OLEFIN POLYMERIZATION CATALYST AND POLYMERIZATION METHOD USING THE SAME

Abstract

A catalyst for olefin polymerization is disclosed, which comprises a main catalyst and a co-catalyst; the main catalyst is a bisphenol metal complex represented by formula I, and the co-catalyst comprises an organoaluminum compound; in formula I, R1, R1', R2, and R2' are the same or different and each independently represent hydrogen and a substituted or unsubstituted C1-C 20 R3 to R7, R3' to R7' are the same or different and each independently selected from hydrogen and substituted or unsubstituted C1 to C 20 hydrocarbyl; R and R are the same or different and each independently represent hydrogen or a substituted or unsubstituted C to C 20 hydrocarbyl; M and M' are the same or different and are selected from Group IV metals; and X is a halogen. [Formula 1] TIFF2023501197000022.tif48169

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to CN201911032105.4, CN201911033274.X, CN201911032074.2, CN201911032096.9, and CN201911033277.3, all filed on October 28, 2019, which are incorporated by reference in their entireties for all purposes.

[0002] [Technical field] The present invention relates to an olefin polymerization catalyst and an olefin polymerization process using the same.

[0003] [Background technology] The application of coordination polymerization catalysts, represented by Ziegler-Natta catalysts, has promoted the rapid development of the polyolefin industry. Today, the development of metal catalysts for solution polymerization has become one of the research hotspots in the field of coordination polymerization, and phenolic ligand-based transition metal catalysts belong to one class among them. This class of catalysts has good catalytic activity for olefin polymerization. For example, 2,6-diisopropylphenoxytitanium catalysts have successfully realized the homopolymerization of ethylene to result in linear polyethylene (Nomura K, Naga N, Miki M, et al., Macromolecules 1998, 31, 7588-7597), and when used in the copolymerization of ethylene with α-olefins, copolymers with high α-olefin content can be obtained, which can be thermoplastic elastomers.

[0004] At the same time, based on the research results of active enzyme catalysts, synergistic catalysts have been gradually developed. Research has revealed that the ethylene polymerization activity and molecular weight of the polymer obtained when using double zirconium metal catalysts are compared with those obtained when using single zirconium metal catalysts, but the ethyl grafting rate in the polymer chain is very high, reaching 12%, while the ethyl grafting rate in the polymer obtained by using a single zirconium metal catalyst to catalyze ethylene polymerization is only 1.1%. At the same time, when using double zirconium metal catalysts, the ethyl grafting rate in the polymer obtained by using double boron cocatalysts (12%) is also higher than the ethyl grafting rate in the polymer obtained by using a single boron cocatalyst (2.7%) (Li, H.; Marks, TJ Proc. Natl. Acad. Sci. 2006, 103, 15295).

[0005] CN201010204671.1 discloses the homopolymerization of ethylene and the copolymerization of ethylene with monomers such as hexene and octene using a double titanium metal catalyst. The polymerization activity at normal pressure is 10 4 g mol -1 (Ti)·h -1 The molecular weight of the copolymer is about 300,000 and the molecular weight distribution is greater than 2.

[0006] There remains a need in the art to develop new metal compounds that exhibit desirable catalytic performance and olefin polymerization processes using such new catalysts.

[0007] Summary of the Invention The present inventors have conducted extensive research and have found that a class of bisphenol metal complexes exhibit high catalytic efficiency and high comonomer incorporation capability when used in olefin polymerization, based on which the present invention has been made.

[0008] The subject of the present invention is therefore a catalyst for the polymerization of olefins, which comprises a main catalyst and a cocatalyst based on a bisphenol metal complex.

[0009] Another object of the present invention is to provide a process for homopolymerizing olefins such as ethylene, which uses a catalyst comprising a main catalyst and a cocatalyst based on a bisphenol metal complex. The molecular weight of the polyethylene prepared by this process can be up to 200,000 or more, with a polydispersity in the range of 1.5 to 20.

[0010] Another object of the present invention is to provide a method for copolymerizing olefins such as ethylene, which uses a catalyst including a main catalyst and a cocatalyst based on a bisphenol metal complex. The weight average molecular weight of the polyethylene prepared by this method can be up to 200,000 or more, the molecular weight distribution can be in the range of 1.5-10, and the comonomer content can be 1-30 mol%.

[0011] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Various specific embodiments, versions of the present invention are described, including preferred embodiments and definitions adopted in the specification. Although the following detailed description provides specific preferred embodiments, those skilled in the art will understand that these embodiments are merely exemplary and that the present invention may be implemented in other ways. Any reference to the "invention" may refer to one or more (but not necessarily all) of the inventions defined by the claims. The use of headings is merely for convenience and does not limit the scope of the invention.

[0012] For purposes of this invention and the claims thereto, the novel numbering scheme for the Groups of the Periodic Table is used as described in Chemical and Engineering News, 63(5), pg. 27 (1985).

[0013] As used herein, the term "substitute" or "substituted" means that one or more hydrogen atoms in the group in question are replaced with C1-C6 alkyl, phenyl, benzyl, halogen atoms, heteroatoms, heteroatom-containing groups (such as C1-C6 alkoxy), or a carbon atom in the backbone is replaced by a heteroatom. Examples of substituents include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, phenyl, benzyl, fluorine, chlorine, bromine, iodine, methoxy, and ethoxy.

[0014] As used herein, the term "halogen" or "halogen atom" refers to at least one of fluorine, chlorine, bromine, and iodine.

[0015] As used herein, the term "heteroatom" refers to at least one of O, S, N, P, B, Si, Ge, and Sn.

[0016] As used herein, the term "organoaluminum compound" has the meaning generally accepted in the art, i.e., a compound having an organic group-Al bond. Examples of organoaluminum compounds include alkylaluminums, alkylaluminum halides, and modified or unmodified aluminoxanes.

[0017] As used herein, the term "polymerization" includes homopolymerization and copolymerization. As used herein, the term "polymer" includes homopolymers, copolymers, and terpolymers.

[0018] As used herein, the term "catalyst component" refers to the main catalyst component or catalyst precursor, which together with conventional cocatalysts, such as alkylaluminum and optional external electron donors, constitute a catalyst for olefin polymerization (such a combination is also referred to in the art as a catalyst system).

[0019] In a first aspect, the present invention provides a catalyst system for the polymerization of olefins comprising a main catalyst and a cocatalyst.

[0020] [Catalytic compound] In the present disclosure, a bisphenol metal complex represented by formula I is used as the catalyst compound:

[0021] [ka]

[0022] In the formula, R1 and R1' are each independently hydrogen and a substituted or unsubstituted C1-C 20 R3-R7, R3'-R7' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted C1-C 20 any two adjacent groups among R3-R7 are optionally joined to form a ring, and any two adjacent groups among R3'-R7' are optionally joined to form a ring; M and M' are each independently a Group 4 metal; each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydrides, amides, alkoxides, alkyl sulfides, alkyl phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof; m and n are independently integers from 1 to 4; and L is a divalent linking group.

[0023] In some embodiments, the divalent linking group L is a divalent hydrocarbyl or substantially hydrocarbon character divalent linking group having 1 to 30 carbon atoms. As used herein, the term "substantially hydrocarbon character divalent linking group" refers to a divalent group that exhibits hydrocarbon character as a whole. Such groups permit one or more heteroatoms to be included in the hydrocarbon chain, but do not have active hydrogens. Divalent linking groups L useful in the present invention may be selected from the group consisting of C1-C30 alkylene, C1-C30 heteroalkylene, C5-C30 cycloalkylene, C4-C30 heterocycloalkylene, C2-C30 alkenylene, C2-C30 heteroalkenylene, C4-C30 cycloalkenylene, C4-C30 heterocycloalkenylene, C2-C30 alkynylene, C2-C30 heteroalkynylene, C6-C30 arylene, and C4-C30 heteroarylene. Examples of L include, but are not limited to, methylene, 1,2-ethylene, 1,3-propylene, 1,2-cyclopentanediyl, 1,3-cyclopentanediyl, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthylene, 1,8-anthrylene, 1,8-fluorenylene, 1,8-carbazolylidene, 4,5-acridinediyl, 4H-dibenzopyran-1,9-diyl, and corresponding groups having one or more alkyl substituents, such as C1-C6 alkyl substituents, on the carbon chain and / or ring of the aforementioned groups.

[0024] In some preferred embodiments, the bisphenol metal complexes of the present disclosure have a structure represented by formula Ia:

[0025] [ka]

[0026] In the formula, R1 and R1' are each independently hydrogen and a substituted or unsubstituted C1-C 20R3-R7, R3'-R7' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted C1-C 20 hydrocarbyl, any two adjacent groups among R3 to R7 are optionally joined to form a ring, any two adjacent groups among R3' to R7' are optionally joined to form a ring; R8 and R9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted C1 to C6 20 hydrocarbyl; each R is independently selected from the group consisting of hydrogen and substituted or unsubstituted C1-C 20 each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydrides, amides, alkoxides, alkyl sulfides, alkyl phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof; and m and n are independently integers from 1 to 4.

[0027] In some preferred embodiments, the bisphenol metal complexes of the present disclosure have a structure represented by formula Ib:

[0028] [ka]

[0029] In the formula, R1, R1', R2, and R2' are each independently hydrogen or a substituted or unsubstituted C1-C 20 R3-R7, R3'-R7' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted C1-C 20 hydrocarbyl, any two adjacent groups among R3 to R7 are optionally joined to form a ring, any two adjacent groups among R3' to R7' are optionally joined to form a ring; R8 and R9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted C1 to C6 20each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydrides, amides, alkoxides, alkyl sulfides, alkyl phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof.

[0030] In some preferred embodiments, in formulas I, Ia, and Ib, R1, R1', R2, and R2' are each independently hydrogen, substituted or unsubstituted, linear or branched C1-C 20 Alkyl, and substituted or unsubstituted C6-C 20 From the group consisting of aryl, preferably hydrogen and substituted or unsubstituted, linear or branched C1-C 10 It is preferably selected from the group consisting of alkyl, more preferably from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C1-C6 alkyl.

[0031] In some preferred embodiments, in formulas I, Ia, and Ib, R3 to R7, R3′ to R7′ are each independently selected from hydrogen and substituted or unsubstituted, linear or branched C1 to C6 20 From the group consisting of alkyl, preferably hydrogen and substituted or unsubstituted, linear or branched C1-C 10 It is preferably selected from the group consisting of alkyl, more preferably from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C1-C6 alkyl.

