Catalyst composition and olefin polymerization method

Abstract

The invention relates to the technical field of olefin polymerization catalysts, and discloses a catalyst composition and an olefin polymerization method. The catalyst composition contains a first metal complex as shown in a formula (I), a second metal complex as shown in a formula (II), a chain shuttling agent and a cocatalyst. The olefin polymerization method comprises the step of carrying out olefin polymerization reaction on an olefin monomer in the presence of the catalyst composition. The catalyst composition provided by the invention still has relatively high polymerization activity at a high temperature (such as 90 DEG C), and a block copolymer can be generated.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization catalyst technology, and more specifically to a catalyst composition and an olefin polymerization method. Background Technology

[0002] The preparation of polymers with novel structures and excellent properties using inexpensive monomers has always been one of the research directions that polymer chemistry researchers have been working tirelessly towards. In 2006, Arriola et al. of Dow Chemical Company in the United States used FI-type zirconium catalyst and aminopyridine hafnium catalyst from Mitsui Chemicals Co., Ltd. in Japan to prepare olefin block copolymers (OBCs) with alternating semi-crystalline and amorphous segment structures under the action of diethylzinc (ZnEt2) (see: Science, 2006, 312(5):714-719). In many properties, OBCs have surpassed other types of thermoplastic polyolefins. For example, in terms of thermal properties, compared with polyolefin elastomers, OBCs exhibit a faster crystallization rate and a more regular crystal morphology, and have better heat resistance. In terms of mechanical properties, OBCs show higher tensile strength, tear strength, elongation at break, and elastic recovery than traditional polyolefin thermoplastic elastomers, making them an ideal alternative to styrene block copolymer TPEs. In terms of processing performance, compared with olefin random copolymers and blends, OBC has the characteristics of easy processing and a balance of rigidity and toughness (see: Elastomers, 2018(3):69-75). Therefore, thanks to its unique properties, it has received widespread attention from the academic and industrial communities at home and abroad.

[0003] In the synthesis of block copolymers, the complexation and separation processes between the catalyst active center and the chain shuttle need to be rapid and reversible. As a novel thermoplastic elastomer, the catalyst olefin block copolymer must have high polymerization activity, but it cannot become a dormant species due to excessively strong binding between the active center and the chain shuttle (see: Macromolecules, 2008, 41(12):4090-4094). Therefore, screening a suitable catalytic system is extremely difficult, and the research progress on the preparation of single-active-center catalysts for OBCs has been relatively slow.

[0004] In 1995, Brookhart et al. pioneered the synthesis of a series of highly active α-diimine nickel / palladium catalysts, which exhibit unique chain-shunt behavior. These catalysts can catalyze the homopolymerization of ethylene to prepare branched polymers with a branching degree of up to 116 branches / 1000C (see: J Am Chem Soc, 1995, 117(23):6414-6415). Furthermore, US6380341B1 and US6169151B1 report the use of stereometallocene catalysts, which exhibit different reaction rates and other polymerization characteristics through interconversion between two stereoconfigurations to form block-structured olefin polymers. Chain shuttle polymerization can prepare novel block polymers with different structures, offering strong product controllability and broad application prospects. Current research reports the use of nickel diimide metallocerocatalysts to achieve chain shuttle polymerization in the presence of diethylzinc (Macromolecules 2009, 42, 1834-1837). However, the polymerization temperature is relatively low, only 20°C, and the "soft" and "hard" segments of the block copolymer lack precise control. This results in poor reactant flowability and low olefin polymerization activity at high temperatures, failing to meet the requirements of existing solution-based ethylene polymerization equipment. Furthermore, the types of olefin polymerization catalysts capable of achieving chain shuttle polymerization in the presence of chain transfer agents are very limited. Therefore, new catalyst systems for olefin polymerization capable of chain shuttle polymerization are still needed to meet industrial requirements. In addition, existing α-diimide nickel catalysts exhibit very low activity in ethylene polymerization at high temperatures, and the molecular weight of the prepared polyethylene decreases rapidly with increasing polymerization temperature. Summary of the Invention

[0005] The purpose of this invention is to address the aforementioned problems in the prior art by providing a catalyst composition and a method for olefin polymerization. Both the first and second metal complexes used can maintain high copolymerization activity of ethylene with C3-C16 α-olefins or cyclic olefins at higher temperatures, and the resulting polymers have high molecular weights and narrow molecular weight distributions. Block polymers can be prepared under the action of chain shuttles, and the structure and crystallinity of the resulting polymers can be controlled by selecting and controlling the amount of C3-C16 α-olefins or cyclic olefins used as comonomers.

[0006] To achieve the above objectives, the present invention provides a catalyst composition comprising a first metal complex, a second metal complex, a chain shuttle agent, and a co-catalyst, wherein...

[0007] The first metal complex is selected from at least one of the complexes shown in formula (I).

[0008]

[0009] In formula (I), M is selected from group IVB transition metals; n is an integer from 1 to 30, and when m is 2 or greater, multiple X groups may be the same or different; m is an integer that satisfies the valence state of M;

[0010] X is selected from halogens, hydrocarbon groups, hydroxyl groups, acid radicals, and amino groups;

[0011] R 1 -R 8 They may be the same or different, each independently selected from hydrogen, halogen, C1-C20 aliphatic hydrocarbon group, C3-C20 cyclic hydrocarbon group and C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group may be optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin heteroatom.

[0012] R 9 and R 10 They may be the same or different, and each is independently selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and substituted or unsubstituted C6-C30 aromatic hydrocarbon groups;

[0013] The second metal complex is selected from at least one of the complexes shown in formula (II).

