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 80 DEG C).

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 first proposed the chain shuttle polymerization method, using FI zirconium catalyst and aminopyridine hafnium catalyst from Mitsui Chemicals Co., Ltd. in Japan, to prepare olefin block copolymers (OBC) with alternating semi-crystalline and amorphous chain segment structures under the action of diethylzinc (ZnEt2) (see: Science, 2006, 312(5):714-719). In many properties, OBC has surpassed other types of thermoplastic polyolefins. For example, in terms of thermal properties, compared with polyolefin elastomers, OBC exhibits a faster crystallization rate and a more regular crystal morphology, and has better heat resistance. In terms of mechanical properties, OBC exhibits higher tensile strength, tear strength, elongation at break, and elastic recovery than traditional polyolefin thermoplastic elastomers, making it an ideal alternative to styrene block copolymer TPE. 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 chain shuttle polymerization, the complexation and separation processes between the catalyst active center and the chain shuttle agent 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 excessive binding between the active center and the chain shuttle agent (see: Macromolecules, 2008, 41(12):4090-4094). Therefore, screening catalytic systems suitable for chain shuttle polymerization is extremely difficult, and research progress on the preparation of single-active-center catalysts for OBC is 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-walking behavior and 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). Salicylaldehyde imine zirconium dichloride complexes can catalyze the polymerization of ethylene with high activity to prepare linear high-density polyethylene with high crystallinity. Novel block polymers with different structures can be prepared through chain shuttle polymerization, offering strong product controllability and broad application prospects. Current research reports the use of nickel diimide metallotolocene catalysts 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 copolymers 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. 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 cycloolefins 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 cycloolefins 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 equation (I), R 1 Selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and C6-C30 aromatic hydrocarbon groups, R 2 -R 5 It is hydrogen, halogen, or C1-C6 hydrocarbon group, R 6It is a C1-C20 aliphatic hydrocarbon group, a C3-C20 cyclic hydrocarbon group, or a C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom.

[0010] M is a group IVB transition metal, X is a halogen, and when n is 2 or greater, multiple X groups may be the same or different; m and n are integers from 1 to 3, and m+n=4;

[0011] The second metal complex is selected from at least one of the complexes shown in formula (II).

[0012]

[0013] In formula (II), R1-R5 may be the same or different, and each is independently selected from hydrogen, C1-C10 hydrocarbon group, C1-C10 hydrocarbon group and halogen; Z is selected from group VIII metal; the two Y are the same or different, and each is a halogen.

[0014] Preferably, in formula (I), R 1 Selected from substituted or unsubstituted C1-C10 alkyl groups and C6-C20 aromatic groups, R 2 -R 5 For hydrogen, R 6 It is a C1-C10 alkyl group, a C3-C10 cyclic hydrocarbon group, or a C6-C12 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom.

[0015] Preferably, in formula (I), M is titanium, zirconium, or hafnium.

[0016] Preferably, in equation (I), both m and n are 2.

[0017] Preferably, in formula (II), R1-R5 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy and halogen.

[0018] Preferably, in formula (II), Z is nickel or palladium.

[0019] Preferably, the second metal complex is selected from at least one of the following complexes:

[0020] Complex 1: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Br;

[0021] Complex 2: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Br;

[0022] Complex 3: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Br;

[0023] Complex 4: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Br;

[0024] Complex 5: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Br;

[0025] Complex 6: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Br;

[0026] Complex 7: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Cl;

[0027] Complex 8: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Cl;

[0028] Complex 9: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Cl;

[0029] Complex 10: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Cl;

[0030] Complex 11: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Cl;

[0031] Complex 12: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Cl.

[0032] 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.

[0033] 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).

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] Preferably, the olefin monomer is selected from at least one of ethylene, C3-C16 α-olefins, and C3-C16 cycloolefins.

[0040] 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.

[0041] According to the technical solution of the present invention, the catalyst composition still exhibits high polymerization activity at high temperatures (e.g., 80°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).

[0042] 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

[0043] 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.

[0044] The catalyst composition of the present invention comprises a first metal complex, a second metal complex, a chain shuttle, and a co-catalyst, wherein,

[0045] The first metal complex is selected from at least one of the complexes shown in formula (I).

[0046]

[0047] In equation (I), R 1 Selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and C6-C30 aromatic hydrocarbon groups, R 2 -R 5 It is hydrogen, halogen, or C1-C6 hydrocarbon group, R 6 It is a C1-C20 aliphatic hydrocarbon group, a C3-C20 cyclic hydrocarbon group, or a C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom.

