aluminum in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (0.01-50): 1;

preferably, the molar ratio of the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) to the chain shuttling agent is 1:1 to 1:20000, preferably 1:1 to 1: 1000.

The catalyst composition of the invention is used for olefin polymerization. In the polymerization reaction, an olefin polymerization catalyst consisting of two different active catalysts can be combined with the chain shuttling agent and other components to prepare block copolymers containing segments with different properties.

The present invention also provides a process for the polymerization of olefins, the process comprising: and contacting the catalyst composition with a monomer for copolymerization.

According to the method provided by the invention, preferably, the monomer is selected from ethylene and C₃～C₁₆And C₃～C₁₆At least one of the cyclic olefins of (1).

Said C is₃～C₁₆Examples of the α -olefin or cycloolefin of (b) include: propylene, 1-butene, 1-pentene, decene, cyclopentene, norbornene, 5-methyl-2-norbornene, 1, 5-hexadiene and the like.

Preferably, the olefin in the olefin polymerization process is ethylene, or ethylene and C₃～C₁₆Or a cyclic olefin (comonomer). In addition, the amount of the comonomer can be adjusted according to the melting point of the block copolymer to be prepared in practical application, and will not be described in detail herein.

According to the process of the present invention, the polymerization is carried out as a continuous polymerization, preferably as a continuous solution polymerization. Wherein the catalyst component, the shuttle agent(s), the monomer, and optionally the solvent, the coagent, the scavenger, and the polymerization coagent are continuously supplied to the reactor, and the polymerization product is continuously removed in the reaction vessel. The solvent used in the solution polymerization is not particularly limited, and may be a solvent conventionally used in olefin polymerization, for example, toluene.

According to one embodiment, preferably, the polymerization conditions comprise: the temperature is-20 to 120 ℃, preferably 20 to 120 ℃, and more preferably 40 to 100 ℃; the pressure is 0.1 to 10MPa, preferably 0.1 to 5.0 MPa.

Continuous solution polymerization processes utilizing the polymerization reaction conditions described above, particularly using two or more active polymerization catalyst components. Allows the use of increased reactor temperatures which results in the production of multi-block polymers or segmented polymers with high efficiency. Homogeneous and plug flow type reaction conditions may be used.

Shuttling from the chain shuttling agent to the catalyst under continuous solution polymerization conditions is an advantage over chain extension and forms the multi-block polymers of the present invention, especially linear multi-block polymers, with high efficiency.

The olefin polymerization method belongs to chain shuttling polymerization reaction, and the catalyst composition still has higher polymerization activity at high temperature (such as 60 ℃). During the polymerization, active chains can be alternately grown in the middle of the activities of two different catalysts (i.e., the first olefin polymerization catalyst a and the second olefin polymerization catalyst B) by the chain shuttling agent, and then block copolymers are produced. High molecular weight segmented polymers (multi-block polymers) are prepared comprising two or more, preferably more than three segments differing in density or other chemical or physical properties. The polymer has a molecular weight distribution Mw/Mn of less than 5.0, preferably less than 4.0. Molecular weight distribution (M) of the block copolymer_w/M_n) Preferably less than 5, more preferably less than 4.

The technical scheme of the invention has the following beneficial effects: in the catalyst composition of the present invention, the olefin polymerization catalyst can be matched with a chain shuttling agent at a higher temperature (for example, 90 ℃) to realize copolymerization of ethylene or ethylene and alpha-olefin or cycloolefin (comonomer), under the condition of preparing a block polymer, the molecular weight of the polymer is higher, and the molecular weight distribution is narrower, and the method of the present invention can also prepare block copolymers with different crystallization performances by selecting and controlling the dosage of the comonomer.

Detailed Description

Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, 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.

Characterization of Polymer molecular weight (Mw) and molecular weight distribution (Mw/Mn):

the molecular weight and the distribution thereof are determined by Gel Permeation Chromatography (GPC), the instrument adopts Waters Alliance GPCV 2000, the solvent is 1,2, 4-trichlorobenzene, the sample concentration is lmg/ml, and the solvent flow rate is 1.0 ml/min; the measurement temperature was 150 ℃. Two measurements were made for each sample.

Example 1

The first olefin polymerization catalyst A1 [ the structure of which is shown in formula (1), and the synthesis process of which is described in Organometallics,1998,17,2152-2154 ];

a second olefin polymerization catalyst B1, the structure of which is shown in formula (2), and the synthesis of which is disclosed in the literatures Organometallics,2013,32, 2291-2299;

the cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).

In a1 liter stainless steel autoclave, which was replaced with nitrogen and ethylene three times each, 500 ml of a toluene solvent was then added, and the cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 2

The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1;

the cocatalyst was methylaluminoxane and the shuttling agent was diethyl zinc (DEZ).