[0014]

[0015] In formula (II), R1-R6 may be the same or different, and each is independently selected from hydrogen, hydrocarbon group, hydrocarbon group, substituted or unsubstituted C1-C20 alkyl group and substituted or unsubstituted C6-C30 aryl group;

[0016] M1 is selected from group VIII metals, and the two X1s may be the same or different, and each is a halogen.

[0017] Preferably, in formula (I), M is titanium, zirconium, or hafnium.

[0018] Preferably, in formula (I), R 1 -R 8 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, and methoxy; R 9 -R 10 Each is independently selected from n-hexyl, cycloalkyl, halophenyl, nitro-substituted phenyl, alkyl-substituted phenyl, alkyl-substituted cycloalkyl, naphthalene, and biphenyl; X is a halogen or C1-C8 hydrocarbon group; n is an integer from 1 to 10.

[0019] Preferably, in formula (II), M1 is nickel or palladium.

[0020] Preferably, in formula (II), R1-R6 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, substituted or unsubstituted C6-C15 aromatic hydrocarbon groups.

[0021] Preferably, the second metal complex is selected from at least one of the following complexes:

[0022] Complex 1: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br;

[0023] Complex 2: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br;

[0024] Complex 3: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br;

[0025] Complex 4: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br;

[0026] Complex 5: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br;

[0027] Complex 6: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br;

[0028] Complex 7: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br;

[0029] Complex 8: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br;

[0030] Complex 9: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Br;

[0031] Complex 10: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl;

[0032] Complex 11: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl;

[0033] Complex 12: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl;

[0034] Complex 13: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl;

[0035] Complex 14: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl;

[0036] Complex 15: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl;

[0037] Complex 16: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl;

[0038] Complex 17: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl;

[0039] Complex 18: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Cl.

[0040] Preferably, the molar ratio of the first metal complex to the second metal complex is 1:100 to 100:1, and more preferably 10:90 to 90:10.

[0041] Preferably, the molar ratio of the sum of the first metal complex and the second metal complex to the chain shuttle is 1:(1-20000), more preferably 1:(1-1000).

[0042] Preferably, the chain shuttle is selected from group IA, IIA, IB, IIB metal compounds or complexes containing at least one C1-C20 hydrocarbon group, and more preferably from aluminum compounds containing C1-C12 hydrocarbon groups, gallium compounds containing C1-C12 hydrocarbon groups, and zinc compounds containing C1-C12 hydrocarbon groups; the hydrocarbon group is preferably alkyl.

[0043] Preferably, the chain shuttle 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.

[0044] Preferably, the cocatalyst is selected from C1-C30 hydrocarbon-substituted Group IIIA compounds, more preferably from at least one of alkylaluminoxanes, arylboranes, and arylborates; more preferably from at least one of methylaluminoxanes, modified methylaluminoxanes, triarylboranes, and tetraarylborates.

[0045] Preferably, the molar ratio of aluminum in the co-catalyst to the sum of the first metal complex and the second metal complex is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first metal complex and the second metal complex is (0.01-50):1.

[0046] A second aspect of the present invention provides a method for olefin polymerization, the method comprising: olefin monomers undergoing an olefin polymerization reaction in the presence of a catalyst composition provided by the present invention.

[0047] Preferably, the olefin monomer is selected from at least one of ethylene, C3-C16 α-olefins, and C3-C16 cycloolefins.

[0048] Preferably, the conditions for the olefin polymerization reaction include: a temperature of -20°C to 150°C and a pressure of 0.1-10 MPa.

[0049] According to the technical solution of the present invention, the catalyst composition still exhibits high polymerization activity at high temperatures (e.g., 90°C). The olefin polymerization process using the catalyst composition of the present invention is a chain shuttle polymerization reaction. During the polymerization reaction, the active chains can alternately grow between the activities of two different catalysts (i.e., the first metal complex and the second metal complex) through the chain shuttle agent, thereby generating block copolymers. The molecular weight distribution (M...) of the block copolymer... w / M n Less than 5 (preferably less than 4).

[0050] According to the olefin polymerization method described in this invention, block copolymers with different crystallinity properties can be prepared by selecting and controlling the amount of comonomers. Detailed Implementation

[0051] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0052] The catalyst composition of the present invention comprises a first metal complex, a second metal complex, a chain shuttle, and a co-catalyst, wherein,

[0053] The first metal complex is selected from at least one of the complexes shown in formula (I).

[0054]

[0055] In formula (I), M is selected from group IVB transition metals; n is an integer from 1 to 30, and when m is 2 or greater, multiple X groups may be the same or different; m is an integer that satisfies the valence state of M;

[0056] X is selected from halogens, hydrocarbon groups, hydroxyl groups, acid radicals, and amino groups;

[0057] R 1 -R 8 They may be the same or different, each independently selected from hydrogen, halogen, C1-C20 aliphatic hydrocarbon group, C3-C20 cyclic hydrocarbon group and C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group may be optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin heteroatom.

[0058] R 9 and R 10 They may be the same or different, and each is independently selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and substituted or unsubstituted C6-C30 aromatic hydrocarbon groups;

[0059] The second metal complex is selected from at least one of the complexes shown in formula (II).

[0060]

[0061] In formula (II), R1-R6 may be the same or different, and each is independently selected from hydrogen, hydrocarbon group, hydrocarbon group, substituted or unsubstituted C1-C20 alkyl group and substituted or unsubstituted C6-C30 aryl group;

[0062] M1 is selected from group VIII metals, and the two X1s may be the same or different, and each is a halogen.

[0063] In formula (I), M is a group IVB transition metal, preferably titanium, zirconium or hafnium.

[0064] In equation (I), in the preferred case, R 1 -R8 Selected from hydrogen, halogens, C1-C20 aliphatic hydrocarbon groups, and C6-C20 aromatic hydrocarbon groups. More preferably, R 1 -R 8 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, and methoxy.