[0048] M is a group IVB transition metal, X is a halogen, and when n is 2 or greater, multiple X groups may be the same or different; m and n are integers from 1 to 3, and m+n=4;

[0049] The second metal complex is selected from at least one of the complexes shown in formula (II).

[0050]

[0051] In formula (II), R1-R5 may be the same or different, and each is independently selected from hydrogen, C1-C10 hydrocarbon group, C1-C10 hydrocarbon group and halogen; Z is selected from group VIII metal; the two Y are the same or different, and each is a halogen.

[0052] In equation (I), in the preferred case, R 1 Selected from substituted or unsubstituted C1-C10 alkyl groups and C6-C20 aromatic groups, R 2 -R 5 For hydrogen, R 6 It is a C1-C10 alkyl group, a C3-C10 cyclic hydrocarbon group, or a C6-C12 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom.

[0053] In formula (I), M is a group IVB transition metal, preferably titanium, zirconium or hafnium.

[0054] In equation (I), in the preferred case, both m and n are 2.

[0055] In this document, C1-C10 alkyl refers to straight-chain alkyl or branched alkyl of C1-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.

[0056] In this document, halogen refers to fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

[0057] In this invention, the first metal complex can be prepared by conventional methods, the specific preparation process of which can be found in, for example, by referring to patent application US20060199930A1. All relevant content disclosed in that patent application is incorporated herein by reference and will not be repeated here.

[0058] In formula (II), preferably, R1-R5 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy and halogen.

[0059] In formula (II), Z is preferably nickel or palladium.

[0060] Most preferably, the second metal complex is selected from at least one of the following complexes:

[0061] Complex 1: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Br;

[0062] Complex 2: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Br;

[0063] Complex 3: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Br;

[0064] Complex 4: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Br;

[0065] Complex 5: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Br;

[0066] Complex 6: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Br;

[0067] Complex 7: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Cl;

[0068] Complex 8: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Cl;

[0069] Complex 9: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Cl;

[0070] Complex 10: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Cl;

[0071] Complex 11: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Cl;

[0072] Complex 12: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Cl.

[0073] In this invention, the preparation method of the second metal complex may include the following steps:

[0074] (1) The diketone compound shown in formula (III) is reacted with the amine compounds shown in formula (IV) and (V) to generate the diimine compound shown in formula (VI);

[0075] (2) The diimine compound is reacted with the Z metal compound ZY n The reaction proceeds to produce the metal complex shown in formula (II);

[0076] The specific reaction process is shown in the following formula:

[0077]

[0078] The definitions of R1-R5, Z, and Y are the same as those described above.

[0079] In the Z metal compound ZY n In this context, n represents the number of Y values ​​that satisfy the Z valence state, such as 1, 2, or 3.

[0080] In step (1), the catalyst used in the reaction is an organic acid. The organic acid may be selected from at least one of formic acid, acetic acid, and p-toluenesulfonic acid.

[0081] In step (1), the reaction is carried out in the presence of an organic solvent. The organic solvent may be selected from at least one of toluene, methanol, and acetonitrile.

[0082] In step (2), the reaction is carried out in the presence of an organic solvent. This organic solvent may be a haloalkane, more preferably at least one selected from dichloromethane, trichloromethane, and 1,2-dichloroethane.

[0083] In step (2), the reaction is preferably carried out at a temperature of 15-40°C.

[0084] In step (2), the Z metal compound ZY n Preferably, it is nickel halide, specifically, for example, at least one of nickel bromide, nickel chloride, and 1,2-dimethoxyethane nickel halide (such as 1,2-dimethoxyethane nickel bromide, 1,2-dimethoxyethane nickel chloride, etc.).

[0085] 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 1:4 to 4:1.

[0086] 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).

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] In the olefin polymerization method described in this invention, the protective gas can be nitrogen or an inert gas.

[0096] 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.

[0097] In the olefin polymerization method of the present invention, the olefin polymerization reaction time can be 0.1-3h, preferably 0.1-1h.

[0098] 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 toluene.

[0099] 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.

[0100] 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.

[0101] 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., 80°C). During the polymerization reaction, the active chains can alternately grow between the activities 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 the present invention can also prepare block copolymers with different crystallinity properties by selecting the comonomer and controlling the amount of comonomer.

[0102] 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.

[0103] 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.