[0032] In some preferred embodiments, in formulas Ia and Ib, R and R are each independently selected from hydrogen and substituted or unsubstituted, linear or branched C1-C 20 From the group consisting of alkyl, preferably hydrogen and substituted or unsubstituted, linear or branched C1-C 10 It is preferably selected from the group consisting of alkyl, more preferably from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C1-C6 alkyl.

[0033] In some preferred embodiments, in formulas I, Ia, and Ib, M and M' are each independently selected from the group consisting of titanium, zirconium, and hafnium, preferably titanium.

[0034] In some preferred embodiments, in formulas I, Ia, and Ib, each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide, and iodide, and is preferably methyl or chloride.

[0035] In some embodiments, the bisphenol metal complex is at least one of the following complexes represented by formula Ib:

[0036] [ka]

[0037] Bisphenol metal complex 1: R1=R2=R1'=R2'=Me, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 2: R1=R2=R1'=R2'=Et, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 3: R1 = R2 = R1' = R2' = iPr, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 4: R1 = R2 = R1' = R2' = tBu, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=R8=R9=H, M=M'=Ti, X=Cl; Bisphenol metal complex 5: R1=R2=R1'=R2'=Me, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=Me, R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 6: R1=R2=R1'=R2'=Et, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=Me, R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 7: R1 = R2 = R1' = R2' = iPr, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=Me, R8=R9=H, M=M′=Ti, X=Cl; Bisphenol metal complex 8: R1 = R2 = R1' = R2' = tBu, R3=R4=R5=R6=R7=R3'=R4'=R5'=R6'=R7'=Me, R8=R9=H, M=M′=Ti, X=Cl; and the corresponding compounds where X=methyl.

[0038] The above bisphenol metal complexes can be prepared by methods known per se. In some embodiments, the bisphenol metal complexes may be prepared by a method comprising the steps of: 1) reacting the corresponding bisphenol compound with a strong base to form a bisphenol disalt; and 2) reacting the bisphenol disalt with a metal complex represented by formula V to obtain a bisphenol metal complex represented by formula I.

[0039] [ka]

[0040] wherein R3-R7, M and X have the same meanings as defined above for formula I.

[0041] In some particular embodiments, the bisphenol metal complexes represented by formula Ib may be prepared by a method comprising the steps of: 1) reacting a bisphenol compound represented by formula II with a metal compound represented by formula III to obtain a bisphenol disalt represented by formula IV; and 2) reacting the bisphenol disalt compound represented by formula IV with a metal complex represented by formula V to obtain a bisphenol metal complex represented by formula Ib;

[0042] [ka]

[0043] wherein in formulas II and IV, R1, R1', R2, R2', R8 and R9 have the same meanings as defined above for formula Ib; In formula III, M1 is a Group IA metal, preferably lithium, sodium or potassium, and R is hydrogen or a linear or branched C1-C 10 is alkyl; and In formula V, R3 through R7, M, and X have the same meanings as defined above for formula Ib.

[0044] In some preferred embodiments of the present invention, the preparation method includes: reacting a bisphenol compound represented by formula II with a metal compound represented by formula III in an organic solvent to obtain a bisphenol disalt compound represented by formula IV; and then reacting the bisphenol disalt compound with a metal complex represented by formula V in an organic solvent to obtain a bisphenol metal complex represented by formula Ib. According to some embodiments of the present invention, the organic solvent is selected from tetrahydrofuran, diethyl ether, 1,4-dioxane, and dichloromethane.

[0045] In some preferred embodiments of the present invention, the bisphenol compound is at least one of the following bisphenol compounds represented by formula II:

[0046] [ka]

[0047] Bisphenol compound 1: R1 = R2 = R1' = R2' = Me, R8 = R9 = H; Bisphenol compound 2: R1 = R2 = R1' = R2' = Et, R8 = R9 = H; Bisphenol compound 3: R1 = R2 = R1' = R2' = iPr, R8 = R9 = H; Bisphenol compound 4: R1=R2=R1'=R2'=tBu, R8=R9=H.

[0048] In some preferred embodiments of the present invention, the metal compound represented by formula III is at least one selected from KH, NaH, MeLi, EtLi, PrLi, and BuLi.

[0049] In some preferred embodiments of the present invention, the compound represented by formula IV is at least one of the following compounds:

[0050] [ka]

[0051] Phenoxide compound 1: R1 = R2 = R1' = R2' = Me, R8 = R9 = H, M1 = Li; Phenoxide compound 2: R1 = R2 = R1' = R2' = Et, R8 = R9 = H, M1 = Li; Phenoxide compound 3: R1 = R2 = R1' = R2' = iPr, R8 = R9 = H, M1 = Li; Phenoxide compound 4: R1 = R2 = R1' = R2' = tBu, R8 = R9 = H, M1 = Li; Phenoxide compound 5: R1 = R2 = R1' = R2' = Me, R8 = R9 = H, M1 = Na; Phenoxide compound 6: R1 = R2 = R1' = R2' = Et, R8 = R9 = H, M1 = Na; Phenoxide compound 7: R1 = R2 = R1' = R2' = iPr, R8 = R9 = H, M1 = Na; Phenoxide compound 8: R1 = R2 = R1' = R2' = tBu, R8 = R9 = H, M1 = Na; Phenoxide compound 9: R1 = R2 = R1' = R2' = Me, R8 = R9 = H, M1 = K; Phenoxide compound 10: R1 = R2 = R1' = R2' = Et, R8 = R9 = H, M1 = K; Phenoxide compound 11: R1 = R2 = R1' = R2' = iPr, R8 = R9 = H, M1 = K; Phenoxide compound 12: R1 = R2 = R1' = R2' = tBu, R8 = R9 = H, M1 = K.

[0052] In some preferred embodiments of the present invention, the metal compound represented by formula V is at least one of the following metal complexes:

[0053] [ka]

[0054] Metal complex 1: R3=R4=R5=R6=R7=H, M=Ti, X=Cl; Metal complex 2: R3=R4=R5=R6=R7=Me, M=Ti, X=Cl.

[0055] In some preferred embodiments of the method of the present invention, the molar ratio of the bisphenol compound represented by formula II to the compound represented by formula III is 1:(1 to 20), for example, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10 0.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5, 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5, 1:20, and any value therebetween, preferably 1:(2-10), and more preferably 1:(4-8).

[0056] In some preferred embodiments of the method of the present invention, the reaction temperature for the reaction between the bisphenol compound represented by formula II and the compound represented by formula III is from -78°C to 60°C, e.g., -60°C, -50°C, -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, and any value therebetween, preferably from -10°C to 40°C.

[0057] In some preferred embodiments of the method of the present invention, the reaction time for the reaction between the bisphenol compound represented by formula II and the compound represented by formula III is 1 to 10 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, and any value therebetween, preferably 1.5 to 3 hours.

[0058] In some preferred embodiments of the method of the present invention, the molar ratio of the compound represented by formula IV to the metal compound represented by formula V is 1:(1.8-2.4), such as 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, and any value therebetween, preferably 1:2. Simply, the number of moles of the bisphenol compound can be considered as the number of moles of the compound represented by formula IV.

[0059] In some preferred embodiments of the method of the present invention, the reaction temperature for the reaction between the compound represented by formula IV and the metal compound represented by formula V is −78° C. to 60° C., for example, −60° C., −50° C., −40° C., −30° C., −20° C., −10° C., 0° C., 10° C., 20° C., 30° C., and any value therebetween, preferably −10° C. to 40° C.

[0060] In some preferred embodiments of the method of the present invention, the reaction time for the reaction of the compound represented by formula IV with the metal compound represented by formula V is 6 to 24 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, and any value therebetween, preferably 6 to 19 hours.

[0061] [Main catalyst of the catalytic system] In some embodiments of the present invention, for example when the catalyst system is used in a solution polymerization, the catalyst compound itself is used as the primary catalyst component.

[0062] In some other embodiments of the present invention, for example when the catalyst system is used in a slurry or gas phase polymerization, the primary catalyst component comprises a catalyst compound, e.g., the primary catalyst component comprises a combination of a catalyst compound and a support material.

[0063] [Activator] In this disclosure, the terms "activator" and "cocatalyst" are generally used interchangeably. According to the present invention, the catalyst compound can be combined with the activator in any manner known in the art, including, for example, directly combining the catalyst compound with the activator for use in solution polymerization, and supporting the catalyst compound and then combining the supported catalyst compound with the activator for use in slurry or gas phase polymerization. The activator is generally any compound that can activate any one of the above catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Examples of activators include organoaluminum compounds such as aluminoxanes and alkylaluminums, ionizing activators (which may be neutral or ionic), and conventional cocatalysts such as alkylaluminum halides. Preferred activators typically include alkylaluminums, alkylaluminum halides, aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds. The ionizing anion precursor compound abstracts one reactive σ-bonded metal ligand, rendering the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

[0064] [Aluminoxane Activator] Aluminoxane activators may be utilized as activators for the catalyst compounds described herein. Aluminoxanes generally have the formula -Al(R 1 )-O-subunits, where R 1 is an alkyl group, for example, C1-C 12 It is preferably an alkyl group, more preferably a C1-C6 alkyl group, particularly a C1-C4 alkyl group, such as methyl or isobutyl. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane.

[0065] Alkyl aluminoxanes and modified alkyl aluminoxanes are suitable as activators for the catalyst compounds of the present invention, especially when the abstractable ligand is an alkyl, halide, alkoxide or amide. A useful aluminoxane is modified methylaluminoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane Type 3A).

[0066] When the activator is a modified or unmodified aluminoxane, some embodiments select a maximum amount of activator relative to the catalyst compound (per metal catalytic site), typically 5000-fold or 4500-fold or 4000-fold or 3000-fold or 2000-fold molar excess (Al / M). The minimum activator to catalyst compound ratio is 1:1 molar ratio, or 1:10 molar ratio, or 1:20 molar ratio, or 1:50 molar ratio, or 1:100 molar ratio, or 1:200 molar ratio. Alternative molar ratio ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, or alternatively 1:1 to 50:1. The molar ratio of the main catalyst to the cocatalyst (M / Al) may range from 1:(200-5000), for example, 1:500, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500 and any value therebetween, with one preferred range being 1:(2000-3000).