[0065] In equation (I), in the preferred case, R 9 -R 10 Selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and substituted or unsubstituted C6-C20 aromatic hydrocarbon groups. More preferably, R 9 -R 10 Each is independently selected from n-hexyl, cycloalkyl, halophenyl, nitro-substituted phenyl, alkyl-substituted phenyl, alkyl-substituted cycloalkyl, naphthalene, and biphenyl.

[0066] In formula (I), preferably, X is a halogen or a C1-C8 hydrocarbon group.

[0067] In equation (I), preferably, n is an integer from 1 to 10.

[0068] In this document, C1-C20 aliphatic hydrocarbon groups refer to straight-chain hydrocarbon groups of C1-C20 or branched hydrocarbon groups of C3-C10, and non-limiting examples 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.

[0069] In this document, the aromatic hydrocarbon group of C6-C20 can be aryl, aralkyl, or alkylaryl, and non-limiting examples include: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, phenyl-tert-butyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0070] In this document, halogen refers to fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

[0071] In this invention, the preparation method of the first metal complex may include: reacting the ligand compound represented by formula (III) with a hydrogen-removing agent, and then reacting it with the M metal compound (MX). m ( ) to react.

[0072] The specific reaction process is shown in the following formula:

[0073]

[0074] Among them, R 1 -R10 The definitions of M and X are the same as those described above; m is the number of X values ​​that satisfy the M valence state, such as 1, 2 or 3.

[0075] In the above method, the M metal compound is selected from at least one of titanium tetrachloride, bis(tetrahydrofuran)titanium tetrachloride, tri(tetrahydrofuran)titanium trichloride, zirconium tetrachloride, bis(tetrahydrofuran)zirconium tetrachloride, hafnium tetrachloride and bis(tetrahydrofuran)hafnium tetrachloride.

[0076] In the above method, the hydrogen-removing agent is selected from at least one of NaH, KH, n-butyllithium, and methyllithium.

[0077] In formula (II), M1 is selected from group VIII metals, preferably nickel or palladium.

[0078] In formula (II), X1 is a halogen, specifically fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

[0079] In formula (II), R1-R6 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, substituted or unsubstituted C6-C15 aromatic hydrocarbon groups. The substituents may be selected from halogens, hydroxyl groups, C1-C10 alkyl groups, halogenated C1-C10 alkyl groups, C1-C10 alkoxy groups, and halogenated C1-C10 alkoxy groups, preferably from halogens, hydroxyl groups, C1-C6 alkyl groups, halogenated C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogenated C1-C6 alkoxy groups.

[0080] In this document, examples of C1-C6 alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, and n-hexyl.

[0081] In this document, examples of C1-C6 alkoxy groups include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, and 3,3-dimethylbutoxy.

[0082] Most preferably, the second metal complex is selected from at least one of the following complexes:

[0083] Complex 1: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br;

[0084] Complex 2: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br;

[0085] Complex 3: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br;

[0086] Complex 4: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br;

[0087] Complex 5: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br;

[0088] Complex 6: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br;

[0089] Complex 7: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br;

[0090] Complex 8: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br;

[0091] Complex 9: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Br;

[0092] Complex 10: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl;

[0093] Complex 11: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl;

[0094] Complex 12: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl;

[0095] Complex 13: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl;

[0096] Complex 14: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl;

[0097] Complex 15: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl;

[0098] Complex 16: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl;

[0099] Complex 17: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl;

[0100] Complex 18: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Cl.

[0101] In this invention, the second metal complex can be prepared by conventional methods, such as those described in Organometallics, 2011, 30, 2418-2424; patent application WO2012122854A1; or Organometallics, 2015, 34, 582-590. All relevant contents disclosed in these documents are incorporated herein by reference and will not be repeated here.

[0102] In the catalyst composition of the present invention, the molar ratio of the first metal complex to the second metal complex can be 1:100 to 100:1, preferably 10:90 to 90:10, and more preferably 1:10 to 10:1.

[0103] In the catalyst composition of the present invention, the molar ratio of the sum of the first metal complex and the second metal complex to the chain shuttle can be 1:(1-20000), preferably 1:(1-1000).

[0104] In the catalyst composition of this invention, the chain shuttle can be a conventional choice in the art. Preferably, the chain shuttle is selected from group IA, IIA, IB, and IIB metal compounds or complexes containing at least one C1-C20 hydrocarbon group; more preferably, it is selected from aluminum compounds containing a C1-C12 hydrocarbon group (such as straight-chain or branched C2-C8 alkyl groups), gallium compounds containing a C1-C12 hydrocarbon group (such as straight-chain or branched C2-C8 alkyl groups), and zinc compounds containing a C1-C12 hydrocarbon group (such as straight-chain or branched C2-C8 alkyl groups). Here, the hydrocarbon group is preferably an alkyl group.

[0105] In a preferred embodiment, the chain shuttle 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.

[0106] In the catalyst composition of the present invention, the olefin polymerization catalyst can be made more active by introducing a co-catalyst. The co-catalyst can be selected from Lewis acids, specifically, for example, Group IIIA compounds containing C1-C30 hydrocarbon groups in their chemical structure. Preferably, the co-catalyst is selected from at least one of alkylaluminoxanes, arylboranes, and arylborates, and more preferably from at least one of methylaluminoxanes, modified methylaluminoxanes, triarylboranes, and tetraarylborates.

[0107] In the catalyst composition of the present invention, preferably, the molar ratio of aluminum in the co-catalyst to the sum of the first metal complex and the second metal complex is (10-20000):1, more preferably (100-5000):1; or the molar ratio of boron in the co-catalyst to the sum of the first metal complex and the second metal complex is (0.01-50):1, more preferably (1-20):1.