[0104] The analytical characterization instruments and testing methods used in the following examples and comparative examples are as follows:

[0105] (1) Nuclear magnetic resonance spectrometer: Bruker DMX 400 (400MHz), with tetramethylsilicon (TMS) as internal standard.

[0106] (2) 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).

[0107] (3) 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).

[0108] (4) Melting point T of the polymer m (°C): The temperature was measured using a DSC 8500 differential scanning calorimeter manufactured by TA Corporation under a dry nitrogen atmosphere. The temperature was increased from 0°C to 160°C, held for 1 min, then decreased to 50°C, held for 3 min, and then increased to 160°C. The heating and cooling rate was 10°C / min.

[0109] Example 1

[0110] First metal complex:

[0111] This embodiment uses the metal complex A1 shown in formula (1-1), namely bis-[N-(3,5-di-tert-butyl-o-hydroxyphenylmethylene)cyclohexylamine]zirconium dichloride, the synthesis method of which can be found in patent application US20060199930A1.

[0112]

[0113] Second metal complex:

[0114] Under a nitrogen atmosphere, 11.60 g (21.5 mmol) of 2,6-bis(di(4-fluorophenyl)methyl)-4-isopropylaniline, 3.64 g (20.0 mmol) of acenaphthene, a catalyst amount of p-toluenesulfonic acid (1.5 g), and 200 mL of toluene were added to a round-bottom flask. The mixture was heated to reflux and stirred for 6.5 hours, then cooled to room temperature. After removing the solvent under reduced pressure using a rotary evaporator, the crude product was recrystallized from dichloromethane and methanol to give a yellow powder C1 (10.13 g, 72% yield). 1 H NMR (400MHz, CDCl3, TMS): δ8.07(t,J=7.4Hz,2H),7.82(d,J=8.4Hz,1H),7.75(t,J=7.6Hz,1H),7.06(t,J=7.8Hz,1H),6.98-6.9 0(m,8H),6.80-6.76(m,6H),6.29(t,J=8.6Hz,4H),5.97(d,J=7.2Hz,1H),5.39(s,2H),2.86-2.76(m,1H),1.14(d,J=6.8Hz,6H).

[0115] Under a nitrogen atmosphere, 1-(2,6-bis(bis(4-fluorophenyl)methyl)-4-isopropylbenzylamine)-2-oneacenaphthene, i.e. C1 (1.41 g, 2.0 mmol), 2,4,6-dimethylaniline (0.41 g, 3.0 mmol), a catalyst amount of p-toluenesulfonic acid, and 30 mL of toluene were added to a 100 mL round-bottom flask. The mixture was refluxed and stirred for 4 hours, then cooled to room temperature. The solvent was removed from the mixture under reduced pressure. The resulting solid was purified by alkaline alumina chromatography, and eluted with a mixture of petroleum ether and ethyl acetate (V:V = 500:7) to give a yellow powder ligand L1 (0.80 g, 49% yield). 1 H NMR (400MHz, CDCl3, TMS): δ7.78(d,J=8.0Hz,1H),7.69(d,J=8.4Hz,1H),7.32( t,J=7.8Hz,1H),7.02-6.99(m,7H),6.95-6.91(m,4H),6.87-6.84(m,4H),6.78 (s,2H),6.63(d,J=6.8Hz,1H),6.30(t,J=8.4Hz,4H),5.94(d,J=6.8Hz,1H),5. 57(s,2H),2.87-2.76(m,1H),2.39(s,3H),2.15(s,6H),1.15(d,J=6.8Hz,6H).

[0116] Under a nitrogen atmosphere, ligand L1 (0.25 g, 0.30 mmol), (DME)NiBr2 (0.092 g, 0.30 mmol), dichloromethane (6 mL), and ethanol (8 mL) were added to a 50 mL Shrek tube. After stirring at room temperature for 12 h, the solvent was removed using a rotary evaporator. 20 mL of anhydrous diethyl ether was added, yielding a red precipitate. The precipitate was washed with anhydrous diethyl ether (3 × 15 mL), filtered, and dried to obtain 0.22 g of the red product B1 (i.e., metal complex B1), with a yield of 70%. Elemental analysis was performed on C. 56 H 44 Br2F4N2Ni(1039.48): Theoretical values ​​are: C, 64.71; H, 4.27; N, 2.70; Test values ​​are: C, 64.53; H, 4.08; N, 2.85.

[0117] The structural formula of the metal complex B1 is shown in formula (2-1).

