Biphenol metal complexes, their preparation and use

Abstract

Biphenol metal complexes are disclosed in the present invention, whose structure can be represented by Formula I, where R and R are each independently hydrogen and a substituted or unsubstituted C-C 20 R3-R7, R3'-R7' are each independently selected from hydrogen and substituted or unsubstituted C1-C 20 hydrocarbyls, any two adjacent groups among R3 to R7 optionally join to form a ring, and any two adjacent groups among R3' to R7' also optionally join to form a ring; M and M' are each independently selected from Group 4 metals; each X is independently selected from the group consisting of hydrocarbyls having 1 to 20 carbon atoms, hydride ions, amino, alkoxy, alkylthio, alkylphosphorus, halides, dienes, amines, phosphines, ethers, or combinations thereof; m and n are each independently an integer of 1 to 4; and L is a divalent linking group. [Formula 1] JPEG2023501196000019.jpg41169

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, filed on October 28, 2019, which are incorporated by reference in their entireties for all purposes.

[0002] [Technical field] The present invention relates to a bisphenol metal complex and its production method and use, which belong to the field of organic synthesis.

[0003] PRIOR ART 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. 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 obtain 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, when using double zirconium metal catalysts, compared with using single zirconium metal catalysts, the ethylene polymerization activity and the molecular weight of the resulting polymer are comparable, but the ethyl grafting rate in the polymer chain is much higher, reaching 12%, while the ethyl grafting rate in the polymer obtained by catalyzing ethylene polymerization with a single zirconium metal catalyst 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 of the order, 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.

[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, which is the basis of the present invention.

[0008] It is therefore an object of the present invention to provide bisphenol metal complexes.

[0009] Another object of the present invention is to provide a method for preparing a bisphenol metal complex.

[0010] Yet another object of the present invention is to provide the use of bisphenol metal complexes as components of catalyst systems in the polymerization of olefins.

[0011] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, various specific embodiments, variants of the present invention will be described, including preferred embodiments and definitions adopted herein. 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 present "invention" refers to one or more, but not necessarily all, of the invention 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 new 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 on the subject group are replaced with a heteroatom-containing group such as C1-C6 alkyl, phenyl, benzyl, halogen atoms, heteroatoms, C1-C6 alkoxy, or a carbon atom in the backbone is replaced with 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 "polymerization" includes homopolymerization and copolymerization. As used herein, the term "polymer" includes homopolymers, copolymers, and terpolymers.

[0017] As used herein, the term "catalyst component" refers to the main catalyst component or catalyst precursor that, together with conventional cocatalysts such as alkylaluminum and optional external electron donors, constitute a catalyst for olefin polymerization (such combinations are also referred to in the art as catalyst systems).

[0018] In a first aspect, the present disclosure provides a bisphenol metal complex having a structure represented by formula I:

[0019] [ka]

[0020] In the formula, R1 and R1' are each independently selected from hydrogen and 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 20any 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.

[0021] In some embodiments, the divalent linking group L is a divalent hydrocarbyl or a divalent linking group having 1 to 30 carbon atoms with substantially hydrocarbon character. As used herein, the term "divalent linking group with substantially hydrocarbon character" refers to a divalent group that exhibits hydrocarbon character as a whole. Such groups allow for 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 can 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 above groups.

[0022] In some preferred embodiments, the bisphenol metal complexes of the present disclosure have a structure represented by formula Ia:

[0023] [ka]

[0024] In the formula, R1 and R1' are each independently selected from hydrogen and 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-C 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.

[0025] In some preferred embodiments, the bisphenol metal complexes of the present disclosure have a structure represented by formula Ib.

[0026] [ka]

[0027] In the formula, R1, R1', R2, and R2' are each independently hydrogen and 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-C 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.

[0028] 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 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 hydrogen, and substituted or unsubstituted, straight or branched C1-C6 alkyl.

[0029] In some preferred embodiments, in formulas I, Ia, and Ib, R3-R7, R3′-R7′ are each independently selected from hydrogen and substituted or unsubstituted, linear or branched C1-C 20 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 hydrogen, and substituted or unsubstituted, straight or branched C1-C6 alkyl.

