Tetrahydronaphthol-phosphine transition metal complex, method for preparing the same, and use

Abstract

The present invention relates to the technical field of olefin polymerization catalysts and discloses a tetrahydronaphthol-phosphine pre-transition metal complex, a method for preparing the same, and its use. The structural formula of the tetrahydronaphthol-phosphine pre-transition metal complex is given by formula (I) (wherein M is selected from group 4 metals, Ar is selected from substituted or unsubstituted C6-C20 aryl groups, X is selected from halogens or C1-C10 hydrocarbon groups, and n is 1 or 2). When the tetrahydronaphthol-phosphine pre-transition metal complex of the present invention is used as the main catalyst for olefin polymerization, the olefin polymerization activity (homopolymerization / copolymerization activity) is relatively good even at relatively high temperatures, and the prepared olefin polymer has relatively good performance. [Formula 1] JPEG2026513594000017.jpg31169

Description

Detailed description of the invention

[0001] [Cross-reference of related applications] This application claims the benefits of Chinese Patent Application No. 202310659028.5, filed on 5 June 2023, the contents of which are incorporated herein by reference.

[0002] [Technical field] The present invention relates to the technical field of olefin polymerization catalysts, and more specifically to tetrahydronaphthol-phosphine pre-transition metal complexes, methods for preparing the same, and their use.

[0003] [Background technology] Polyethylene materials possess excellent chemical resistance, low cost, ease of preparation, low density, and superior mechanical properties, and are also expected to be a potential substitute for rubber. Furthermore, by introducing polar functional groups into polyolefins composed of saturated carbon chains, the usability of the material can be significantly improved, expanding the direction of material development. Therefore, the development of high-value-added, high-performance polyolefin products is urgently needed.

[0004] Metal complexes are currently the most commonly used olefin polymerization catalysts, and mainly include two types: homogeneous and heterogeneous. Among the various types of olefin polymerization catalysts, homogeneous early transition metal catalysts have attracted much attention from researchers due to their many advantages, such as high polymerization activity, high molecular weight of the resulting polymers, the ability to perform living polymerization, and controllability (e.g., Angew. Chem. Int. Ed. 2020, 59, 14726-147; Chemical Rapid Report, 2014, 77, 951-960). By changing the steric hindrance effect near the active site, the electronic effect, and the number of metal centers, it is possible to achieve objectives such as adjusting polymerization activity, polymerization products, and product distribution. However, China is relatively behind in the production of high-grade polyolefins, and the lack of olefin polymerization catalysts with superior performance is a major factor hindering development in this field. Currently, conventional ethylene vapor-phase polymerization processes generally require polymerization temperatures of 85°C or higher, while ethylene solution polymerization processes generally require polymerization temperatures of 130-250°C. However, conventional olefin polymerization catalysts all had the problem of not being able to maintain high catalytic activity and high polymerization performance at high temperatures.

[0005] [Overview of the prefecture] [Problems the invention aims to solve] The object of the present invention is to overcome the problem that conventional olefin polymerization catalysts cannot maintain high catalytic activity and high polymerization performance at high temperatures, and to provide a tetrahydronaphthol-phosphine transition metal complex, a method for preparing the same, and its use. The tetrahydronaphthol-phosphine transition metal complex has excellent thermal stability, and when the tetrahydronaphthol-phosphine transition metal complex of the present invention is used as the main catalyst for olefin polymerization in an olefin polymerization process, the olefin polymerization activity is relatively good even at relatively high temperatures, and the prepared olefin polymer has relatively good performance (for example, relatively high molecular weight and a relatively narrow molecular weight distribution). [Means for solving the problem] To achieve the above objective, one aspect of the present invention provides a tetrahydronaphthol-phosphine early transition metal complex whose structural formula is given by formula (I).

[0006] [ka]

[0007] (Here, M is selected from group 4 metals, Ar is selected from substituted or unsubstituted C6-C20 aryl groups, X is selected from halogens and C1-C10 hydrocarbon groups, and n is 1 or 2.) Preferably, the structural formula of the tetrahydronaphthol-phosphine pre-transition metal complex is represented by formula (II).

[0008] [ka]

[0009] (Here, R7~R 11 Each of these is independently selected from hydrogen, halogen, hydroxyl group, and substituted or unsubstituted C1-C20 hydrocarbon group. A second aspect of the present invention provides a method for preparing a tetrahydronaphthol-phosphine early transition metal complex, the method being: Step (1) involves reacting the compound shown in formula (III) with the compound shown in formula (IV) to produce a ligand, The process includes (2) mixing the ligand with a hydrogen extractant and reacting it, then removing the hydrogen extractant, and reacting the resulting product with an M metal compound. The metal M in the aforementioned M metal compound is selected from Group 4 metals.