[0108] In this invention, the components of the catalyst composition (including the first metal complex, the second metal complex, the chain shuttle, and the co-catalyst) can be stored independently or in combination. Preferably, to achieve better reaction results during olefin polymerization, each component of the catalyst composition is added independently; therefore, it is preferable that the components of the catalyst composition are stored independently.

[0109] This invention also provides an olefin polymerization method, comprising: an olefin monomer undergoing an olefin polymerization reaction in the presence of a catalyst composition provided by this invention. According to the olefin polymerization method of this invention, the catalyst used, through a combination of two different metal complexes and a chain shuttle, can prepare block copolymers containing segments with different properties.

[0110] In the olefin polymerization method described in this invention, the components of the catalyst composition (including the first metal complex, the second metal complex, the chain shuttle, and the co-catalyst) can be added independently or in a mixed state. To obtain better reaction results, it is preferable that the components of the catalyst composition be added independently.

[0111] In some embodiments, the specific process of the olefin polymerization method may include: purging the reactor several times with a protective gas and ethylene, then adding an organic solvent to the reactor, followed by adding a co-catalyst and a chain shuttle, then adding a first metal complex and a second metal complex, as well as optional other olefin monomers (comonomers other than ethylene, especially α-olefins and cycloolefins), then increasing the pressure of the reactor to the reaction pressure, and then heating to the reaction temperature to carry out the reaction.

[0112] In the olefin polymerization method described in this invention, the protective gas can be nitrogen or an inert gas.

[0113] In the olefin polymerization method described in this invention, the conditions for the olefin polymerization reaction may include: a temperature of -20°C to 150°C, preferably 20-90°C, more preferably 40-90°C; and a pressure of 0.1-10 MPa, preferably 0.5-3 MPa. In this document, the "pressure" of the polymerization reaction refers to the ethylene pressure in the polymerization system, expressed in absolute pressure.

[0114] In the olefin polymerization method of the present invention, the olefin polymerization reaction time can be 0.1-3h, preferably 0.1-1h.

[0115] In the olefin polymerization method described in this invention, the organic solvent is not particularly limited and can be any conventional choice used in olefin polymerization reactions, such as n-heptane.

[0116] In the olefin polymerization method described in this invention, the olefin monomer may be selected from ethylene and at least one of C3-C16 α-olefins or cycloolefins. Examples of C3-C16 α-olefins or cycloolefins include: propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, cyclopentene, norbornene, 5-methyl-2-norbornene, 1,5-hexadiene, etc.

[0117] In the olefin polymerization method described in this invention, preferably, the olefin is ethylene, or a combination of ethylene and C3-C16 α-olefins or cycloolefins (comonomers). Furthermore, the amount of comonomer used can be adjusted according to the melting point required for the prepared block copolymer in practical applications, which will not be elaborated further here.

[0118] The olefin polymerization method of this invention belongs to chain shuttle polymerization, and the catalyst composition still exhibits high polymerization activity at high temperatures (e.g., 90°C). During the polymerization reaction, the active chains can alternately grow between the active and reactive states of two different metal complexes (i.e., the first metal complex and the second metal complex) through the chain shuttle agent, thereby generating a block copolymer. The molecular weight distribution (M...) of the block copolymer... w / M n The content of the copolymer is less than 5 (preferably less than 4). The method of this invention can also prepare block copolymers with different crystallinity properties by selecting the comonomer and controlling its dosage.

[0119] The catalyst composition and olefin polymerization method of the present invention are further illustrated below through examples. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0120] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0121] The analytical characterization instruments and testing methods used in the following examples and comparative examples are as follows:

[0122] (1) Molecular weight and molecular weight distribution of polymers (PDI = M w / M n The determination was performed using a PL-GPC220 chromatograph with trichlorobenzene as solvent at 150℃ (standard: PS, flow rate: 1.0 mL / min, column: 3×PL gel 10um M1×ED-B, 300×7.5 nm).

[0123] (2) Activity measurement method: The polymer was washed with hydrochloric acid ethanol solution, vacuum dried, and the weight of the polymer was obtained. The polymerization activity was calculated as: polymer weight (g) / metal (mol) × 60 / polymerization time (min).

[0124] Example 1

[0125] First metal complex:

[0126] Metal complex A1: The complex shown in formula (I), where M is Zr and R is... 1 -R 8 For H, R 9 and R 10 X is phenyl, and n = 2.

[0127]

[0128] In a nitrogen atmosphere, compound L1 (M is Zr, R is R) of formula (III) was added to a three-necked flask. 1 -R 8 For H, R 9 and R 10 0.49 g (1.26 mmol) of phenyl group was dissolved in 25 mL of tetrahydrofuran, and then the temperature was lowered to below -70 °C. 1.06 mL (1.68 mmol) of n-butyllithium solution was slowly added dropwise. The reaction was carried out at this temperature for 1 hour, then slowly heated to room temperature and reacted for 4 hours. The reaction solution was transferred to a constant-pressure dropping funnel and slowly added dropwise at below -70 °C to 20 mL of tetrahydrofuran solution containing 0.32 g (0.84 mmol) of ZrCl4(THF)2. After the addition was complete, the temperature was gradually raised to room temperature, and the reaction was carried out for approximately 18 hours, followed by reflux for 5 hours. The solution was then distilled under reduced pressure until dry, dissolved in 20 mL of dichloromethane, and the insoluble matter was filtered off. The filtrate was then evaporated under reduced pressure until dry, washed with n-heptane, and dried under vacuum to obtain 0.50 g of the metal complex A1 (golden yellow powder), with a yield of 80%. Elemental analysis: Theoretical values ​​are C, 62.56; H, 3.77; N, 5.61; Test values ​​are C, 62.21; H, 3.56; N, 5.78.