[0030] 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 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 hydrogen, and substituted or unsubstituted, straight or branched C1-C6 alkyl.

[0031] 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.

[0032] 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.

[0033] In some embodiments, the bisphenol metal complex is at least one of the following complexes represented by formula Ib:

[0034] [ka]

[0035] 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.

[0036] In a second aspect, the present invention provides a method for preparing a bisphenol metal complex as described above, the 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 of formula V to obtain a bisphenol metal complex of formula I.

[0037] [ka]

[0038] wherein R3-R7, M and X have the same meanings as defined above for formula I.

[0039] In some specific embodiments, the present invention provides a method for preparing the above-mentioned bisphenol metal complexes represented by formula Ib, the method comprising the steps of: 1) reacting a bisphenol compound of formula II with a metal compound of formula III to obtain a bisphenol disalt of formula IV; and 2) reacting a bisphenol disalt compound of formula IV with a metal complex of formula V to obtain a bisphenol metal complex of formula Ib.

[0040] [ka]

[0041] wherein in formula II and formula IV, R1, R1', R2, R2', R8 and R9 have the same meanings as defined above for formula Ib; In formula III, M1 is a metal of Group IA, preferably lithium, sodium, or potassium, and R is hydrogen or a linear or branched C1-C 10 is alkyl; In formula V, R3-R7, M and X have the same meanings as defined above for formula Ib.

[0042] In some preferred embodiments of the present invention, the preparation method comprises reacting a bisphenol compound of formula II with a metal compound of formula III in an organic solvent to obtain a bisphenol disalt compound of formula IV; and then reacting the bisphenol disalt compound with a metal complex of formula V in an organic solvent to obtain a bisphenol metal complex of formula Ib.

[0043] According to some embodiments of the invention, the organic solvent is selected from tetrahydrofuran, diethyl ether, 1,4-dioxane, and dichloromethane.

[0044] In some preferred embodiments of the present invention, the bisphenol compound is at least one of the following bisphenol compounds represented by formula II:

[0045] [ka]

[0046] 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.

[0047] 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.

[0048] In some preferred embodiments of the invention, the compound of formula IV is at least one of the following compounds:

[0049] [ka]

[0050] 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.

[0051] In some preferred embodiments of the present invention, the metal compound of formula V is at least one of the following metal complexes:

[0052] [ka]

[0053] 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.

[0054] 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:(1-20), 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, 1:10.5 , 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 to 10), and more preferably 1:(4 to 8).

[0055] In some preferred embodiments of the method of the present invention, the reaction temperature of the reaction between the bisphenol compound represented by formula II and the compound represented by formula III 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.

[0056] In some preferred embodiments of the method of the present invention, the reaction time of the reaction of the bisphenol compound represented by formula II with the compound represented by formula III is 1 to 10 hours, for example, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 hours, and any time therebetween, preferably 1.5 to 3 hours.

[0057] 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. The number of moles of the bisphenol compound may simply be regarded as the number of moles of the compound represented by formula IV.

[0058] In some preferred embodiments of the method of the present invention, the reaction temperature of 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.

[0059] In some preferred embodiments of the method of the present invention, the reaction time of 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, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 hours, and any value therebetween, preferably 6 to 19 hours.

[0060] In a third aspect, the present invention provides the use of a bisphenol metal complex as described above in the polymerization of olefins, wherein the bisphenol metal complex is used as the main catalyst (or catalyst compound) of an olefin polymerization catalyst.

[0061] In some embodiments, the olefin polymerization catalyst further comprises a co-catalyst selected from an organoaluminum compound and an organoboron compound.

[0062] [Example] The present invention is further described below with specific examples, which do not constitute any limitation to the present invention.

[0063] The evaluation and test methods included in the following examples are as follows:

[0064] 1. Proton and carbon nuclear magnetic spectra were recorded at 110° C. on a Bruker-300 nuclear magnetic resonance spectrometer using deuterated chloroform as the solvent.

[0065] 2. High resolution mass spectra are recorded on a Bruker ESI-Q / TOF MS mass spectrometer using acetonitrile as the dispersing solvent.