[0118]

[0119] Co-catalyst: Methylaluminoxane;

[0120] Chain shuttle: Diethylzinc (ZnEt2).

[0121] Olefin polymerization reaction:

[0122] 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 toluene solvent was added. Along with the toluene, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.5 M toluene solution) were added via syringe. Next, metal complex A1 (5 mL of a 1.0 mM toluene solution) and metal complex B1 (5 mL of a 1.0 mM toluene solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 80 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0123] Example 2

[0124] First metal complex: Metal complex A1 (same as in Example 1);

[0125] Second metal complex: Metal complex B2, as shown in formula (2-2):

[0126]

[0127] The synthetic route for metal complex B2 was the same as that for metal complex B1, yielding 0.25 g of red product B2 (i.e., metal complex B2) with a yield of 78%. Elemental analysis was performed.59 H 50 Br2F4N2Ni(1081.56): Theoretical values ​​are: C, 65.52; H, 4.66; N, 2.59; Test values ​​are: C, 65.66; H, 4.67; N, 2.34.

[0128] Co-catalyst: Methylaluminoxane;

[0129] Chain shuttle: Diethylzinc (ZnEt2).

[0130] 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.

[0131] Example 3

[0132] First metal complex: Metal complex A1 (same as in Example 1);

[0133] Second metal complex: Metal complex B3, as shown in formula (2-3):

[0134]

[0135] The synthetic route for metal complex B3 was the same as that for metal complex B1, yielding 0.21 g of red product B3 (i.e., metal complex B3) in 68% yield. Elemental analysis was performed. 57 H 46 Br2F4N2Ni(1053.50): Theoretical values ​​are: C, 64.99; H, 4.40; N, 2.66; Test values ​​are: C, 64.71; H, 4.51; N, 2.82.

[0136] Co-catalyst: Methylaluminoxane;

[0137] Chain shuttle: Diethylzinc (ZnEt2).

[0138] Olefin polymerization reaction:

[0139] 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.

[0140] Example 4

[0141] First metal complex:

[0142] This embodiment uses metal complex A2 as shown in formula (1-2), namely bis-[N-(3-phenyl-o-hydroxyphenylmethylene)aniline]zirconium dichloride, the synthesis method of which can be found in patent application US20060199930A1.

[0143]

[0144] Second metal complex: Metal complex B4, as shown in formula (2-4):

[0145]

[0146] The synthetic route for metal complex B4 is the same as that for metal complex B1, yielding a red product B4 (i.e., metal complex B4) in 72% yield. Elemental analysis test C... 55 H 42 Br2F4N2Ni(1025.45): Theoretical values ​​are: C, 64.42; H, 4.13; N, 2.73; Test values ​​are: C, 64.18; H, 4.01; N, 2.89.

[0147] Co-catalyst: Methylaluminoxane;

[0148] Chain shuttle: Diethylzinc (ZnEt2).

[0149] Olefin polymerization reaction:

[0150] 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, and the metal complex B4 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0151] Example 5

[0152] First metal complex: Metal complex A2 (same as Example 4);

[0153] Second metal complex: Metal complex B1 (same as in Example 1);

[0154] Co-catalyst: Methylaluminoxane;

[0155] Chain shuttle: Diethylzinc (ZnEt2).

[0156] Olefin polymerization reaction:

[0157] 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.

[0158] Example 6

[0159] First metal complex: Metal complex A1 (same as in Example 1);

[0160] Second metal complex: Metal complex B1 (same as in Example 1);

[0161] Co-catalyst: Methylaluminoxane;

[0162] Chain shuttle: Diethylzinc (ZnEt2).

[0163] Olefin polymerization reaction:

[0164] 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 toluene solvent was added. Along with the toluene, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.5 M toluene solution) were added via syringe. Then, metal complex A1 (5 mL of a 1.0 mM toluene solution), metal complex B1 (5 mL of a 1.0 mM toluene solution), and 10 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 80 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0165] Example 7

[0166] First metal complex: Metal complex A1 (same as in Example 1);

[0167] Second metal complex: Metal complex B1 (same as in Example 1);

[0168] Co-catalyst: N,N-dimethylaniline tetra(pentafluorophenyl)borate;

[0169] Chain shuttle: Diethylzinc (ZnEt2).

[0170] Olefin polymerization reaction:

[0171] The olefin polymerization reaction was carried out in accordance with Example 1, except that the cocatalyst N,N-dimethylaniline tetra(pentafluorophenyl)borate was used instead of methylaluminoxane. The specific polymerization results are listed in Table 1.