[0129] First metal complex:

[0130] This embodiment uses the metal complex B1 shown in the following formula, and its synthesis method can be found in the literature Organometallics, 2011, 30, 2418-2424.

[0131]

[0132] Co-catalyst: Methylaluminoxane;

[0133] Chain shuttle: Diethylzinc (ZnEt2).

[0134] Olefin polymerization reaction:

[0135] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.0 M toluene solution) were added via syringe. Next, metal complex A1 (5 mL of a 1.0 mM n-heptane solution) and metal complex B1 (5 mL of a 1.0 mM n-heptane solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, and the polymer was collected and weighed. The specific polymerization results are listed in Table 1.

[0136] Example 2

[0137] First metal complex: Metal complex A1 (same as in Example 1);

[0138] Second metal complex: Metal complex B1 (same as in Example 1);

[0139] Co-catalyst: Methylaluminoxane;

[0140] Chain shuttle: Diethylzinc (ZnEt2).

[0141] Olefin polymerization reaction:

[0142] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.0 M toluene solution) were added via syringe. Then, metal complex A1 (5 mL of a 1.0 mM n-heptane solution), metal complex B1 (5 mL of a 1.0 mM n-heptane solution), and 15 mL of 1-hexene were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The reactor was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0143] Example 3

[0144] First metal complex: Metal complex A1 (same as in Example 1);

[0145] Second metal complex: Metal complex B1 (same as in Example 1);

[0146] Co-catalyst: Methylaluminoxane;

[0147] Chain shuttle: Diethylzinc (ZnEt2).

[0148] Olefin polymerization reaction:

[0149] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.0 M toluene solution) were added via syringe. Then, metal complex A1 (5 mL of a 1.0 mM n-heptane solution), metal complex B1 (5 mL of a 1.0 mM n-heptane solution), and 15 mL of 1-decene were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The reactor was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0150] Example 4

[0151] First metal complex: Metal complex A1 (same as in Example 1);

[0152] Second metal complex: Metal complex B1 (same as in Example 1);

[0153] Co-catalyst: Methylaluminoxane;

[0154] Chain shuttle: Diethylzinc (ZnEt2).

[0155] Olefin polymerization reaction:

[0156] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.0 M toluene solution) were added via syringe. Next, metal complex A1 (2 mL of a 1.0 mM n-heptane solution) and metal complex B1 (8 mL of a 1.0 mM n-heptane solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0157] Example 5

[0158] First metal complex: Metal complex A1 (same as in Example 1);

[0159] Second metal complex: Metal complex B1 (same as in Example 1);

[0160] Co-catalyst: Methylaluminoxane;

[0161] Chain shuttle: Diethylzinc (ZnEt2).

[0162] Olefin polymerization reaction:

[0163] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.0 M toluene solution) were added via syringe. Next, metal complex A1 (6 mL of a 1.0 mM n-heptane solution) and metal complex B1 (4 mL of a 1.0 mM n-heptane solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, and the polymer was collected and weighed. The specific polymerization results are listed in Table 1.

[0164] Example 6

[0165] First metal complex: Metal complex A1 (same as in Example 1);

[0166] Second metal complex: Metal complex B1 (same as in Example 1);

[0167] Co-catalyst: Triphenylmethyltetra(pentafluorophenyl)borate / triisobutylaluminum;

[0168] Chain shuttle: Diethylzinc (ZnEt2).

[0169] Olefin polymerization reaction:

[0170] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the n-heptane, the co-catalyst (3.0 mL of a 1.0 mM solution of triphenylmethyltetra(pentafluorophenyl)borate in n-heptane and 2 mL of a 1.0 M solution of triisobutylaluminum in toluene) and ZnEt2 (1 mL of a 1.0 M solution of toluene) were added via syringe. Next, metal complex A1 (5 mL of a 1.0 mM solution of n-heptane) and metal complex B1 (5 mL of a 1.0 mM solution of n-heptane) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, and the polymer was collected and weighed. The specific polymerization results are listed in Table 1.

[0171] Example 7

[0172] First metal complex: Metal complex A1 (same as in Example 1);

[0173] Second metal complex:

[0174] This embodiment uses the metal complex B2 shown in the following formula, the synthesis method of which can be found in the literature Organometallics, 2011, 30, 2418-2424.

[0175]

[0176] Co-catalyst: Methylaluminoxane;

[0177] Chain shuttle: Diethylzinc (ZnEt2).

[0178] Olefin polymerization reaction:

[0179] The olefin polymerization reaction was carried out in accordance with Example 1, except that the metal complex B2 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0180] Example 8

[0181] First metal complex: Metal complex A1 (same as in Example 1);

[0182] Second metal complex:

[0183] This embodiment uses the metal complex B3 shown in the following formula, and its synthesis method can be found in the literature Organometallics, 2015, 34, 582-590.

[0184]

[0185] Co-catalyst: Methylaluminoxane;

[0186] Chain shuttle: Diethylzinc (ZnEt2).

[0187] Olefin polymerization reaction:

[0188] The olefin polymerization reaction was carried out in accordance with Example 1, except that the metal complex B3 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0189] Example 9

[0190] First metal complex: Metal complex A1 (same as in Example 1);

[0191] Second metal complex:

[0192] This embodiment uses the metal complex B4 shown in the following formula, and its synthesis method can be found in the literature Organometallics, 2015, 34, 582-590.

[0193]

[0194] Co-catalyst: Methylaluminoxane;

[0195] Chain shuttle: Diethylzinc (ZnEt2).