[0066] 3. Polymerization activity: The polymer obtained by polymerization is dried and weighed, and the catalyst activity is calculated by dividing the weight of the polymer by the amount of catalyst added during polymerization.

[0067] 4. Molecular weight and molecular weight distribution (PDI) of polymer (PDI=Mw / Mn): Measured using PL-GPC220 at 150°C with 1,2,4-trichlorobenzene as solvent (standard: PS; flow rate: 1.0 mL / min; column: 3×Plgel 10 um M1×ED-B 300×7.5 nm).

[0068] 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 METTLER DSC1 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 are recorded.

[0069] 6. The content of comonomers in the polymer is determined by high temperature nuclear magnetic carbon spectroscopy.

[0070] Example 1 - Preparation of bisphenol metal complex 7 Bisphenol compound 3 (2.24 mmol) was dissolved in diethyl ether solvent, and pure 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. The solution was then transferred by transport 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-colored target product in 90% yield. Characterization data are as follows:

[0071] 1 H NMR (CDCl3, 400MHz): δ=7.45(dd, J=7.6, 2.0Hz, 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).

[0072] 13C NMR (CDCl3, 100MHz): 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.

[0073] C 59 H 72 ESI-MS for Cl4O3Ti2: M=1064.34.

[0074] Example 2 - Preparation of bisphenol metal complex 4 Bisphenol compound 4 (2.00 mmol) was dissolved in tetrahydrofuran solvent, and pure 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. The solution was then transferred by transport 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 give the orange desired product in 92% yield.

[0075] The characterization data are as follows: 51 H 56 ESI-MS for Cl4O3Ti2: M / Z=954.21.

[0076] Example 3 - Preparation of bisphenol metal complex A

[0077] [ka]

[0078] 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. The solution was then transferred by transport 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 desired product in purple-red color in 60% yield.

[0079] 1 H NMR (CDCl3, 400MHz): δ=7.74(dd, J=6.4, 2.8Hz, 4H, Aryl-H), 7.47(t, J=4.8Hz, 2H, Aryl-H), H=7.37(dd, 6.4, 2.8Hz, 4H, Aryl-H), 7.22(s, 4H, Aryl-H), 7.18(d, J=4.8 Hz, 4H, Aryl-H), 6.78(d, J=3.6Hz, 4H, Aryl-H), 6.42(t, J=3.2Hz, 2H, Aryl-H), 3.2 5(sept, 4H, CH), 2.18(s, 30H, CH3), 1.82(s, 6H, CH3), 1.08(d, J=6.8Hz, 24H, CH3).

[0080] 13 C NMR (CDCl3, 100MHz): 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.

[0081] Example 4 - Preparation of bisphenol metal complex B

[0082] [ka]

[0083] 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. The solution was then transferred by transport 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 desired purple product in 21% yield.

[0084] 1 H NMR (CDCl3, 400MHz): δ=7.40(dd, J=7.4, 2.2Hz, 2H, Aryl-H), 7.16-7.11(m, 4H, Aryl-H), 7.08(s, 4 H, 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).

[0085] Example 5 After drying by heating, the 500 mL polymerization autoclave was evacuated and filled with nitrogen gas twice, then evacuated and filled with ethylene gas once. Next, 10 mL of a toluene solution of 2 mmol / mL methylaluminoxane (MAO), 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of a toluene solution of 5 μmol / mL bisphenol metal complex 7 were added in sequence. Ethylene under a pressure of 1.0 MPa was introduced while mechanically stirring, and the reaction was continued at 20 °C for 20 minutes under that pressure, 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 -1The melting point measured by DSC was 133.5°C; the Mw measured by GPC was 1.9×10 5 , Mw / Mn was 4.82.