[0172] Example 8

[0173] First metal complex: Metal complex A1 (same as in Example 1);

[0174] Second metal complex: Metal complex B2 (same as in Example 2);

[0175] Co-catalyst: N,N-dimethylaniline tetra(pentafluorophenyl)borate;

[0176] Chain shuttle: Diethylzinc (ZnEt2).

[0177] Olefin polymerization reaction:

[0178] The olefin polymerization reaction was carried out in accordance with Example 7, except that the metal complex B2 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0179] Example 9

[0180] First metal complex: Metal complex A1 (same as in Example 1);

[0181] Second metal complex: Metal complex B1 (same as in Example 1);

[0182] Co-catalyst: Methylaluminoxane;

[0183] Chain shuttle: Diethylzinc (ZnEt2).

[0184] Olefin polymerization reaction:

[0185] 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 toluene solvent was added. Along with the toluene, the co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) and ZnEt2 (1 mL of a 1.5 M toluene solution) were added via syringe. Next, metal complex A1 (2 mL of a 1.0 mM toluene solution) and metal complex B1 (8 mL of a 1.0 mM toluene solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 80 °C for 30 min. The mixture was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0186] Example 10

[0187] First metal complex: Metal complex A1 (same as in Example 1);

[0188] Second metal complex: Metal complex B1 (same as in Example 1);

[0189] Co-catalyst: Methylaluminoxane;

[0190] Chain shuttle: Diethylzinc (ZnEt2).

[0191] Olefin polymerization reaction:

[0192] 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 toluene solvent was added. Along with the toluene, the co-catalyst (2 mL of 1.53 M methylaluminoxane toluene solution) and ZnEt2 (1 mL of 1.5 M toluene solution) were added via syringe. Next, metal complex A1 (5 mL of 1.0 mM toluene solution), metal complex B1 (5 mL of 1.0 mM toluene 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 80 °C for 30 min. The reactor was then cooled, the polymer was collected, and weighed. The specific polymerization results are listed in Table 1.

[0193] Comparative Example 1

[0194] First metal complex: Metal complex A1 (same as in Example 1);

[0195] Second metal complex: Metal complex B1 (same as in Example 1);

[0196] Co-catalyst: Methylaluminoxane.

[0197] 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.

[0198] Comparative Example 2

[0199] First metal complex: Metal complex A1 (same as Example 9);

[0200] Second metal complex: Metal complex B1 (same as Example 9);

[0201] Co-catalyst: Methylaluminoxane.

[0202] Olefin polymerization reaction:

[0203] 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 toluene solvent was added. Along with the toluene, a co-catalyst (2 mL of a 1.53 M toluene solution of methylaluminoxane) was added via syringe. Next, metal complex A1 (2 mL of a 1.0 mM toluene solution) and metal complex B1 (8 mL of a 1.0 mM toluene solution) were added via syringe. The pressure was increased to and maintained at 1.0 MPa, and the polymerization reaction was carried out at 80 °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.

[0204] Comparative Example 3

[0205] First metal complex: Metal complex A1 (same as in Example 1);

[0206] Second metal complex: The metal complex B5 shown in formula (2-5) is used. The synthesis process can be found in J AmChem Soc, 1995, 117(23):6414-6415.

[0207]

[0208] Co-catalyst: Methylaluminoxane;

[0209] Chain shuttle: Diethylzinc (ZnEt2).

[0210] Olefin polymerization reaction:

[0211] The olefin polymerization reaction was carried out in accordance with Example 1, except that the metal complex B5 was used instead of the metal complex B1. The specific polymerization results are listed in Table 1.

[0212] Comparative Example 4

[0213] First metal complex: Metal complex A1 (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 a second metal complex, namely the metal complex B1, was not added. The specific polymerization results are listed in Table 1.

[0218] Comparative Example 5

[0219] Second metal complex: Metal complex B1 (same as in Example 1);

[0220] Co-catalyst: Methylaluminoxane;

[0221] Chain shuttle: Diethylzinc (ZnEt2).

[0222] Olefin polymerization reaction:

[0223] The olefin polymerization reaction was carried out in accordance with the method of Example 1, except that the first metal complex, namely the metal complex A1, was not added. The specific polymerization results are listed in Table 1.