[0067] In one class of embodiments, little or no aluminoxane is used in the polymerization processes described herein, for example, the aluminoxane may be present in a molar ratio of aluminum to catalyst compound metal of less than 100:1, or less than 300:1, or less than 500:1.

[0068] Ionizing / Non-Coordinating Anion Activators The present disclosure also uses ionizing / non-coordinating anion activators. The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation or coordinates only weakly to a cation, thereby remaining sufficiently unstable to be displaced by a neutral Lewis base. A "compatible" non-coordinating anion is an anion that does not decompose neutrally when the initially formed complex decomposes. Furthermore, the anion does not transfer an anionic substituent or fragment to the cation to form a neutral transition metal compound and neutral by-products from the anion.

[0069] Useful noncoordinating anions consistent with the present disclosure are those that are compatible and stabilize the transition metal cation in the sense of balancing the ionic charge of the transition metal cation with +1, yet retain sufficient lability to permit displacement during polymerization. In the present disclosure, useful ionizing activators typically include NCAs, particularly compatible NCAs.

[0070] It is within the scope of the present invention to use neutral or ionic ionizing activators such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tris-perfluorophenyl boron metalloid precursors or tris-perfluoronaphthyl boron metalloid precursors, polyhalogenated heteroborane anions, boric acid, or combinations thereof. Such ionizing activators are also sometimes called organoboron compounds. It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with aluminoxane or modified aluminoxane activators.

[0071] In this disclosure, these boron-containing ionizing / non-coordinating anion activators are also sometimes referred to as organoboron compounds.

[0072] In some embodiments, the activator comprises one or more of the following: trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkyl Ammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, bis(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, where the alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.

[0073] In other embodiments, the activator comprises one or more triarylcarbonium borates, such as triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0074] Examples of preferred activators are N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, trimethylammonium tetrakis(perfluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, trimethylammonium Includes tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(perfluorophenyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tributylammonium tetrakis(perfluorophenyl)borate, tributylammonium tetrakis(perfluoronaphthyl)borate, tributylammonium tetrakis(perfluorobiphenyl)borate, tributylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; 1-(4-(tris(pentafluorophenyl))borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0075] A typical ratio of non-coordinating anionic activator to catalyst, e.g., the ratio of all NCA activators to catalyst (metal equivalent), is about a 1:1 molar ratio. Alternative preferred ranges include 0.5:1 to 3:1, or 0.2:1 to 5:1, or 0.1:1 to 10:1, or 0.1:1 to 30:1. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 5:1.

[0076] Scavenger, Chain Transfer Agent and / or Coactivator Scavenger, chain transfer agent or coactivator may also be used. Alkyl aluminum compounds, hydrogen alkyl aluminum compounds, and alkyl aluminum halide compounds may be used as scavengers or coactivators in the catalyst system described herein. Examples of alkyl aluminum compounds include those represented by the formula AlR3, where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof, particularly trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum or mixtures thereof. Examples of hydrogen alkyl aluminum compounds and alkyl aluminum halide compounds include diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride.

[0077] In some embodiments, the catalyst system of the present invention comprises a main catalyst, an organoboron compound as an activator, and an organoaluminum compound as a coactivator (such as alkylaluminum / alkylaluminum halide and / or aluminoxane), and the appropriate molar ratio thereof is within the knowledge of a person skilled in the art. For example, the molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the organoboron compound (in terms of boron) to the organoaluminum compound (in terms of aluminum) may be 1:(1-10):(100-2000), preferably 1:(2-8):(200-1000).

[0078] Useful chain transfer agents that may be used herein are typically represented by the formula AlR 20 3 or ZnR 20 2 (wherein each R 20 are independently a C1 to C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or an isomer thereof), or a combination thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

[0079] [Support material] In some embodiments, the main catalyst component may optionally include a support or be disposed on at least one support. For example, the catalyst compound may be supported on at least one "support" (sometimes also referred to as a "carrier"), thereby providing the main catalyst component of the catalyst system of the present invention. Here, the terms "support" and "support" are used interchangeably. Suitable supports include, but are not limited to, synthetic or naturally occurring zeolites, as well as inorganic materials such as clays and / or inorganic oxides. The inorganic oxides include, for example, Group 2, 4, 13 and 14 metal oxides, such as silica, alumina, silica-alumina, zirconia, titania, ceria, magnesia, montmorillonite, phyllosilicates, talc, or combinations thereof. In particular, the support may be silica-alumina, silica, alumina, zirconia and / or zeolite. The silica-alumina may be naturally occurring or in the form of a gelled precipitate or gel, including a mixture of silica and alumina. Preferably, the support material is an inorganic oxide in finely divided form. However, other suitable support materials, such as finely divided polyethylene and finely divided polystyrene, can also be used. Furthermore, combinations of these support materials can be used.

[0080] In a second aspect, the present invention relates to a process for the polymerization of olefins, in which an olefin monomer, such as ethylene, and an optional comonomer are contacted with the catalyst system of the present invention as described above. The main catalyst components, including the catalyst compound and optional support, and the activator / cocatalyst may be combined in any order, typically prior to contact with the monomer.

[0081] Therefore, the application of the above-mentioned catalyst system of the present invention in olefin polymerization (including homopolymerization and copolymerization) is also within the scope of the present invention.

[0082] 〔monomer〕 Monomers that can be used in the olefin polymerization process of the present invention include C2-C12 olefin monomers, preferably C2-C12 α-olefin monomers, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and combinations thereof. Preferably, the olefin monomer is ethylene.

[0083] In some embodiments of the present invention where a copolymerization reaction occurs, the copolymerization reaction includes the copolymerization reaction of ethylene with other α-olefins. Exemplary comonomers include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, and substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives. Preference is given to norbornene, norbornadiene and dicyclopentadiene.Preferably, the α-olefin comonomer comprises a C3 to C12 α-olefin, preferably one or more of the isomers thereof, such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and 4-methyl-1-pentene.

[0084] In some embodiments of the present invention in which a copolymerization reaction occurs, the comonomer is present in an amount of up to 40 mol%, e.g., up to 30 mol%, or up to 20 mol%, or up to 18 mol%, or up to 16 mol%, or up to 14 mol%, based on the total amount of monomer and comonomer.

[0085] In some embodiments, one or more dienes are present in the polymers produced herein in an amount up to 10 wt%, preferably 0.00001-1.0 wt%, preferably 0.002-0.5 wt%, and even more preferably 0.003-0.2 wt%, based on the total weight of the polymer. In some embodiments, 500 ppm or less, preferably 400 ppm or less, preferably 300 ppm or less of diene is added to the polymerization. In other embodiments, at least 50 ppm, or at least 100 ppm, or at least 200 ppm of diene is added to the polymerization.

[0086] Diolefin monomers useful in the present invention include any hydrocarbon structure, preferably C4-C30, having at least two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into the polymer by either stereospecific or non-stereospecific catalysis. Preferably, the diolefin monomer is selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin monomer is a linear divinyl monomer, most preferably one containing from 4 to 30 carbon atoms. Examples of preferred dienes are butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, henicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexadecadiene ... Particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbomadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene, or higher ring-containing diolefins with or without substitution at various ring positions.

[0087] [Polymerization method] The polymerization process of the present invention can be carried out in any manner known in the art. Any solution, suspension, slurry, high pressure loop or tank, or gas phase polymerization process known in the art can be used under conditions that permit polymerization. Such processes can be operated in batch, semi-batch, or continuous modes.

[0088] The preferred polymerizations may be carried out at any temperature and / or pressure suitable for obtaining the desired olefin polymer. Typical temperatures include those in the range of 30 to 150° C., preferably 50 to 140° C., or preferably 60 to 130° C., or preferably 70 to 120° C. Typical pressures include those in the range of about 0.35 MPa to about 10 MPa, preferably about 0.45 MPa to about 6 MPa, or preferably about 0.5 MPa to about 4 MPa.

[0089] In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), and more preferably from 0.1 to 10 psig (0.7 to 70 kPa).

[0090] In some embodiments, the polymerization process of the present disclosure is carried out as a heterogeneous polymerization process (e.g., gas phase and slurry phase process). The heterogeneous process is defined as a process in which the catalyst system is insoluble in the reaction medium. In some embodiments, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process in which a supported catalyst is used and monomer is polymerized on the supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent). Suitable diluents / solvents for polymerization include non-coordinating inert liquids. Examples include straight and branched chain aliphatic hydrocarbons, typically alkanes having 3-7 carbon atoms, preferably branched alkanes (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof); cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof); halogenated hydrocarbons (e.g., perfluorinated C4-10 alkanes and chlorobenzene); and aromatic and alkyl-substituted aromatic compounds (e.g., benzene, toluene, 1,3,5-trimethylbenzene, and xylene). Suitable solvents also include liquid olefins that may be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In one embodiment, the solvent is not aromatic, and preferably aromatic hydrocarbons are present in the solvent in an amount less than 1 wt%, preferably less than 0.5 wt%, preferably 0 wt%, based on the weight of the solvent. In one embodiment, the feed concentration of monomers and comonomers used in the polymerization is 60% by volume or less, preferably 40% by volume or less, more preferably 20% by volume or less, based on the total volume of the feed stream.

[0091] Slurry polymerization processes are generally operated at pressures of 1 to about 50 atm (15 psi to 735 psi, 103 kPa to 5068 kPa) and in the temperature ranges described above. In slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomer are added along with a catalyst. The suspension, including the diluent, is intermittently or continuously removed from the reactor, and the volatile components are separated from the polymer and recycled to the reactor, optionally after distillation. The diluent medium employed should be liquid under the polymerization conditions and relatively inert. When a propane medium is used, the process is typically operated above the critical temperature and critical pressure of the reaction diluent. Often, hexane or isobutane medium is employed. In slurry polymerization processes, the preferred temperature is within the range of about 85°C to about 110°C. Two preferred slurry polymerization processes are those employing a loop reactor and those using multiple stirred reactors in series, parallel, or a combination thereof. In one embodiment, the slurry process is carried out continuously in a loop reactor. The catalyst is injected periodically into the reactor loop as a slurry in isobutane or as a dry free-flowing powder, which is itself filled with a circulating slurry of growing polymer particles in a diluent of isobutane containing monomers and comonomers. Optionally, hydrogen may be added as molecular weight control. For example, 500 ppm or less, or 400 ppm or less, or 300 ppm or less of hydrogen is added. The lower limit of the hydrogen concentration can be 50 ppm, or 100 ppm, or 150 ppm. The heat of reaction may be removed through the loop wall. The slurry can exit the reactor at regular intervals or continuously, in order, into a heated low-pressure flash vessel, a rotary dryer, and a nitrogen purge column to remove the isobutane diluent and any unreacted monomers and comonomers. The resulting hydrocarbon-free powder is then formulated for use in various applications.