[0196] Olefin polymerization reaction:

[0197] The olefin polymerization reaction was carried out in accordance with Example 1, except that the metal complex B4 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0198] Example 10

[0199] First metal complex:

[0200] Metal complex A2: The complex shown in formula (I), where M is Zr and R is... 1 -R 8 For H, R 9 and R 10X is cyclohexyl, and n = 2.

[0201]

[0202] In a nitrogen atmosphere, compound L2 (M is Zr, R is R) of formula (III) is added to a three-necked flask. 1 -R 8 For H, R 9 and R 10 0.51 g (1.26 mmol) of cyclohexyl was dissolved in 25 mL of tetrahydrofuran, then cooled to below -70 °C, and 1.06 mL (1.68 mmol) of n-butyllithium solution was slowly added dropwise. The reaction was carried out at this temperature for 1 hour, then slowly heated to room temperature and reacted for 4 hours. The reaction solution was transferred to a constant pressure dropping funnel and slowly added dropwise to 20 mL of tetrahydrofuran solution containing 0.32 g (0.84 mmol) of ZrCl4(THF)2 at below -70 °C. After the addition was complete, the temperature was gradually raised to room temperature, and the reaction was carried out for about 18 hours, then refluxed for 5 hours. The solution was distilled under reduced pressure, evaporated to dryness, dissolved in 20 mL of dichloromethane, and the insoluble matter was filtered off. The filtrate was then evaporated to dryness under reduced pressure, washed with n-heptane, and dried under vacuum to give 0.50 g of metal complex A2 (golden yellow powder), with a yield of 78%. Elemental analysis: Theoretical values ​​are C, 61.08; H, 6.05; N, 5.48; Test values ​​are C, 61.37; H, 5.91; N, 5.18.

[0203] Second metal complex: Metal complex B1 (same as in Example 1);

[0204] Co-catalyst: Methylaluminoxane;

[0205] Chain shuttle: Diethylzinc (ZnEt2).

[0206] Olefin polymerization reaction:

[0207] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that the metal complex A2 was used instead of the metal complex A1. The specific polymerization results are listed in Table 1.

[0208] Example 11

[0209] First metal complex:

[0210] Metal complex A3: The complex shown in formula (I), where M is Zr and R is... 1 -R 8 For H, R 9 and R 10 It is 2-methylcyclohexyl, X is Cl, n = 2.

[0211]

[0212] In a nitrogen atmosphere, compound L3 (M is Zr, R is R) of formula (III) is added to a three-necked flask. 1 -R 8 For H, R 9 and R 10 0.55 g (1.26 mmol) of 2-methylcyclohexyl was dissolved in 25 mL of tetrahydrofuran, then cooled to below -70 °C, and 1.06 mL (1.68 mmol) of n-butyllithium solution was slowly added dropwise. The reaction was carried out at this temperature for 1 hour, then slowly heated to room temperature and reacted for 4 hours. The reaction solution was transferred to a constant pressure dropping funnel and slowly added dropwise to 20 mL of tetrahydrofuran solution containing 0.32 g (0.84 mmol) of ZrCl4(THF)2 at below -70 °C. After the addition was complete, the temperature was gradually raised to room temperature, and the reaction was carried out for about 18 hours, then refluxed for 5 hours. The solution was distilled under reduced pressure, evaporated to dryness, dissolved in 20 mL of dichloromethane, and the insoluble matter was filtered off. The filtrate was then evaporated to dryness under reduced pressure, washed with n-heptane, and dried under vacuum to give 0.56 g of metal complex A3 (golden yellow powder), with a yield of 82%. Elemental analysis: Theoretical values ​​are C, 62.35; H, 6.48; 6; N, 5.19; Test values ​​are C, 61.94; H, 6.77; N, 5.32.

[0213] Second metal complex: Metal complex B1 (same as in Example 1);

[0214] Co-catalyst: Methylaluminoxane;

[0215] Chain shuttle: Diethylzinc (ZnEt2).

[0216] Olefin polymerization reaction:

[0217] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that the metal complex A3 was used instead of the metal complex A1. The specific polymerization results are listed in Table 1.

[0218] Example 12

[0219] First metal complex:

[0220] Metal complex A4: The complex shown in formula (I), where M is Zr and R is... 1 -R 8 For H, R 9 and R 10 It is 2,3,4,5,6-pentafluorophenyl, X is Cl, and n = 2.

[0221]

[0222] In a nitrogen atmosphere, compound L4 (M is Zr, R is R) of formula (III) was added to a three-necked flask.1 -R 8 For H, R 9 and R 10 0.72 g (1.26 mmol) of 2,3,4,5,6-pentafluorophenyl was dissolved in 25 mL of tetrahydrofuran. The mixture was then cooled to below -70 °C, and 1.06 mL (1.68 mmol) of n-butyllithium solution was slowly added dropwise. The reaction was carried out at this temperature for 1 hour, and then slowly heated to room temperature for 4 hours. The reaction solution was transferred to a constant pressure dropping funnel and slowly added dropwise to 20 mL of tetrahydrofuran solution containing 0.32 g (0.84 mmol) of ZrCl4(THF)2 at below -70 °C. After the addition was complete, the temperature was gradually raised to room temperature, and the reaction was carried out for about 18 hours, followed by reflux for 5 hours. The mixture was then distilled under reduced pressure until dry, dissolved in 20 mL of dichloromethane, and the insoluble matter was filtered off. The filtrate was then evaporated to dryness under reduced pressure, washed with n-heptane, and dried under vacuum to give 0.64 g of metal complex A4 (golden yellow powder), with a yield of 75%. Elemental analysis: Theoretical values ​​are C, 45.99; H, 1.29; N, 4.13; Test values ​​are C, 45.65; H, 1.66; N, 4.01.