[0086] Example 6 After drying by heating, the 500 mL polymerization autoclave was evacuated and filled with nitrogen gas twice, then evacuated and filled with ethylene gas once. Next, 2 mL of 0.5 mmol / mL triisobutylaluminum n-hexane solution, 150 mL of deoxygenated and dehydrated n-hexane, and 1 mL of 2.5 μmol / mL toluene solution of bisphenol metal complex 7 were added in sequence, followed by 2 mL (5 μmol / mL) of boron-containing reagent [Ph3C][B(C6F5)4]. Ethylene under a pressure of 1.0 MPa was introduced while mechanically stirring, and the reaction was continued at 80 °C for 20 minutes under that pressure, 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 , Mw / Mn was 6.84.

[0087] Example 7 After drying by heating, the 500 mL polymerization autoclave was evacuated and filled with nitrogen gas twice, then evacuated and filled with ethylene gas once. Next, 6.8 mL of a toluene solution (10% by mass) of methylaluminoxane (MAO), 15 mL of 1-hexene, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of a toluene solution of 2.5 μmol / mL bisphenol metal complex 7 were added in sequence. Ethylene under a pressure of 3 atm was introduced while mechanically stirring, and the reaction was continued at 25°C for 20 minutes under that pressure, 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 5The Mw / Mn was 1.92. The molar content of 1-hexene was found to be 5.3% via high temperature nuclear magnetic carbon spectroscopy.

[0088] Example 8 After drying by heating, the 500 mL polymerization autoclave was evacuated and filled with nitrogen gas twice, then evacuated and filled with ethylene gas once. Next, 2 mL of 0.5 mmol / mL triisobutylaluminum n-hexane solution, 150 mL of deoxygenated and dehydrated n-hexane, and 2 mL of 2.5 μmol / mL bisphenol metal complex A toluene solution were added in sequence, followed by 3 mL (5 μmol / mL) of boron-containing reagent [Ph3C][B(C6F5)4]. Ethylene under a pressure of 0.4 MPa was introduced while mechanically stirring, and the reaction was continued at 40 °C for 10 minutes under that pressure, 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 polyethylene measured by GPC was 3.4×10 5 , Mw / Mn was 8.53.

[0089] Example 9 After drying by heating, the 500 mL polymerization autoclave was evacuated and filled with nitrogen gas twice, then evacuated and filled with ethylene gas once. Next, 2 mL of 0.5 mmol / mL triisobutylaluminum in n-hexane, 9.3 mL of 1-octene, 150 mL of 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 (5 μmol / mL) of boron-containing reagent [Ph3C][B(C6F5)4]. Ethylene under a pressure of 0.4 MPa was introduced while mechanically stirring, and the reaction was continued at 40 °C for 10 minutes under that pressure, 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 -1The melting point measured by DSC was 125.5°C; the Mw of the polyethylene measured by GPC was 5.6×10 4 The Mw / Mn was 2.91. The molar content of 1-octene was found to be 2.4% via high temperature nuclear magnetic carbon spectroscopy.

[0090] 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 a component 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 may 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 value and maximum value are similarly considered to be disclosed.

[0091] It should be noted that the above examples are for the purpose of illustrating 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 it is not meant that the present invention is limited to the specific examples disclosed herein. On the contrary, the present invention can be extended to all other methods and applications having the same functions.

Claims

1. Formula Ia 【Chemistry 1】 (In the formula, R １ and R １ Each ' is 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; R ３ ~R ７ , R ３ ´~R ７ Each ' is independently hydrogen, and a 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 may be optionally bonded to form a ring; ３ ´~R ７ any two adjacent groups among 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 R is independently selected from the group consisting of hydrogen, and substituted or unsubstituted C １ ~C ２０ each M and M' is independently selected from the group consisting of titanium, zirconium and hafnium; 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. Bisphenol metal complexes.

2. Formula Ib 【Chemistry 2】 (In the formula, R １ , R １ ', R ２ , R ２ Each ' is 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; R ３ ~R ７ , R ３ ´~R ７ Each ' is independently hydrogen, and a 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 may be optionally bonded to form a ring; ３ ´~R ７ any two adjacent groups among 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 M and M' is independently selected from the group consisting of titanium, zirconium and hafnium; 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; The bisphenol metal complex of claim 1.

3. Having at least one of the following features: 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; R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, straight or branched chain C 1 -C 20 alkyl; and - each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide; The bisphenol metal complex of claim 1.