[0092] In some embodiments, the polymerization process is carried out as a gas phase process, preferably as a fluidized bed gas phase process.Generally, in the fluidized bed gas phase process used to produce polymer, a gas stream containing one or more monomers is continuously cycled through a fluidized bed under polymerization conditions in the presence of a catalyst.The gas stream is removed from the fluidized bed and recycled back to the reactor.At the same time, the polymer product is removed from the reactor and new monomer is added to replace the polymerized monomer.

[0093] In another embodiment, the polymerization process is homogeneous. A homogeneous polymerization process is defined as one in which at least 90% by weight of the product is soluble in the reaction medium. In another embodiment, the polymerization process is a bulk process. A bulk process is defined as one in which the monomer concentration in all feeds to the reactor is 70% by volume or greater.

[0094] In some embodiments, the polymerization is carried out in a solution process. The temperature for the polymerization may be from -30 to 150°C, preferably from 25 to 100°C or from 50 to 110°C. The pressure for the polymerization may be from 0.1 to 10 MPa, preferably from 0.5 to 4 MPa. The duration of the polymerization may be from 10 to 60 minutes. The polymerization reaction may be carried out in an inert solvent. The solvent used may be an arene or alkane, such as benzene, toluene, hexane, heptane, or a mixture thereof.

[0095] A "reaction zone", also called a "polymerization zone", is a vessel in which polymerization occurs, such as a continuous or batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerizations in batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization is carried out in one reaction zone.

[0096] For the production of polyolefin polymers, useful reactor types and / or processes include UNIPOL TMGas phase reactor (available from Univation Technologies); INEOS TM Gas phase reactors and methods; continuous flow stirred tank (CSTR) reactors (solution and slurry); plug flow tube reactors (solution and slurry); slurries (e.g., slurry loop (single loop or double loop) (available from Chevron Phillips Chemical Company) and reactors in series (available from Mitsui Chemicals); BORSTAR TM Processes and reactors (combined slurry and gas phase reactors); and multi-zone circulation reactors (MZCRs), e.g., SPHERIZONE TM These include, but are not limited to, reactors and processes (available from Lyondell Basell).

[0097] In some embodiments, the present invention provides an ethylene homopolymerization process comprising polymerizing ethylene monomer in the presence of a catalyst comprising a main catalyst, the main catalyst comprising a bisphenol metal complex as described above and an optional support, and a cocatalyst. The molecular weight of the polyethylene prepared by the ethylene homopolymerization process can be greater than 200,000 and the polydispersity can range from 1.5 to 20.

[0098] In some embodiments, the ethylene homopolymerization is 1) in the presence of a catalyst system comprising a main catalyst and a co-catalyst, the co-catalyst comprising an organoaluminum compound and an organoboron compound; In some embodiments, the organoaluminum compound is selected from the group consisting of alkylaluminum, alkylaluminum halides, and alkylaluminoxanes, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, and modified methylaluminoxane; In some embodiments, the organoboron compound is selected from the group consisting of aromatic hydrocarbyl boron compounds and borates, such as substituted or unsubstituted phenylborons, such as tris(pentafluorophenyl)boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and triphenylcarbonium tetrakis(pentafluorophenyl)borate; In some embodiments, the molar ratio of the main catalyst (in terms of the metal in the catalyst compound) to the organoboron compound (in terms of boron) to the organoaluminum compound (in terms of aluminum) is 1:(1-10):(100-2000), preferably 1:(2-8):(200-1000); or 2) in the presence of a catalyst system comprising a main catalyst and a cocatalyst, the cocatalyst comprising an aluminoxane; In some embodiments, the molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the aluminoxane (in terms of aluminum) is 1:(200 to 5000), preferably 1:(2000 to 3000); In some embodiments, the aluminoxane has the general formula:

[0099] [ka]

[0100] In the formula, R is C1 to C 12 Preferably, the hydrocarbyl is methyl or isobutyl, and preferably, the aluminoxane is methylaluminoxane (MAO) or a modified methylaluminoxane, more preferably methylaluminoxane.

[0101] Further, in some embodiments, the ethylene homopolymerization is 3) carried out at a temperature of -30 to 150°C, preferably 50 to 110°C; 4) The reaction is carried out under a pressure of 0.1 to 10 MPa, preferably 0.5 to 4 MPa; 5) takes place over a period of 10 to 60 minutes; and / or 6) carried out in an inert solvent, where said solvent may be an arene or an alkane, such as benzene, toluene, hexane, heptane and mixtures thereof.

[0102] In some embodiments, the present invention provides an ethylene copolymerization process, in which ethylene and a comonomer are polymerized in the presence of a catalyst comprising a bisphenol metal complex-containing main catalyst and a cocatalyst. The weight average molecular weight of the polyethylene prepared by the ethylene copolymerization process can be greater than 200,000, the molecular weight distribution is between 2-10, and the molar content of the comonomer is 1-30%, based on the total monomers.

[0103] In some embodiments, the ethylene copolymerization comprises: 1) in the presence of a catalyst system comprising a main catalyst and a co-catalyst, the co-catalyst comprising an organoaluminum compound and an organoboron compound; In some embodiments, the organoaluminum compound is selected from the group consisting of alkylaluminum, alkylaluminum halides, and alkylaluminoxanes, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, and modified methylaluminoxane; In some embodiments, the organoboron compound is selected from the group consisting of aromatic hydrocarbyl boron compounds and borates, such as substituted or unsubstituted phenylborons, such as tris(pentafluorophenyl)boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and triphenylcarbonium tetrakis(pentafluorophenyl)borate; In some embodiments, the molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the organoboron compound to the organoaluminum compound is 1:(1-10):(100-2000), preferably 1:(2-8):(200-1000); alternatively, the molar ratio of the main catalyst to the organoboron compound to the organoaluminum compound is 1:(1-20):(200-2000), preferably 1:(1-10):(200-2000) or 1:(4-16):(300-1000); or 2) in the presence of a catalyst system comprising a main catalyst and a cocatalyst, the cocatalyst comprising an aluminoxane; In some embodiments, the molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the aluminoxane (in terms of aluminum) is 1:(200 to 5000), preferably 1:(2000 to 3000); In some embodiments, the aluminoxane has the general formula:

[0104] [ka]

[0105] In the formula, R is C1 to C 12 Preferably, the hydrocarbyl is methyl or isobutyl, and preferably, the aluminoxane is methylaluminoxane (MAO) or a modified methylaluminoxane, more preferably methylaluminoxane.

[0106] Further, in some embodiments, the ethylene copolymerization is 3) utilizing comonomers including α-olefins and / or dienes, preferably C4 to C10 α-olefins and / or dienes, such as one or more of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene; 4) The reaction is carried out at a temperature of -30 to 150°C, preferably 25 to 100°C; 5) The reaction is carried out under a pressure of 0.1 to 10 MPa, preferably 0.5 to 4 MPa; 6) takes place over a period of 10 to 60 minutes; and / or 7) carried out in an inert solvent, where said solvent may be an arene or an alkane, such as benzene, toluene, hexane, heptane and mixtures thereof.

[0107] [Polyethylene products] In one embodiment, the process described herein produces a polyethylene composition comprising a homopolymer of ethylene and a copolymer of ethylene and one, two, three, four or more C3-C20 olefin monomers, such as C3-C12 α-olefin monomers. For example, the polyethylene composition comprises a copolymer of ethylene and one, two or three different C3-C20 olefins, where the C3-C20 olefins are preferably C3-C12 α-olefins, preferably propylene, butene, hexene, octene, decene, dodecene, more preferably propylene, butene, hexene, octene, or mixtures thereof.

[0108] The polyethylene composition may comprise 99.0 to about 80.0 wt%, 99.0 to 85.0 wt%, 99.0 to 87.5 wt%, 99.0 to 90.0 wt%, 99.0 to 92.5 wt%, 99.0 to 95.0 wt%, or 99.0 to 97.0 wt% of polymer units derived from ethylene, and about 1.0 to about 20.0 wt%, 1.0 to 15.0 wt%, 0.5 to 12.5 wt%, 1.0 to 10.0 wt%, 1.0 to 7.5 wt%, 1.0 to 5.0 wt%, or 1.0 to 3.0 wt% of polymer units derived from one or more of a C3 to C12 α-olefin comonomer, preferably a C3 to C12 α-olefin, more preferably a C4 to C8 α-olefin, for example, hexene and octene. The α-olefin comonomer may be linear or branched, and two or more comonomers may be used if desired. Examples of suitable comonomers include propylene; butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl substituted 1-decene; 1-dodecene; and styrene. Particularly suitable comonomers include 1-butene, 1-hexene, 1-octene and mixtures thereof.

[0109] The polyethylene composition has a desired melt index (I 2.16 ) can have a suitable melt index (I 2.16 The lower limit of the melt index (I) may be, for example, about 0.01 g / 10 min, about 0.05 g / 10 min, about 0.1 g / 10 min, about 0.15 g / 10 min, about 0.20 g / 10 min, about 0.30 g / 10 min, about 0.50 g / 10 min, about 1.0 g / 10 min, about 2.0 g / 10 min, or about 3.0 g / 10 min, and the appropriate melt index (I 2.16) may be, for example, about 200 g / 10 min, about 150 g / 10 min, about 100 g / 10 min, about 50 g / 10 min, about 40 g / 10 min, about 30 g / 10 min, about 20 g / 10 min, about 10 g / 10 min, about 5 g / 10 min, about 3.0 g / 10 min, about 2.0 g / 10 min, about 1.0 g / 10 min, about 0.7 g / 10 min, as measured according to ASTM D-1238 test method at 190° C. under a load of 2.16 kg. Expressly disclosed ranges include, but are not limited to, ranges formed by combining the upper limits recited above with the lower limits, provided that the upper limit is greater than the lower limit.