[0223] Second metal complex: Metal complex B1 (same as in Example 1);

[0224] Co-catalyst: Methylaluminoxane;

[0225] Chain shuttle: Diethylzinc (ZnEt2).

[0226] Olefin polymerization reaction:

[0227] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that the metal complex A4 was used instead of the metal complex A1. The specific polymerization results are listed in Table 1.

[0228] Comparative Example 1

[0229] First metal complex: Metal complex A1 (same as in Example 1);

[0230] Second metal complex: Metal complex B1 (same as in Example 1);

[0231] Co-catalyst: Methylaluminoxane;

[0232] Chain shuttle: No chain shuttle is added.

[0233] Olefin polymerization reaction:

[0234] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that no chain shuttle was added. The specific polymerization results are listed in Table 1.

[0235] Comparative Example 2

[0236] First metal complex: Metal complex A1 (same as Example 4);

[0237] Second metal complex: Metal complex B1 (same as Example 4);

[0238] Co-catalyst: Methylaluminoxane;

[0239] Chain shuttle: No chain shuttle is added.

[0240] Olefin polymerization reaction:

[0241] The olefin polymerization reaction was carried out in accordance with the method of Example 4, except that no chain shuttle was added. The specific polymerization results are listed in Table 1.

[0242] Comparative Example 3

[0243] First metal complex:

[0244] The metal complex A5 shown in the following formula is used, and its synthesis method can be found in patent application US20060199930A1.

[0245]

[0246] Second metal complex:

[0247] The metal complex B5 shown in the following formula is used. The synthesis method can be found in the literature J Am Chem Soc, 1995, 117(23):6414-6415.

[0248]

[0249] Co-catalyst: Methylaluminoxane;

[0250] Chain shuttle: Diethylzinc (ZnEt2).

[0251] Olefin polymerization reaction:

[0252] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that the metal complex A5 was used instead of the metal complex A1, and the metal complex B5 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0253] Comparative Example 4

[0254] First metal complex: Metal complex A1 (same as in Example 1);

[0255] Second metal complex: No second metal complex is added;

[0256] Co-catalyst: Methylaluminoxane;

[0257] Chain shuttle: Diethylzinc (ZnEt2).

[0258] Olefin polymerization reaction:

[0259] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (1 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (0.5 mL of a 1.0 M n-heptane solution) were added via syringe. Next, the metal complex A1 (5 mL of a 1.0 mM n-heptane solution) was added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0260] Comparative Example 5

[0261] First metal complex: No first metal complex is added;

[0262] Second metal complex: Metal complex B1 (same as in Example 1);

[0263] Co-catalyst: Methylaluminoxane;

[0264] Chain shuttle: Diethylzinc (ZnEt2).

[0265] Olefin polymerization reaction:

[0266] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, the co-catalyst (1 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (0.5 mL of a 1.0 M toluene solution) were added via syringe. Next, metal complex B1 (5 mL of a 1.0 mM n-heptane solution) was added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0267] Comparative Example 6

[0268] First metal complex: Metal complex A1 (same as in Example 1);

[0269] Second metal complex: Metal complex B1 (same as in Example 1);

[0270] Co-catalyst: Methylaluminoxane;

[0271] Chain shuttle: No chain shuttle is added.

[0272] Olefin polymerization reaction:

[0273] In a 1-liter stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene. Then, 500 mL of n-heptane solvent was added. Along with the addition of n-heptane, a co-catalyst (2 mL of a 1.53 M methylaluminoxane-toluene solution) was added via syringe. Next, metal complex A1 (5 mL of a 1.0 mM n-heptane solution), metal complex B1 (5 mL of a 1.0 mM n-heptane solution), and 10 mL of 1-decene were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 90 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0274] Table 1

[0275] Example <![CDATA[Polymerization activity (10 6 g / mol cat·h)]]> <![CDATA[M w ×10 -4 ]]> <![CDATA[M w / M n ]]> Example 1 4.67 13.13 2.67 Example 2 6.45 13.01 2.88 Example 3 7.01 15.25 3.14 Example 4 4.03 17.50 3.71 Example 5 5.42 12.43 2.95 Example 6 5.36 14.87 3.25 Example 7 5.27 15.12 2.73 Example 8 6.01 15.93 3.01 Example 9 4.86 13.87 3.27 Example 10 5.43 9.55 2.88 Example 11 6.44 15.49 2.37 Example 12 5.02 14.80 3.43 Comparative Example 1 7.19 37.15 14.85 Comparative Example 2 7.45 43.74 15.68 Comparative Example 3 2.21 6.20 2.13 Comparative Example 4 5.32 4.21 4.07 Comparative Example 5 3.27 32.46 2.54 Comparative Example 6 7.53 36.63 16.47

[0276] As can be seen from Table 1, compared with Comparative Examples 1-2 and 6 (using metal complexes A1 and B1, but without the addition of chain shuttles), the molecular weight distribution of the polymers obtained in the examples using the catalyst composition of the present invention is significantly lower than that of the polymer mixtures prepared in the comparative examples.

[0277] Compared with Comparative Example 3 (which used metal complexes A5 and B5, but whose structures differed from those of the present invention), the catalyst composition of the present invention still exhibits high polymerization activity under high temperature conditions, and the molecular weight of the resulting polymer is significantly higher than that of Comparative Example 3, indicating that the catalyst composition of the present invention has superior chain shuttle polymerization performance.

[0278] Comparative Example 4, using only metal complex A1, yielded a polymer with a smaller molecular weight under the same conditions. Comparative Example 5, using only metal complex B1, yielded a polymer with a larger molecular weight. Furthermore, both the first and second metal complexes used maintained high ethylene polymerization activity at higher temperatures, resulting in polymers with a narrower molecular weight distribution.