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and the cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Catalyst A1(6ml of a 1.0mM toluene solution) and catalyst B1(4ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 3

In a1 liter stainless steel autoclave, which was replaced with nitrogen and ethylene three times each, 500 ml of a toluene solvent was then added, and the cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 1

the cocatalyst is methylaluminoxane without adding a shuttling agent.

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and a cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) was added through a syringe with the addition of toluene. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 2

the cocatalyst is methylaluminoxane without adding a shuttling agent.

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and a cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) was added through a syringe with the addition of toluene. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 3

First olefin polymerization catalyst A1 As in example 1, no second olefin polymerization catalyst B1 was added;

In a1 liter stainless steel autoclave, which was replaced with nitrogen and ethylene three times each, 500 ml of a toluene solvent was then added, and the cocatalyst (3.2ml of a 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Catalyst A1(5ml of a 1.0mM toluene solution) was then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 4

Second olefin polymerization catalyst B1 As in example 1, the first olefin polymerization catalyst A1 was not added;

In a1 liter stainless steel autoclave, which was replaced with nitrogen and ethylene three times each, 500 ml of a toluene solvent was then added, and the cocatalyst (3.2ml of a 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then, catalyst B1(5ml of a 1.0mM toluene solution) was added via a syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was lowered, and the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 5

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, a cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(6ml of a 1.0mM toluene solution) and catalyst B1(4ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 6

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 5

the cocatalyst is methylaluminoxane without adding a shuttling agent.

In a1 liter stainless steel autoclave, nitrogen and ethylene were each replaced three times, then 500 ml of toluene solvent was added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane solution in toluene) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 6

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and 10ml of decene, a cocatalyst (3.2ml of a 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Catalyst A1(5ml of a 1.0mM toluene solution) was then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 7

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and 10ml of decene, a cocatalyst (3.2ml of a 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then, catalyst B1(5ml of a 1.0mM toluene solution) was added via a syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was lowered, and the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 7

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 8

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 9

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(8ml of a 1.0mM toluene solution) and catalyst B1(2ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, the reaction was allowed to proceed at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 8

the cocatalyst was methylaluminoxane and no shuttling agent was added.

In a 1-liter stainless steel autoclave, each of nitrogen and ethylene was substituted three times, and then 500 ml of a toluene solvent was added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene in toluene), and a cocatalyst (6.5ml of 1.53M methylaluminoxane in toluene) were added by syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 10

The first olefin polymerization catalyst A1 is the same as in example 1, and the second olefin polymerization catalyst B2 has the structure shown in formula (3);

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B2(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 11

A first olefin polymerization catalyst A2, the structure of which is shown in formula (4), and the synthesis of which is shown in Macromolecules,1998, 31, 7588-7597);

the second olefin polymerization catalyst B1 was the same as in example 1;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A2(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 12

The first olefin polymerization catalyst A3 has a structure shown in formula (5), and the synthesis is shown in Macromolecules,1998, 31, 7588-7597;

the second olefin polymerization catalyst B1 was the same as in example 1;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A3(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 13

The first olefin polymerization catalyst A4, the result of which is shown in formula (6), and the synthesis of which is shown in J.mol.Catal.A 2009,303, 102-109;

the second olefin polymerization catalyst B3, the result of which is shown by the formula (7),

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A4(5ml of a 1.0mM toluene solution) and catalyst B3(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 14

the cocatalyst is tetrakis (pentafluorophenyl) borate Ph₃CB(C₆F₅)₄The shuttling agent is diethyl zinc (DEZ);

in a1 liter stainless steel autoclave, nitrogen and ethylene were each replaced three times, and then 500 ml of a toluene solvent was added, and with the addition of toluene, 20ml of decene, a co-catalyst (10ml of Ph at a concentration of 1.0 mM) were added₃CB(C₆F₅)₄Toluene solution of tetrakis (pentafluorophenyl) borate, 5ml of a 1.0M solution of triisobutylaluminum in toluene) and DEZ (1ml of a 1.5M solution in toluene) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, the pressure was raised and maintained at 1.0MPa, the mixture was polymerized at 90 ℃ for 30 minutes, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 15

The first olefin polymerization catalyst A1 was the same as in example 1;

the second olefin polymerization catalyst B4 has a structure shown in formula (8),

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 16

The first olefin polymerization catalyst A1 was the same as in example 1, and the second olefin polymerization catalyst B4 was the same as in example 15;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, a cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(6ml of a 1.0mM toluene solution) and catalyst B4(4ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 17

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B4(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 9

the cocatalyst was methylaluminoxane and no shuttling agent was added.

Specific polymerization results are listed in table 1.