[0110] The polyethylene composition has a desired high load melt index (HLMI) ( 21.6 ) can have a suitable high load melt index (HLMI) (I 21.6 The lower limit of the high load melt index (HLMI) (I) may be, for example, 1 g / 10 min, 2 g / 10 min, 3 g / 10 min, 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 50 g / 10 min, and a suitable high load melt index (HLMI) (I 21.6 ) may be, for example, 500g / 10min, 400g / 10min, 300g / 10min, 200g / 10min, 100g / 10min, 80g / 10min, 70g / 10min, 60g / 10min, or 50g / 10min, as measured in accordance with ASTM D-1238 test method at 190°C under a load of 21.6 kg (HLMI). Expressly disclosed ranges include, but are not limited to, ranges formed by combining an upper limit recited above with a lower limit, provided that the upper limit is greater than the lower limit.

[0111] The polyethylene composition may have a melt index ratio (MIR) of 4 to 100, or 5 to 90, or 7 to 90, or 10 to 80, or 10 to 60, or 20 to 60, or 25 to 60, or 30 to 55, or 35 to 55, or 35 to 50. MIR is defined as 21.6 / I 2.16 It is defined as:

[0112] The polyethylene composition can have a desired density. A suitable lower limit of the density range is, for example, about 0.880 g / cm. 3 , about 0.890g / cm 3 , about 0.900g / cm 3 , about 0.910g / cm 3 , about 0.918g / cm 3 , about 0.919g / cm 3 , about 0.920g / cm 3 , about 0.925g / cm 3 , about 0.930g / cm 3 , or about 0.932 g / cm 3 and the upper limit of the suitable density range is, for example, about 0.960 g / cm 3 , about 0.950g / cm 3 , about 0.945g / cm 3 , about 0.940g / cm 3 , about 0.937g / cm 3 , about 0.935g / cm 3 , about 0.933g / cm 3 , about 0.930g / cm 3 , about 0.920g / cm 3 , or about 0.915 g / cm 3 The ranges explicitly disclosed include, but are not limited to, the ranges formed by combining the upper limit recited above with the lower limit, provided that the upper limit is greater than the lower limit. Density is determined by ASTM D1505 method. Samples are molded according to ASTM D4703-10a Procedure C, then conditioned according to ASTM D618-08 (23°C ± 2°C and 50 ± 10% relative humidity) for 40 hours before testing.

[0113] The polyethylene composition can have a molecular weight distribution (MWD, defined as Mw / Mn) of from about 2 to about 12, from about 2 to about 10, or from about 2 to about 8, from about 2.2 to about 5.5, or from about 2.4 to 5.0.

[0114] In any of the embodiments described herein, the polyethylene composition may be a multimodal polyethylene composition, such as a bimodal polyethylene composition, or the polyethylene composition may be a non-bimodal polyethylene composition, such as a unimodal polyethylene composition. As used herein, "multimodal" means that there are at least two distinguishable peaks in the molecular weight distribution curve (determined by gel permeation chromatography (GPC) or other recognized analytical technique) of the polyethylene composition. For example, if there are two distinguishable peaks in the molecular weight distribution curve, such a composition can be referred to as a bimodal composition. Typically, if there is only one peak (e.g., a single peak) and no clear valley between the peaks, one of the peaks is not considered to be a distinguishable peak or both peaks are not considered to be distinguishable peaks, and such a composition can be said to be non-bimodal. Often, a bimodal molecular weight distribution is characterized by having a distinguishable high molecular weight component (or distribution) and a distinguishable low molecular weight component (or distribution). Representative non-bimodal molecular weight distribution curves include unimodal molecular weight distribution curves and distribution curves that include two peaks that cannot be easily distinguished, separated, or deconvoluted.

[0115] In any of the embodiments described herein, the polyethylene composition may have a total internal unsaturation / 1000 carbon atoms greater than 0.2, or greater than 0.3, or greater than 0.32, or greater than 0.38, or greater than 0.4, 1 Measured by H NMR.

[0116] [Example] The present invention is further described below in conjunction with specific examples, which do not constitute any limitation to the present invention.

[0117] The evaluation and test methods included in the following examples are as follows: 1. Proton and carbon nuclear magnetic spectra of the catalysts are recorded at room temperature on a Bruker-400 nuclear magnetic resonance spectrometer using deuterated chloroform as the solvent.

[0118] 2. High resolution mass spectra are recorded on a Bruker ESI-Q / TOF MS mass spectrometer using acetonitrile as the dispersing solvent.

[0119] 3. Polymerization activity: The polymer obtained by polymerization is dried and weighed, and the catalyst activity is obtained by dividing the weight of the polymer by the amount of catalyst added during polymerization.

[0120] 4. Molecular weight and molecular weight distribution PDI (PDI=Mw / Mn) of polymer: Measured using 1,2,4-trichlorobenzene as a solvent at 150°C using PL-GPC220 (standard: PS; flow rate: 1.0 mL / min; column: 3 x Plgel 10 um M1 x ED-B 300 x 7.5 nm).

[0121] 5. The melting point of the polymer is determined by differential scanning calorimetry (DSC) as follows: 10 mg of sample is placed in a crucible and measured on a Pekin Elmer DSC 8500 differential scanning calorimeter. Under nitrogen atmosphere, the temperature is increased from -70°C to 200°C at a ramp rate of 10°C / min and maintained for 1 minute, then the temperature is decreased to -70°C at a rate of 10°C / min and maintained for 3 minutes. The temperature is then increased again to 200°C at a rate of 10°C / min and the data of the second heating scan is recorded.

[0122] 6. The content of comonomers in the polymer is determined by high temperature nuclear magnetic carbon spectroscopy.

[0123] Example 1 - Preparation of bisphenol metal complex 7 Bisphenol compound 3 (2.24 mmol) was dissolved in diethyl ether solvent, and neat KH solid (8.96 mmol) was added to the resulting solution at -78 °C. After reacting for 1 h, the reaction mixture was warmed to room temperature, and then the reaction was continued for another 2 h. This solution was then transferred by transfer conduction to a solution of metal complex 2 (4.48 mmol) in dichloromethane at -78 °C. After reacting for 1 h at that temperature, the reaction mixture was gradually warmed to room temperature, and then the reaction was continued for another 12 h. Upon completion of the reaction, the solvent was removed on a vacuum line, and the residue was washed with dichloromethane and filtered through Celite. The filtrate was evaporated to dryness under vacuum, and the crude product was recrystallized with dichloromethane / n-hexane to obtain the orange target product in 90% yield. The orange product was characterized as follows: 1 H NMR (CDCl3, 400 MHz): δ = 7.45 (dd, J = 7.6, 2.0 Hz, 2H, aryl-H), 7.25 (s, 4H, aryl-H), 7.14-7.21 (m, 4H, aryl-H), 3.13 (m, 4H, CH), 2.18 (s, 30H, CH3), 1.80 (s, 6H, CH3), 1.03 (d, J=6.8Hz, 24H, CH3).

[0124] 13 C NMR (CDCl3, 100 MHz): δ = 159.1, 146.9, 138.9, 133.5, 132.8, 130.6, 130.4, 130.0, 124.5, 122.9, 34.3, 33.9, 26.3, 24.3, 13.1.

[0125] ESI-MS for C 59 H 72 Cl4O3Ti2(M / Z=1064.32), found: M=1064.34.

[0126] Example 2 - Preparation of bisphenol metal complex 7 Bisphenol compound 3 (2.24 mmol) was dissolved in diethyl ether solvent, and neat KH solid (22.4 mmol) was added to the resulting solution at 40°C. After reacting for 1 h, the reaction mixture was cooled to room temperature, and then the reaction was continued for another 0.5 h. This solution was then transferred by transfer conduction to a solution of metal complex 2 (4.93 mmol) in dichloromethane at 40°C, and the mixture was reacted at that temperature for 6 h. Upon completion of the reaction, the solvent was removed on a vacuum line, and the residue was washed with dichloromethane and filtered through Celite. The filtrate was evaporated to dryness under vacuum, and the crude product was recrystallized with dichloromethane / n-hexane to give the orange target product in 73% yield.

[0127] Example 3 - Preparation of bisphenol metal complex 4 Bisphenol compound 4 (2.00 mmol) was dissolved in tetrahydrofuran solvent, and neat NaH solid (12.00 mmol) was added to the resulting solution at -10 °C. After reacting for 1 h, the reaction mixture was warmed to room temperature, and then the reaction was continued for another 1 h. This solution was then transferred by transfer conduction to a solution of metal complex 1 (4.00 mmol) in tetrahydrofuran at -10 °C. After reacting at that temperature for 0.5 h, the reaction mixture was gradually warmed to room temperature, and then the reaction was continued for another 8 h. Upon completion of the reaction, the solvent was removed on a vacuum line, and the residue was washed with dichloromethane and filtered through Celite. The filtrate was evaporated to dryness under vacuum, and the crude product was recrystallized with dichloromethane / n-hexane to obtain the orange target product in 92% yield. The orange product was characterized as follows: ESI-MS for C 51 H 56 Cl4O3Ti2: M / Z = 954.21.

[0128] Example 4 - Preparation of Bisphenol Metal Complex A

[0129] [ka]

[0130] Bisphenol compound 3 (2.24 mmol) was dissolved in diethyl ether solvent, and n-BuLi (4.48 mmol, 1.6 mol / L) was added to the resulting solution at -78 °C. After reacting for 1 h, the reaction mixture was warmed to room temperature, and then the reaction was continued for another 2 h. This solution was then transferred by transfer conduction to a solution of indenyl titanium complex (4.48 mmol) in diethyl ether at -78 °C. After reacting for 1 h at that temperature, the reaction mixture was gradually warmed to room temperature, and then the reaction was continued for another 12 h. Upon completion of the reaction, the solvent was removed on a vacuum line, and the residue was washed with dichloromethane and filtered through Celite. The filtrate was evaporated to dryness under vacuum, and the crude product was recrystallized with dichloromethane / n-hexane to obtain the purple-red target product in 60% yield.

[0131] 1 H NMR (CDCl3, 400 MHz): δ = 7.74 (dd, J = 6.4, 2.8 Hz, 4H, aryl-H), 7.47 (t, J = 4.8 Hz, 2H, aryl-H), 7.37 (dd, J = 6.4, 2.8 Hz, 4H, aryl-H), 7.22 (s, 4H, aryl-H), 7.18 (d, J = 4.8 Hz, 4H, aryl-H), 6.78 (d, J = 3.6 Hz, 4H, aryl-H), 6.42 (t, J = 3.2 Hz, 2H, aryl-H), 3.25 (sept, 4H, CH), 2.18 (s, 30H, CH3), 1.82(s, 6H, CH3), 1.08 (d, J=6.8Hz, 24H, CH3).