[0279] Comparative Examples 1-2 and 6 (using two metal complexes A1 and B1, but without the addition of a chain shuttler) only yielded polymer mixtures, not block polymers. The molecular weight distribution M of the polymers in Examples 1-12... w / M n The M values ​​are all significantly smaller than those of polymers prepared without a chain shuttler, indicating that when the first and second metal complexes are used in combination with a chain shuttler, a block polymer is formed, which is completely different from the mixtures of polymers prepared using only the first and second metal complexes in Comparative Examples 1, 2, and 6. Otherwise, the M values ​​of the polymers obtained in Examples 1-12 would be significantly lower. w / M n It should be much greater than 4.

[0280] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst composition, characterized in that, The catalyst composition contains a first metal complex, a second metal complex, a chain shuttle, and a co-catalyst, wherein, The first metal complex is selected from at least one of the complexes shown in formula (I). In formula (I), M is selected from group IVB transition metals; n is an integer from 1 to 30, and when m is 2 or greater, multiple X groups may be the same or different; m is an integer that satisfies the valence state of M; X is selected from halogens, hydrocarbon groups, hydroxyl groups, acid radicals, and amino groups; R 1 -R 8 They may be the same or different, each independently selected from hydrogen, halogen, C1-C20 aliphatic hydrocarbon group, C3-C20 cyclic hydrocarbon group and C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group may be optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin heteroatom. R 9 and R 10 They may be the same or different, and each is independently selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and substituted or unsubstituted C6-C30 aromatic hydrocarbon groups; The second metal complex is selected from at least one of the complexes shown in formula (II). In formula (II), R1-R6 may be the same or different, and each is independently selected from hydrogen, hydrocarbon group, hydrocarbon group, substituted or unsubstituted C1-C20 alkyl group and substituted or unsubstituted C6-C30 aryl group; M1 is selected from group VIII metals, and the two X1s may be the same or different, and each is a halogen.

2. The catalyst composition according to claim 1, characterized in that, In formula (I), M is titanium, zirconium or hafnium.

3. The catalyst composition according to claim 1 or 2, characterized in that, In equation (I), R 1 -R 8 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, and methoxy; R 9 -R 10 Each is independently selected from n-hexyl, cycloalkyl, halophenyl, nitro-substituted phenyl, alkyl-substituted phenyl, alkyl-substituted cycloalkyl, naphthalene, and biphenyl; X is a halogen or C1-C8 hydrocarbon group; n is an integer from 1 to 10.

4. The catalyst composition according to claim 1, characterized in that, In formula (II), M1 is nickel or palladium.

5. The catalyst composition according to claim 1 or 3, characterized in that, In formula (II), R1-R6 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, substituted or unsubstituted C6-C15 aromatic hydrocarbon groups.

6. The catalyst composition according to claim 1, 4 or 5, characterized in that, The second metal complex is selected from at least one of the following complexes: Complex 1: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br; Complex 2: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br; Complex 3: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br; Complex 4: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br; Complex 5: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Br; Complex 6: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Br; Complex 7: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Br; Complex 8: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Br; Complex 9: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Br; Complex 10: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl; Complex 11: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl; Complex 12: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl; Complex 13: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CHPh2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl; Complex 14: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4 and R6 are methyl groups, R5 is hydrogen, and X1 is Cl; Complex 15: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are ethyl, R5 is hydrogen, and X1 is Cl; Complex 16: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 is methyl, R4 and R6 are isopropyl, R5 is hydrogen, and X1 is Cl; Complex 17: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2 and R5 are methyl, R4 and R6 are ethyl, and X1 is Cl; Complex 18: The complex shown in formula (II), wherein M1 is Ni, R1 and R3 are -CH(p-FPh)2, R2, R4, R5 and R6 are methyl groups, and X1 is Cl.

7. The catalyst composition according to any one of claims 1-6, characterized in that, The molar ratio of the first metal complex to the second metal complex is 1:100 to 100:1, preferably 10:90 to 90:

10.

8. The catalyst composition according to claim 1, characterized in that, The molar ratio of the sum of the first metal complex and the second metal complex to the chain shuttle is 1:(1-20000), preferably 1:(1-1000).

9. The catalyst composition according to claim 1 or 8, characterized in that, The chain shuttle is selected from group IA, IIA, IB, IIB metal compounds or complexes containing at least one C1-C20 hydrocarbon group, preferably from aluminum compounds containing C1-C12 hydrocarbon groups, gallium compounds containing C1-C12 hydrocarbon groups, and zinc compounds containing C1-C12 hydrocarbon groups; the hydrocarbon group is preferably alkyl. Preferably, the chain shuttle 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.

10. The catalyst composition according to claim 1, characterized in that, The cocatalyst is selected from C1-C30 hydrocarbon-substituted group IIIA compounds, preferably selected from at least one of alkylaluminoxanes, arylboranes and arylborates; more preferably selected from at least one of methylaluminoxanes, modified methylaluminoxanes, triarylboranes and tetraarylborates.

11. The catalyst composition according to claim 10, characterized in that, The molar ratio of aluminum in the co-catalyst to the sum of the first metal complex and the second metal complex is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first metal complex and the second metal complex is (0.01-50):

1.

12. A method for olefin polymerization, characterized in that, The method comprises: an olefin monomer undergoing an olefin polymerization reaction in the presence of a catalyst composition according to any one of claims 1-11.

13. The method according to claim 12, characterized in that, The olefin monomer is selected from at least one of ethylene, C3-C16 α-olefins, and C3-C16 cycloolefins.

14. The method according to claim 12 or 13, characterized in that, The conditions for the olefin polymerization reaction include: a temperature of -20°C to 150°C and a pressure of 0.1-10 MPa.

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