Comparative example 10

Second olefin polymerization catalyst B4 As in example 15, the first olefin polymerization catalyst A1 was not added;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and 10ml of decene, a cocatalyst (3.2ml of a 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of a 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then, catalyst B4(5ml of a 1.0mM toluene solution) was added via a syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was lowered, and the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 18

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B4(8ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 19

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 20

In a 1-liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe. Catalyst A1(8ml of a 1.0mM toluene solution) and catalyst B4(2ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, the reaction was allowed to proceed at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 11

the cocatalyst was methylaluminoxane and no shuttling agent was added.

In a 1-liter stainless steel autoclave, each of nitrogen and ethylene was substituted three times, and then 500 ml of a toluene solvent was added, and with the addition of toluene, 20ml of norbornene (5.0M norbornene in toluene), and a cocatalyst (6.5ml of 1.53M methylaluminoxane in toluene) were added by syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised to and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 21

The first olefin polymerization catalyst A1 was the same as in example 1, and the second olefin polymerization catalyst B5 was represented by the following formula (9),

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B5(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 22

The first olefin polymerization catalyst A2 was the same as in example 11, and the second olefin polymerization catalyst B4 was the same as in example 15;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A2(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 23

The first olefin polymerization catalyst A3 was the same as in example 12, and the second olefin polymerization catalyst B4 was the same as in example 15;

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A3(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 24

The first olefin polymerization catalyst A4 was the same as in example 13, and the second olefin polymerization catalyst B6 was represented by the following formula (10),

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A4(5ml of a 1.0mM toluene solution) and catalyst B6(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Example 25

the cocatalyst is tetrakis (pentafluorophenyl) borate Ph₃CB(C₆F₅)₄The shuttling agent is diethyl zinc (DEZ).

In a1 liter stainless steel high pressure polymerizer,the mixture was replaced three times with nitrogen and ethylene, 500 ml of toluene solvent were added, and with the addition of toluene, 20ml of decene, cocatalyst (10ml of 1.0mM Ph) were added₃CB(C₆F₅)₄Toluene solution of tetrakis (pentafluorophenyl) borate, 5ml of a 1.0M solution of triisobutylaluminum in toluene) and DEZ (1ml of a 1.5M solution in toluene) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B4(5ml of a 1.0mM toluene solution) were added via syringe, the pressure was raised and maintained at 1.0MPa, the mixture was polymerized at 90 ℃ for 30 minutes, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

Comparative example 12

The first olefin polymerization catalyst A1 was the same as in example 1, and the second olefin polymerization catalyst B7 was represented by the following formula (11),

In a1 liter stainless steel autoclave, each of which was replaced with nitrogen and ethylene three times, 500 ml of a toluene solvent was then added, and with the addition of toluene, 20ml of decene, cocatalyst (6.5ml of a 1.53M methylaluminoxane toluene solution) and DEZ (1ml of a 1.5M DEZ toluene solution) were added via syringe. Catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B7(5ml of a 1.0mM toluene solution) were then added via syringe, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 90 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.

Specific polymerization results are listed in table 1.

TABLE 1 ethylene and C₃-C₁₆As a result of copolymerization of alpha-olefins or cyclic olefins

In Table 1, "-" indicates that the resulting polymer had no melting point, and nd indicates that no test was conducted.

As can be seen from Table 1, the molecular weight distribution of the polymer obtained using the catalyst composition of the present invention example is significantly lower than that of the comparative example (using catalyst A and catalyst B, but without adding a chain transfer agent). Comparative example using catalyst A alone, the polymer obtained under the same conditions was lower in molecular weight, comparative example using catalyst B alone, the polymer obtained was higher in molecular weight, and the polymer molecular weight distributions Mw/Mn of examples 1-25 were lower, indicating that when a composition comprising catalyst A and catalyst B was used, a block polymer was formed under the action of the chain shuttling agent, rather than the mixture of polymers prepared using catalyst A, B alone in the comparative example, otherwise the Mw/Mn of the polymers obtained in examples 1-25 should be much greater than 4. Compared with comparative example 12 (using catalyst A1 and catalyst B7, but the structure of catalyst B7 is different from that of the present invention), the catalyst composition using the present invention still has higher polymerization activity under high temperature conditions, and the molecular weight of the resulting polymer is significantly higher than that of comparative example 12.

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

1. A catalyst composition for the polymerization of olefins, wherein the catalyst composition is a mixture or reaction product comprising:

(3) a chain shuttling agent;

(4) a cocatalyst.

2. The catalyst composition of claim 1,

(1) a first olefin polymerization catalyst (A) selected from at least one metal complex represented by the general formula III:

in the general formula III, R¹～R⁵，R⁷，R⁹，R¹¹The same or different, each independently selected from hydrogen and C₁～C₂₀Aliphatic hydrocarbon group of (C)₆～C₃₀Aromatic hydrocarbon groups of (a) or halogen; and optionally, R¹And R⁴Are connected to each other in a loop, and-Or R²And R⁵Are connected with each other to form a ring; m is titanium, zirconium or hafnium, and X is halogen.