[0132] 13 C NMR (CDCl3, 100 MHz): δ = 164.5, 146.8, 138.5, 134.6, 130.6, 130.3, 129.9, 129.7, 128.3, 125.9, 125.8, 124.5, 123.0, 120.4, 113.3, 34.2, 34.0, 26.8, 23.8.

[0133] Example 5 - Preparation of bisphenol metal complex B

[0134] [ka]

[0135] Bisphenol compound 3 (1.00 mmol) was dissolved in tetrahydrofuran solvent, and n-BuLi (2.00 mmol, 1.6 mol / L) was added to the resulting solution at -78 °C. After reacting for 1 h, the reaction mixture was warmed to room temperature, and then the reaction was continued for another 2 h. This solution was then transferred by transfer conduction to a solution of pentamethylcyclopentadienyl hafnium complex (2.00 mmol) in tetrahydrofuran at -78 °C. After reacting at that temperature for 1 h, the reaction mixture was gradually warmed to room temperature, then heated to 50 °C, and then the reaction was continued for another 12 h. Upon completion of the reaction, the solvent was removed on a vacuum line, and the residue was washed with dichloromethane and filtered through Celite. The filtrate was evaporated to dryness under vacuum, and the crude product was recrystallized with dichloromethane / n-hexane to obtain the purple target product in 21% yield.

[0136] 1 H NMR (CDCl3, 400 MHz): δ = 7.40 (dd, J = 7.4, 2.2 Hz, 2H, aryl-H), 7.16-7.11 (m, 4H, aryl-H), 7.08 (s, 4H, aryl-H), 2.93 (sept, 4H, CH), 2.22 (s, 30H, CH3), 1.77 (s, 6H, CH3), 1.04 (d, J=6.8Hz, 24H, CH3).

[0137] Example 6 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 10 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 2.8 g of polyethylene polymer was obtained. The polymerization activity was 8.4 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 133.5°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 4.82.

[0138] Example 7 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.5 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 2.0 g of polyethylene polymer was obtained. The polymerization activity was 6.0 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.9°C; the Mw measured by GPC was 2.1×10 5 and Mw / Mn was found to be 6.02.

[0139] Example 8 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.1 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 2.79 g of polyethylene polymer was obtained. The polymerization activity was 1.7 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 132.7°C; the Mw measured by GPC was 1.8×10 5 and Mw / Mn was found to be 7.87.

[0140] Example 9 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 3.1 g of polyethylene polymer was obtained. The polymerization activity was 9.3 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.4°C; the Mw measured by GPC was 2.2×10 5 and Mw / Mn was found to be 5.17.

[0141] Example 10 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 0 °C for 20 minutes, and then ethanol was added to stop the reaction. 3.6 g of polyethylene polymer was obtained. The polymerization activity was 1.1 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 134.2°C; the Mw measured by GPC was 8.0×10 4 and Mw / Mn was found to be 3.95.

[0142] Example 11 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 2.9 g of polyethylene polymer was obtained. The polymerization activity was 8.7 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.0°C; the Mw measured by GPC was 2.1×10 5 and Mw / Mn was found to be 10.1.

[0143] Example 12 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2.5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 2.6 g of polyethylene polymer was obtained. The polymerization activity was 7.8 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 133.2°C; the Mw measured by GPC was 2.3×10 5 and Mw / Mn was found to be 8.08.

[0144] Example 13 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 1 mmol / mL modified methylaluminoxane (MMAO) in toluene solution, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a 5.0 μmol / mL toluene solution of bisphenol metal complex 7 were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 20 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 3.3 g of polyethylene polymer was obtained. The polymerization activity was 9.9 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 132.5°C; the Mw measured by GPC was 1.7×10 5 and Mw / Mn was found to be 6.81.

[0145] Example 14 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (5 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 6.8 g of polyethylene polymer was obtained. The polymerization activity was 1.02 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 132.4°C; the Mw measured by GPC was 2.5×10 5 and Mw / Mn was found to be 9.03.

[0146] Example 15 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 1.81 g of polyethylene polymer was obtained. The polymerization activity was 1.09 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 135.3°C; the Mw measured by GPC was 2.5×10 5 and Mw / Mn was found to be 7.84.

[0147] Example 16 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 30 minutes, and then ethanol was added to stop the reaction. 3.5 g of polyethylene polymer was obtained. The polymerization activity was 7.0 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.2°C; the Mw measured by GPC was 2.6×10 5 and Mw / Mn was found to be 6.99.

[0148] Example 17 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1.0 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 10 min, and then ethanol was added to stop the reaction. 1.94 g of polyethylene polymer was obtained. The polymerization activity was 1.16 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 132.6°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 4.79.

[0149] Example 18 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Next, 5 mL of a 2 mmol / mL toluene solution of methylaluminoxane (MAO), 100 mL of deoxygenated and dehydrated toluene, and 1.0 mL of a toluene solution of bisphenol metal complex 7 (5.0 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 20 °C for 20 minutes, and then ethanol was added to stop the reaction. 3.7 g of polyethylene polymer was obtained. The polymerization activity was 1.11 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.9°C; the Mw measured by GPC was 2.0×10 5 and Mw / Mn was found to be 6.69.

[0150] Example 19 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 1.0 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 5.1 g of polyethylene polymer was obtained. The polymerization activity was 3.06 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 133.3°C; the Mw measured by GPC was 1.8×10 5 and Mw / Mn was found to be 6.84.

[0151] Example 20 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 40 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 2.6 g of polyethylene polymer was obtained. The polymerization activity was 1.56 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 130.6°C; the Mw measured by GPC was 2.0×10 5 and Mw / Mn was found to be 7.05.

[0152] Example 21 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.1 MPa was introduced therein, and the reaction was continued at 0 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 1.15 g of polyethylene polymer was obtained. The polymerization activity was 6.90 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.5°C; the Mw measured by GPC was 1.7×10 5and Mw / Mn was found to be 8.97.

[0153] Example 22 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Next, 5 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 4 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 3.4 g of polyethylene polymer was obtained. The polymerization activity was 2.04 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 130.3°C; the Mw measured by GPC was 1.5×10 5 and Mw / Mn was found to be 4.10.

[0154] Example 23 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 1.5 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 8 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 2.3 g of polyethylene polymer was obtained. The polymerization activity was 1.38 × 10 6 g mol -1 (Ti)·h-1 The melting point measured by DSC was 134.1°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 5.93.

[0155] Example 24 After drying by heating, the 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 4 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 4 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 5.9 g of polyethylene polymer was obtained. The polymerization activity was 1.77 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 134.3°C; the Mw measured by GPC was 2.0×10 5 and Mw / Mn was found to be 7.94.

[0156] Example 25 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a toluene solution of 0.5 mmol / mL triisobutylaluminum, 150 mL of deoxygenated and dehydrated toluene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 40 minutes, and then ethanol was added to stop the reaction. 6.3 g of polyethylene polymer was obtained. The polymerization activity was 1.89 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 131.0°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 5.54.

[0157] Example 26 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a toluene solution of 0.5 mmol / mL triisobutylaluminum, 150 mL of deoxygenated and dehydrated n-heptane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 10 minutes, and then ethanol was added to stop the reaction. 2.6 g of polyethylene polymer was obtained. The polymerization activity was 3.12 × 10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 133.0°C; the Mw measured by GPC was 1.6×10 5 and Mw / Mn was found to be 4.99.

[0158] Example 27 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 5.21 g of polymer was obtained. The activity was 1.56×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 103°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 1.92. The molar content of 1-hexene was found to be 5.3% by high temperature nuclear magnetic carbon spectroscopy.

[0159] Example 28 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 3.4 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 4.97 g of polymer was obtained. The activity was 1.49×10 6 g mol -1 (Ti)·h -1The melting point measured by DSC was 107°C; the Mw measured by GPC was 2.2×10 5 and Mw / Mn was found to be 2.17. The molar content of 1-hexene was found to be 4.8% by high temperature nuclear magnetic carbon spectroscopy.

[0160] Example 29 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 13.6 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 5.07 g of polymer was obtained. The activity was 1.52×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 104°C; the Mw measured by GPC was 1.9×10 5 and Mw / Mn was found to be 2.31. The 1-hexene content was found to be 4.7% by high temperature nuclear magnetic carbon spectroscopy.

[0161] Example 30 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 5 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 7.43 g of polymer was obtained. The activity was 2.23×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 123°C; the Mw measured by GPC was 1.8×10 5 and Mw / Mn was found to be 1.86. The 1-hexene content was found to be 2.7% by high temperature nuclear magnetic carbon spectroscopy.

[0162] Example 31 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 10 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 8.87 g of polymer was obtained. The activity was 2.66×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 116°C; the Mw measured by GPC was 2.5×10 5and Mw / Mn was found to be 2.20. The 1-hexene content was found to be 3.4% by high temperature nuclear magnetic carbon spectroscopy.

[0163] Example 32 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 50 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 6.77 g of polymer was obtained. The activity was 2.03×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 70°C; the Mw measured by GPC was 1.8×10 5 and Mw / Mn was found to be 2.30. The molar content of 1-hexene was found to be 12.4% by high temperature nuclear magnetic carbon spectroscopy.

[0164] Example 33 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 300 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 13.6 g of polymer was obtained. The activity was 4.08×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 119°C; the Mw measured by GPC was 2.1 x 10 5 and Mw / Mn was found to be 2.04. The 1-hexene content was found to be 3.3% by high temperature nuclear magnetic carbon spectroscopy.

[0165] Example 34 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 2.14 g of polymer was obtained. The activity was 1.28×10 6 g mol -1 h -1 The melting point measured by DSC was 107°C; the Mw measured by GPC was 1.9×10 5and Mw / Mn was found to be 1.91. The 1-hexene content was found to be 4.9% by high temperature nuclear magnetic carbon spectroscopy.

[0166] Example 35 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 4 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 14.0 g of polymer was obtained. The activity was 2.1×10 6 g mol -1 h -1 The melting point measured by DSC was 93°C; the Mw measured by GPC was 2.5×10 5 and Mw / Mn was found to be 2.27. The 1-hexene content was found to be 6.8% by high temperature nuclear magnetic carbon spectroscopy.