4. It has at least one of the following characteristics: -R ３ ~R ７ , R ３ ´~R ７ Each ' is independently hydrogen, and a substituted or unsubstituted, straight or branched chain C １ ~C ２０ selected from the group consisting of alkyl; -R ８ and R ９ are each independently hydrogen, and substituted or unsubstituted, linear or branched C １ ~C ２０ alkyl; and - each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide; The bisphenol metal complex of claim 2.

5. Having at least one of the following features: - R 1 , R 1 ' are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 10 alkyl; - 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 10 alkyl; R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, straight or branched chain C 1 -C 10 alkyl; and - each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide; The bisphenol metal complex according to claim 3.

6. Having at least one of the following features: - 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; R 3 to R 7 , R 3 ' to R 7 ' are each independently selected from the group consisting of hydrogen, and substituted or unsubstituted, straight or branched chain C 1 to C 6 alkyl; R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, straight or branched chain C 1 -C 6 alkyl; and - each X is independently selected from the group consisting of methyl and chloride; The bisphenol metal complex according to claim 3.

7. Having at least one of the following features: - R 1 , R 1 ', R 2 , R 2 ' are each independently selected from the group consisting of hydrogen, and substituted or unsubstituted, linear or branched C 1 -C 10 alkyl; - 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 10 alkyl; R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, straight or branched chain C 1 -C 10 alkyl; and - each X is independently selected from the group consisting of methyl, fluoride, chloride, bromide and iodide; The bisphenol metal complex according to claim 4.

8. Having at least one of the following features: - R 1 , R 1 ', R 2 , R 2 ' are each independently selected from the group consisting of hydrogen, and substituted or unsubstituted, straight or branched chain C 1 -C 6 alkyl; R 3 to R 7 , R 3 ' to R 7 ' are each independently selected from the group consisting of hydrogen, and substituted or unsubstituted, straight or branched chain C 1 to C 6 alkyl; R 8 and R 9 are each independently selected from the group consisting of hydrogen and substituted or unsubstituted, straight or branched chain C 1 -C 6 alkyl; and - each X is independently selected from the group consisting of methyl and chloride; The bisphenol metal complex according to claim 4.

9. 3. The bisphenol metal complex of claim 2, which is at least one selected from the following complexes represented by formula Ib: 【Chemistry 3】 -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.

10. 2. A method for producing the bisphenol metal complex of claim 1, 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 of formula V to obtain the bisphenol metal complex of formula Ia 【Chemistry 4】 (In the formula, R ３ ~R ７ , M and X have the same meanings as defined for formula Ia in claim 1).

11. A method for producing the bisphenol metal complex of claim 2, comprising the steps of: 1) reacting a bisphenol compound of formula II with a metal compound of formula III to obtain a bisphenol disalt of formula IV; and 2) reacting the bisphenol disalt compound of formula IV with a metal complex of formula V to obtain the bisphenol metal complex of formula Ib. 【Chemistry 5】 (In Formula II and Formula IV, R １ , R １ ', R ２ , R ２ ', R ８ and R ９ has the same meaning as defined for formula Ib in claim 2; In formula III, M １ is a Group IA metal; R is hydrogen or a straight or branched chain C １ ~C １０ is alkyl; In formula V, R ３ ~R ７ , M and X have the same meanings as defined for formula Ib in claim 2).

12. 12. The method of claim 11, having at least one of the following features: the molar ratio of said bisphenol compound of formula II to said compound of formula III is 1:(1-20); the reaction temperature of the reaction of the bisphenol compound of formula II with the compound of formula III is between −78° C. and 60° C.; the reaction time of the reaction of the bisphenol compound of formula II with the compound of formula III is between 1 and 10 hours; the molar ratio of said compound of formula IV to said metal compound of formula V is 1:(1.8-2.4); the reaction temperature of the reaction of the compound of formula IV with the metal compound of formula V is between −78° C. and 60° C.; The reaction time of the reaction of said compound of formula IV with said metal compound of formula V is between 6 and 24 hours.

13. Use of the bisphenol metal complex according to any one of claims 1 to 9 in olefin polymerization.

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