3. The catalyst composition of claim 1, wherein in formula II, R₁-R₁₀The same or different, each independently selected from hydrogen and C₁～C₂₀Saturated hydrocarbon group of (C)₂～C₂₀Unsaturated hydrocarbon group of (C)₁～C₂₀Hydrocarbyloxy or halogen of (a); r₂₁、R₂₂The same or different, each independently selected from hydrogen and C₁～C₂₀Saturated hydrocarbon group of (C)₂～C₂₀Unsaturated hydrocarbon group of (C)₁～C₂₀Hydrocarbyloxy or halogen of (a); m is nickel or palladium, and X is selected from halogen.

4. The catalyst composition of claim 3, wherein in formula II, R₁-R₁₀The same or different, each independently selected from hydrogen and C₁～C₁₀Saturated hydrocarbon group of (C)₂-C₁₀Unsaturated hydrocarbon group of (C)₁～C₁₀Alkoxy or halogen of (a).

5. The catalyst composition of claim 4, wherein in formula II, R₁-R₁₀The same or different, each independently selected from hydrogen and C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a).

6. The catalyst composition of claim 3, wherein in formula II, R₂₁、R₂₂The same or different, each independently selected from hydrogen and C₁～C₁₀A hydrocarbon group of₁～C₁₀Alkoxy or halogen of (a).

7. The catalyst composition of claim 6, wherein in formula II, R₂₁、R₂₂Are the same or different and are each independently selected fromHydrogen, C₁～C₆Alkyl of (C)₂～C₆Alkenyl of, C₁～C₆Alkoxy or halogen of (a).

8. The catalyst composition according to claim 1, wherein the second olefin polymerization catalyst (B) is selected from at least one of the following metal complexes; in the general formula II, R₇-R₁₀Are both hydrogen, M is nickel:

The complex 22: r₂₁＝R₂₂＝H，R₁＝R₃＝R₄＝R₆＝Br，R₂＝R₅＝H，X＝Cl；

9. The catalyst composition according to claim 1, wherein the molar ratio of the first olefin polymerization catalyst (a) to the second olefin polymerization catalyst (B) is from 1:100 to 100: 1.

10. The catalyst composition according to claim 9, wherein the molar ratio of the first olefin polymerization catalyst (a) to the second olefin polymerization catalyst (B) is 10:90 to 90: 10.

11. The catalyst composition of any of claims 1-10, wherein the chain shuttling agent is selected from the group consisting of at least one C₁-C₂₀Hydrocarbyl group IA, II A, IB, IIB metal compounds or complexes.

12. According toThe catalyst composition of claim 1, wherein the chain shuttling agent is selected from the group consisting of C₁-C₁₂Aluminum compound of hydrocarbon group, C₁-C₁₂Gallium compounds containing hydrocarbon radicals or containing C₁-C₁₂A zinc compound of a hydrocarbon group.

13. The catalyst composition of claim 11, wherein the hydrocarbyl group is an alkyl group.

14. The catalyst composition of claim 12, wherein the hydrocarbyl group is an alkyl group.

15. The catalyst composition of claim 12, wherein the chain shuttling agent is selected from at least one of a trialkyl aluminum, a dialkyl zinc, and a trialkyl gallium.

16. The catalyst composition of claim 15, wherein the chain shuttling agent is selected from at least one of triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, diethylzinc, and trimethylgallium.

17. The catalyst composition of any of claims 1-10, wherein the co-catalyst is selected from C₁-C₃₀Hydrocarbyl-substituted group IIIA compounds.

18. The catalyst composition of claim 17, wherein the cocatalyst is selected from at least one of alkylaluminoxane, arylborane, and arylborate.

19. The catalyst composition of claim 18, wherein said cocatalyst is selected from at least one of methylaluminoxane, modified methylaluminoxane, triarylborane, and tetraarylborate.

20. The catalyst composition according to claim 1, wherein the molar ratio of aluminum in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (0.01-50): 1;

the molar ratio of the sum of the first olefin polymerization catalyst (A) and the second olefin polymerization catalyst (B) to the chain shuttling agent is 1: 1-1: 20000.

21. The catalyst composition of claim 1, wherein the molar ratio of the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) to the chain shuttling agent is from 1:1 to 1: 1000.

22. A process for the polymerization of olefins, the process comprising: contacting the catalyst composition of any one of claims 1-21 with a monomer for polymerization.

23. The method of claim 22, wherein the monomer is selected from ethylene, C₃～C₁₆And C₃～C₁₆At least one of the cyclic olefins of (a);

the polymerization conditions include: the temperature is-20 to 150 ℃, and the pressure is 0.1 to 10 MPa.