[0167] Example 36 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 10 minutes, and then ethanol was added to stop the reaction. 2.67 g of polymer was obtained. The activity was 1.60×106 g mol -1 h -1 The melting point measured by DSC was 102°C; the Mw measured by GPC was 1.7×10 5 and Mw / Mn was found to be 1.85. The 1-hexene content was found to be 5.0% by high temperature nuclear magnetic carbon spectroscopy.

[0168] Example 37 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 30 minutes, and then ethanol was added to stop the reaction. 10.11 g of polymer was obtained. The activity was 2.02×10 6 g mol -1 h -1 The melting point measured by DSC was 108°C; the Mw measured by GPC was 2.3×10 5 and Mw / Mn was found to be 1.99. The 1-hexene content was found to be 4.9% by high temperature nuclear magnetic carbon spectroscopy.

[0169] Example 38 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.1 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 1.81 g of polymer was obtained. The activity was 5.4×10 5 g mol -1 h -1 The melting point measured by DSC was 63°C; the Mw measured by GPC was 2.1 x 10 5 and Mw / Mn was found to be 2.03. The 1-hexene content was found to be 8.7% by high temperature nuclear magnetic carbon spectroscopy.

[0170] Example 39 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 10.48 g of polymer was obtained. The activity was 3.14×10 6 g mol -1 h -1 The melting point measured by DSC was 125°C; the Mw measured by GPC was 2.3 x 10 5and Mw / Mn was found to be 2.42. The 1-hexene content was found to be 2.8% by high temperature nuclear magnetic carbon spectroscopy.

[0171] Example 40 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution (10% by weight) of methylaluminoxane (MAO), 100 mL of 1-hexene, 250 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution (2.5 μmol / mL) of bisphenol metal complex 7 were added in sequence. Ethylene under a pressure of 3.0 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 17.47 g of polymer was obtained. The activity was 5.29×10 6 g mol -1 h -1 The melting point measured by DSC was 127°C; the Mw measured by GPC was 2.5×10 5 and Mw / Mn was found to be 2.18. The 1-hexene content was found to be 1.8% by high temperature nuclear magnetic carbon spectroscopy.

[0172] Example 41 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 40° C. for 20 minutes, and then ethanol was added to stop the reaction. 3.59 g of polymer was obtained. The activity was 1.08×10 6 g mol -1 h -1 The melting point measured by DSC was 89°C; the Mw measured by GPC was 2.1 x 10 5 and Mw / Mn was found to be 1.72. The 1-hexene content was found to be 7.4% by high temperature nuclear magnetic carbon spectroscopy.

[0173] Example 42 - Synthesis of ethylene and 1-hexene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 80° C. under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 2.66 g of polymer was obtained. The activity was 7.98×10 5 g mol -1 h -1 The melting point measured by DSC was 57°C; the Mw measured by GPC was 1.8×10 5and Mw / Mn was found to be 2.41. The 1-hexene content was found to be 12.1% by high temperature nuclear magnetic carbon spectroscopy.

[0174] Example 43 - Synthesis of ethylene and 1-octene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-octene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 5.84 g of polymer was obtained. The activity was 1.75×10 6 g mol -1 h -1 The melting point measured by DSC was 95°C; the Mw measured by GPC was 1.9 x 10 5 and Mw / Mn was found to be 2.07. The 1-octene content was found to be 6.7% by high temperature nuclear magnetic carbon spectroscopy.

[0175] Example 44 - Synthesis of ethylene and 1-decene copolymer After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 6.8 mL of a toluene solution of methylaluminoxane (MAO) (10% by weight), 15 mL of 1-decene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence. Ethylene under a pressure of 0.3 MPa was introduced thereto while mechanically stirring, and the reaction was continued under that pressure at 25° C. for 20 minutes, and then ethanol was added to stop the reaction. 4.73 g of polymer was obtained. The activity was 1.42×106 g mol -1 h -1 The melting point measured by DSC was 102°C; the Mw measured by GPC was 2.3×10 5 and Mw / Mn was found to be 2.09. The 1-decene content was found to be 5.5% by high temperature nuclear magnetic carbon spectroscopy.

[0176] Example 45 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 87 mL of deoxygenated and dehydrated n-hexane, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 0.5 MPa was introduced therein while mechanically stirring, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 9.6 g of polymer was obtained. The polymerization activity was 5.76 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer was 94°C as measured by DSC; the Mw of the polymer was 1.16×10 5 and Mw / Mn was found to be 4.08. The 1-octene content was found to be 8.9% by high temperature nuclear magnetic carbon spectroscopy.

[0177] Example 46 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 87 mL of deoxygenated and dehydrated n-hexane, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 0.1 MPa was introduced therein while mechanically stirring, and the reaction was continued under that pressure at 0 °C for 20 minutes, and then ethanol was added to stop the reaction. 3.9 g of polymer was obtained. The polymerization activity was 2.34 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer could not be measured by DSC; the Mw of the polymer measured by GPC was 7.3 × 10 4 and Mw / Mn was found to be 3.87. The 1-octene content was found to be 19.4% by high temperature nuclear magnetic carbon spectroscopy.

[0178] Example 47 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 87 mL of deoxygenated and dehydrated n-hexane, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 2.0 MPa was introduced therein while mechanically stirring, and the reaction was continued under that pressure at 40 °C for 20 minutes, and then ethanol was added to stop the reaction. 18.0 g of polymer was obtained. The polymerization activity was 1.08 × 10 7 g mol -1 (Ti)·h -1The melting point of the polymer measured by DSC was 113°C; the Mw of the polymer measured by GPC was 1.51 x 10 5 and Mw / Mn was found to be 3.47. The 1-octene content was found to be 3.3% by high temperature nuclear magnetic carbon spectroscopy.

[0179] Example 48 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 79 mL of deoxygenated and dehydrated n-hexane, 16 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 0.5 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 12.3 g of polymer was obtained. The polymerization activity was 7.38 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer was 56°C as measured by DSC; the Mw of the polymer was 1.0×10 5 and Mw / Mn was found to be 2.58. The 1-octene content was found to be 13.8% by high temperature nuclear magnetic carbon spectroscopy.

[0180] Example 49 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 81 mL of deoxygenated and dehydrated n-hexane, 14 mL of 1-hexene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 8.8 g of polymer was obtained. The polymerization activity was 5.28 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer could not be measured by DSC; the Mw of the polymer measured by GPC was 9.7×10 4 and Mw / Mn was found to be 2.44. The 1-hexene content was found to be 14.8% by high temperature nuclear magnetic carbon spectroscopy.

[0181] Example 50 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 81 mL of deoxygenated and dehydrated n-hexane, 3.73 g of 1-butene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 8.4 g of polymer was obtained. The polymerization activity was 5.04 × 10 6 g mol -1 (Ti)·h -1The melting point of the polymer was determined to be 123°C by DSC; the Mw of the polymer was calculated to be 1.7×10 by GPC. 5 and Mw / Mn was found to be 2.34. The 1-butene content was found to be 4.6% by high temperature nuclear magnetic carbon spectroscopy.

[0182] Example 51 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triethylaluminum in n-hexane, 81 mL of deoxygenated and dehydrated n-hexane, 16 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [PhNMe2][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 0.5 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 11.2 g of polymer was obtained. The polymerization activity was 6.72 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer was 53°C as measured by DSC; the Mw of the polymer was 8.1×10 as measured by GPC. 4 and Mw / Mn was found to be 2.63. The 1-octene content was found to be 15.3% by high temperature nuclear magnetic carbon spectroscopy.

[0183] Example 52 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a toluene solution of 0.5 mmol / mL triisobutylaluminum, 87 mL of deoxygenated and dehydrated toluene, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [PhNMe2][B(C6F5)4] (5 μmol / mL). Ethylene under a pressure of 0.5 MPa was introduced thereto while mechanically stirring, and the reaction was continued at 80 °C under that pressure for 20 minutes, and then ethanol was added to stop the reaction. 9.9 g of polymer was obtained. The polymerization activity was 5.94 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer was 91°C as measured by DSC; the Mw of the polymer was 1.6×10 5 and Mw / Mn was found to be 2.23. The 1-octene content was found to be 9.3% by high temperature nuclear magnetic carbon spectroscopy.

[0184] Example 53 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 87 mL of deoxygenated and dehydrated toluene, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [PhNMe2][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 10 minutes, and then ethanol was added to stop the reaction. 5.8 g of polymer was obtained. The polymerization activity was 6.96 × 10 6 g mol -1 (Ti)·h -1The melting point of the polymer was determined to be 91°C by DSC; the Mw of the polymer was calculated to be 1.4 x 10 by GPC. 5 and Mw / Mn was found to be 2.03. The 1-octene content was found to be 9.7% by high temperature nuclear magnetic carbon spectroscopy.

[0185] Example 54 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 87 mL of deoxygenated and dehydrated n-hexane, 8 mL of 1-octene, and 1 mL of a toluene solution of bisphenol metal complex 7 (2.5 μmol / mL) were added in sequence, followed by 2 mL of a toluene solution of boron-containing reagent [PhNMe2][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.5 MPa was introduced therein, and the reaction was continued at 80 °C under that pressure for 40 minutes, and then ethanol was added to stop the reaction. 15.7 g of polymer was obtained. The polymerization activity was 4.71 × 10 6 g mol -1 (Ti)·h -1 The melting point of the polymer was 95°C as measured by DSC; the Mw of the polymer was 1.7×10 as measured by GPC. 5 and Mw / Mn was found to be 2.33. The 1-octene content was found to be 8.5% by high temperature nuclear magnetic carbon spectroscopy.

[0186] Example 55 After drying by heating, a 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of a 0.5 mmol / mL solution of triisobutylaluminum in n-hexane, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a 2.5 μmol / mL solution of bisphenol metal complex A in toluene were added in sequence, followed by 3 mL of boron-containing reagent [Ph3C][B(CF5)4] (5 μmol / mL). Ethylene under a pressure of 0.4 MPa was introduced therein while mechanically stirring, and the reaction was continued at 40 °C under that pressure for 10 minutes, and then ethanol was added to stop the reaction. 1.3 g of polyethylene polymer was obtained. The polymerization activity was 7.8 × 10 5 g mol -1 (Ti)·h -1 The melting point measured by DSC was 130.0°C; the Mw of the polyethylene measured by GPC was 3.4×10 5 and Mw / Mn was found to be 8.53.