[0224] Table 1

[0225]

[0226]

[0227] As can be seen from Table 1, compared with Comparative Example 1 (which used metal complex A1 and catalytic metal complex B1, but without the addition of a chain shuttler), the molecular weight distribution of the polymer obtained in Example 1 was significantly lower than that of the polymer mixture prepared in Comparative Example 1. Similarly, the situation in Example 9 was similar to that in Comparative Example 2. Furthermore, the melting point value (T... m It can be seen that the polymer obtained without the addition of the chain shuttle has two melting peaks, which is the result of mixing the polymers obtained by the two complex catalysts.

[0228] Compared with Comparative Example 3 (which used metal complex A1 and metal complex B5, but the structure of metal complex B5 is different from that of the present invention), the catalyst composition of the present invention still has high polymerization activity under high temperature conditions, and the molecular weight of the resulting polymer is significantly higher than that of Comparative Example 3.

[0229] Comparative Example 4, using only the first metal complex, 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.

[0230] In Comparative Examples 1 and 2, using only two catalysts (metal complex A1 and catalytic metal complex B1, but without the addition of a chain shuttle) only yielded polymer mixtures, not block polymers. The polymer molecular weight distribution M of Examples 1-10 of the present invention... w / M n The melting peaks of the polymers were significantly smaller than those of the polymers prepared without a chain shuttler, and the resulting polymers exhibited only a single melting peak. This indicates that when the first and second metal complexes were used in combination with the chain shuttler, a block polymer was formed, which is entirely different from the mixtures of polymers prepared using only the first and second metal complexes in Comparative Examples 1 and 2. Furthermore, the structure and crystallinity of the resulting polymers can be controlled by adjusting the type and amount of catalyst and the selection of comonomers.

[0231] 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 equation (I), R 1 Selected from substituted or unsubstituted C1-C20 aliphatic hydrocarbon groups and C6-C30 aromatic hydrocarbon groups, R 2 -R 5 It is hydrogen, halogen, or C1-C6 hydrocarbon group, R 6 It is a C1-C20 aliphatic hydrocarbon group, a C3-C20 cyclic hydrocarbon group, or a C6-C20 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom. M is a group IVB transition metal, X is a halogen, and when n is 2 or greater, multiple X groups may be the same or different; m and n are integers from 1 to 3, and m+n=4; The second metal complex is selected from at least one of the complexes shown in formula (II). In formula (II), R1-R5 may be the same or different, and each is independently selected from hydrogen, C1-C10 hydrocarbon group, C1-C10 hydrocarbon group and halogen; Z is selected from group VIII metal; the two Y are the same or different, and each is a halogen.

2. The catalyst composition according to claim 1, characterized in that, In equation (I), R 1 Selected from substituted or unsubstituted C1-C10 alkyl groups and C6-C20 aromatic groups, R 2 -R 5 For hydrogen, R 6 It is a C1-C10 alkyl group, a C3-C10 cyclic hydrocarbon group, or a C6-C12 aromatic hydrocarbon group, and any hydrogen or carbon atom on the hydrocarbon group is optionally replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium, or tin heteroatom.

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

4. The catalyst composition according to claim 1 or 2, characterized in that, In equation (I), both m and n are 2.

5. The catalyst composition according to claim 1, characterized in that, In formula (II), R1-R5 are each independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy and halogen.

6. The catalyst composition according to claim 1 or 5, characterized in that, In formula (II), Z is nickel or palladium.

7. The catalyst composition according to claim 1, 5, or 6, 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 Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Br; Complex 2: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Br; Complex 3: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Br; Complex 4: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Br; Complex 5: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Br; Complex 6: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Br; Complex 7: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl groups, R2, R3 and R4 are H groups, and Y is Cl; Complex 8: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl groups, R2, R3 and R4 are H groups, and Y is Cl; Complex 9: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are isopropyl, R2, R3 and R4 are H, and Y is Cl; Complex 10: The complex shown in formula (II), wherein Z is Ni, R1, R3 and R5 are methyl groups, R2 and R4 are H groups, and Y is Cl; Complex 11: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are ethyl, R3 is methyl, R2 and R4 are H, and Y is Cl; Complex 12: The complex shown in formula (II), wherein Z is Ni, R1 and R5 are methyl, R3 is ethyl, R2 and R4 are H, and Y is Cl.

8. The catalyst composition according to any one of claims 1-7, 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.

9. 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).

10. The catalyst composition according to claim 1 or 9, 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.

11. 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.

12. The catalyst composition according to claim 11, 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.

13. 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 1-12.

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

15. The method according to claim 13 or 14, 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.

Images