[0187] Example 56 After drying by heating, the 500 mL polymerization autoclave was evacuated and then filled with nitrogen gas twice, then evacuated and then filled with ethylene gas once. Then, 2 mL of 0.5 mmol / mL triisobutylaluminum in n-hexane, 9.3 mL 1-octene, 150 mL deoxygenated and dehydrated n-hexane, and 2 mL of 2.5 μmol / mL bisphenol metal complex A in toluene were added in sequence, followed by 3 mL of boron-containing reagent [Ph3C][B(C6F5)4] (5 μmol / mL). With mechanical stirring, ethylene under a pressure of 0.4 MPa was introduced therein, and the reaction was continued at 40° C. under that pressure for 10 minutes, and then ethanol was added to stop the reaction. 2.25 g of polyethylene polymer was obtained. The activity was 1.35×10 6 g mol -1 (Ti)·h -1 The melting point measured by DSC was 125.5°C; the Mw of the polyethylene measured by GPC was 5.6×10 4and Mw / Mn was found to be 2.91. The molar content of 1-octene was found to be 2.4% by high temperature nuclear magnetic carbon spectroscopy.

[0188] For any numerical value described in the present invention, if there is only a two-unit interval between any minimum value and any maximum value, all values ​​having one-unit increments from the minimum value to the maximum value are included. For example, if the amount of an ingredient or the value of a process variable such as temperature, pressure, time, etc. is described as being 50-90, it is meant herein that values ​​such as 51-89, 52-88, ..., 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001, or 0.0001 can be appropriately considered as one unit. These are merely examples of specific references. In the present application, all possible combinations of numerical values ​​between the recited minimum and maximum values ​​are similarly considered to be disclosed.

[0189] It should be noted that the above examples are merely illustrative of the present invention and do not constitute any limitation to the present invention. Although the present invention has been described with reference to typical examples, it should be understood that the terms used herein are descriptive and explanatory terms, rather than limiting terms. The present invention may be modified within the scope of the claims of the present invention as defined, and the present invention may be modified without departing from the scope and spirit of the present invention. The present invention described herein relates to specific methods, materials, and embodiments, but this is not meant to limit the present invention to the specific examples disclosed herein. On the contrary, the present invention may be extended to all other methods and applications having the same functions.

Claims

1. A catalyst comprising a main catalyst and a cocatalyst, The main catalyst is A catalyst for olefin polymerization comprising a bisphenol metal complex represented by formula Ia: [Case 2] In the formula, R １ and R １ ' are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ R is selected from the group consisting of hydrocarbyl; ３ ~R ７ , R ３ '~R ７ ' are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ R is selected from the group consisting of hydrocarbyl; ３ ~R ７ Any two adjacent groups among R are optionally joined to form a ring; ３ '~R ７ any two adjacent groups of R′ are optionally joined to form a ring; ８ and R ９ are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ hydrocarbyl; each R is independently selected from the group consisting of hydrogen, and substituted or unsubstituted C １ ~C ２０ each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydrides, amides, alkoxides, alkyl sulfides, alkyl phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof; and m and n are independently integers from 1 to 4, and The co-catalyst comprises an organoaluminum compound.

2. The olefin polymerization catalyst of claim 1, wherein the bisphenol metal complex has a structure represented by formula Ib: [C3] In the formula, R １ , R １ ', R ２ , R ２ ' are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ R is selected from the group consisting of hydrocarbyl; ３ ~R ７ , R ３ '~R ７ ' are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ R is selected from the group consisting of hydrocarbyl; ３ ~R ７ Any two adjacent groups among R are optionally joined to form a ring; ３ '~R ７ any two adjacent groups of R′ are optionally joined to form a ring; ８ and R ９ are each independently hydrogen and substituted or unsubstituted C １ ~C ２０ each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydrides, amides, alkoxides, alkyl sulfides, alkyl phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof.

3. The catalyst of claim 1 having at least one of the following characteristics: In formula Ia, R １ , R 1 ′ are each independently hydrogen, a substituted or unsubstituted, linear or branched C １ ~C ２０ Alkyl, and substituted or unsubstituted C ６ ~C ２０ aryl; In formula Ia, R ３ ~R ７ , R ３ '~R ７ ' are each independently hydrogen and substituted or unsubstituted, linear or branched C １ ~C ２０ selected from the group consisting of alkyl; In formula Ia, R ８ and R ９ are each independently hydrogen and substituted or unsubstituted, linear or branched C １ ~C ２０ selected from the group consisting of alkyl; In formula Ia, M and M' are each independently selected from the group consisting of titanium, zirconium and hafnium; and In formula Ia, each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide.

4. The catalyst of claim 1, having at least one of the following characteristics: In formula Ia, R 1 , R 1 ', are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; In formula Ia, R 3 to R 7 , R 3 ' to R 7 ' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; In formula Ia, R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; in formula Ia, M and M' are titanium; and In formula Ia, each X is independently selected from the group consisting of methyl and chloride.

5. The catalyst of claim 2, having at least one of the following characteristics: In formula Ib, R 1 , R 1 ', R 2 , R 2 ' are each independently selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C 1 -C 20 alkyl, and substituted or unsubstituted C 6 -C 20 aryl; In formula Ib, R 3 to R 7 , R 3 ' to R 7 ' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 to C 20 alkyl; In formula Ib, R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 20 alkyl; in formula Ib, M and M' are each independently selected from the group consisting of titanium, zirconium and hafnium; and In formula Ib, each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide.

6. The catalyst of claim 2, having at least one of the following characteristics: In formula Ib, R 1 , R 1 ', R 2 , R 2 ' are each independently selected from hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; In formula Ib, R 3 to R 7 , R 3 ' to R 7 ' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; In formula Ib, R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 6 alkyl; in formula Ib, M and M' are titanium; and In formula Ib, each X is independently selected from the group consisting of methyl and chloride.

7. 2. The catalyst of claim 1, wherein the bisphenol metal complex is at least one selected from the following complexes represented by formula Ib: [C4] Bisphenol metal complex 1:R １ = R ２ = R １ '=R ２ '=Me, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 2: R １ = R ２ = R １ '=R ２ '=Et, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 3: R １ = R ２ = R １ '=R ２ '=iPr, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 4:R １ = R ２ = R １ '=R ２ '=tBu, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 5:R １ = R ２ = R １ '=R ２ '=Me, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=Me, R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 6:R １ = R ２ = R １ '=R ２ '=Et, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=Me, R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 7:R １ = R ２ = R １ '=R ２ '=iPr, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=Me, R ８ = R ９ =H, M=M'=Ti, X=Cl; Bisphenol metal complex 8:R １ = R ２ = R １ '=R ２ '=tBu, R ３ = R ４ = R ５ = R ６ = R ７ = R ３ '=R ４ '=R ５ '=R ６ '=R ７ '=Me, R ８ = R ９ =H, M=M'=Ti, X=Cl; and the corresponding compounds where X=methyl.

8. The catalyst of any one of claims 1 to 7, wherein the organoaluminum compound comprises an aluminoxane having the general formula: [C5] In the formula, R is C １ ~C １２ It is a hydrocarbyl.

9. The catalyst of claim 8, wherein the aluminoxane is methylaluminoxane (MAO) or a modified methylaluminoxane.

10. 9. The catalyst of claim 8, wherein the molar ratio of the main catalyst to the cocatalyst (in terms of metal for the main catalyst and in terms of aluminum for the cocatalyst) is in the range of 1:200 to 1:5000.

11. The co-catalyst comprises a combination of an organoaluminum compound and an organoboron compound; the organoaluminum compound is selected from the group consisting of alkylaluminum and alkylaluminum halide; or The organoaluminum compound is selected from the group consisting of aluminoxanes and modified aluminoxanes; The catalyst of any one of claims 1 to 7, wherein the organoboron compound is selected from the group consisting of aromatic hydrocarbyl boron and borates.

12. 12. The catalyst of claim 11, wherein the molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the organoboron compound (in terms of boron) to the organoaluminum compound (in terms of aluminum) is in the range of 1:1:100 to 1:10:2000.

13. The catalyst of any one of claims 1 to 12, wherein the main catalyst comprises the bisphenol metal complex represented by formula Ia and a support material.

14. Use of the catalyst according to any one of claims 1 to 13 in olefin polymerization.

15. A process for homopolymerizing ethylene, comprising polymerizing ethylene monomer in the presence of the catalyst according to any one of claims 1 to 13.

16. The polymerization is 1) in the presence of a catalyst system comprising a main catalyst and a co-catalyst, the co-catalyst comprising an organoaluminum compound and an organoboron compound; the molar ratio of the main catalyst (based on the metal in the catalyst compound) to the organoboron compound (based on boron) to the organoaluminum compound (based on aluminum) is in the range of 1:1:100 to 1:10:2000; or 2) in the presence of a catalyst system comprising a main catalyst and a cocatalyst, said cocatalyst comprising an aluminoxane; The molar ratio of the main catalyst (in terms of metal in the catalyst compound) to the aluminoxane (in terms of aluminum) is in the range of 1:200 to 1:5000; The ethylene homopolymerization process according to claim 15.

17. The polymerization is 1) carried out at a temperature of -30 to 150°C; 2) carried out under a pressure of 0.1 to 10 MPa; 3) occurs over a period of 10 to 60 minutes; and / or 4) carried out in an inert solvent; The process for homopolymerizing ethylene according to claim 15 or 16.

18. An ethylene copolymerization process, wherein ethylene and a comonomer are polymerized in the presence of a catalyst according to any one of claims 1 to 13.

19. The polymerization is 1) in the presence of a catalyst system comprising a main catalyst and a co-catalyst, the co-catalyst comprising an organoaluminum compound and an organoboron compound; the molar ratio of the main catalyst (in terms of the metal in the main catalyst) to the organoboron compound (in terms of boron) to the organoaluminum compound (in terms of aluminum) is in the range of 1:1:100 to 1:10:2000; or 2) in the presence of a catalyst system comprising a main catalyst and a cocatalyst, said cocatalyst comprising an aluminoxane; The molar ratio of the main catalyst (in terms of the metal in the main catalyst) to the aluminoxane (in terms of aluminum) is in the range of 1:200 to 1:5000; The ethylene copolymerization process according to claim 18.

20. The polymerization is 1) Utilizing α-olefins and / or dienes; 2) carried out at a temperature of -30 to 150°C; 3) carried out under a pressure of 0.1 to 10 MPa; 4) occurs over a period of 10 to 60 minutes; and / or 5) carried out in an inert solvent; The ethylene copolymerization process according to claim 18 or 19.

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