[0010] [ka]

[0011] (Here, in formula (IV), Ar is selected from substituted or unsubstituted C6-C20 aryl groups, and Y is a halogen.) A third aspect of the present invention provides an olefin polymerization catalyst containing a main catalyst and a co-catalyst, wherein the main catalyst is the tetrahydronaphthol-phosphine early transition metal complex provided in the present invention.

[0012] A fourth aspect of the present invention provides an olefin polymerization method comprising the step of carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst provided in the present invention.

[0013] [Effects of the invention] According to the technical solution of the present invention, when the tetrahydronaphthol-phosphine-pre-transition metal complex of the present invention is used as the main catalyst for olefin polymerization in an olefin polymerization reaction process, the olefin polymerization activity (homopolymerization / copolymerization activity) is relatively excellent even at relatively high temperatures, and the prepared olefin polymer has relatively excellent performance (for example, relatively high molecular weight and relatively narrow molecular weight distribution).

[0014] [Modes for carrying out the invention] The following describes specific embodiments of the present invention in detail. It should be understood that the specific embodiments described herein are for illustrative and interpretive purposes only and do not limit the present invention.

[0015] The structural formula of the tetrahydronaphthol-phosphine early transition metal complex of the present invention is shown by formula (I).

[0016] [ka]

[0017] (Here, M is selected from group 4 metals, Ar is selected from substituted or unsubstituted C6-C20 aryl groups, X is selected from halogens and C1-C10 hydrocarbon groups, and n is 1 or 2.) Preferably, Ar is a substituted or unsubstituted C6-C15 aryl group, and more preferably a substituted or unsubstituted C6-C8 aryl group.

[0018] In a preferred embodiment, the structural formula of the tetrahydronaphthol-phosphine pre-transition metal complex is shown by formula (II).

[0019] [ka]

[0020] (Here, R7~R 11 Each of these is independently selected from hydrogen, halogen, hydroxyl group, and substituted or unsubstituted C1-C20 hydrocarbon group. In the complexes represented by formulas (I) and (II), M is preferably Ti, Zr, or Hf.

[0021] In the complexes represented by formulas (I) and (II), X is preferably a halogen or a C1-C8 hydrocarbon group (e.g., a C1-C6 alkyl group).

[0022] In the complex represented by formula (II), preferably, R7~R 11 Each of these is independently selected from hydrogen, halogen, hydroxyl group, substituted or unsubstituted C1-C10 alkyl group, and substituted or unsubstituted C6-C15 aryl group.

[0023] In the complexes represented by formulas (I) and (II), n is either 1 or 2, and n represents the number of X groups linked to the metal M.

[0024] In the present invention, "substituted" in "substituted or unsubstituted" means containing a substituent, and the substituent may be selected from halogens, hydroxyl groups, C1-C6 alkyl groups, halo-C1-C6 alkyl groups, C1-C6 alkoxy groups, or halo-C1-C6 alkoxy groups.

[0025] In the present invention, the alkyl group (for example, C1-C6 alkyl group, C1-C10 alkyl group) may be selected from methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, or 3,3-dimethylbutyl group.

[0026] In the present invention, the alkoxy group (for example, a C1-C6 alkoxy group) may be selected from a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an n-pentoxy group, an isopentoxy group, an n-hexyloxy group, an isohexyloxy group, or a 3,3-dimethylbutoxy group.

[0027] In the present invention, the aryl group (for example, a C6-C10 aryl group or a C6-C15 aryl group) may be selected from a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a dimethylphenyl group, or a vinylphenyl group.

[0028] In the present invention, the halogen is selected from fluorine, chlorine, bromine, or iodine.

[0029] In a more preferred embodiment, the tetrahydronaphthol-phosphine pre-transition metal complex is selected from the group consisting of the following complexes.

[0030] Complex 1: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=1). Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). Complex 3: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is a methyl group, and n=2). Complex 4: Equation (II) (where M is Ti, and R7~R 11is H, X is -CH2C6H5, and n = 2), the complex Complex 5: Formula (II) (where M is Ti, R8 to R 11 is H, R7 is a methoxy group, X is Cl, and n = 1), the complex Complex 6: Formula (II) (where M is Ti, R8 to R 11 is H, R7 is a methoxy group, X is Cl, and n = 2), the complex Complex 7: Formula (II) (where M is Ti, R8 to R 11 is H, R7 is a methoxy group, X is a methyl group, and n = 2), the complex Complex 8: Formula (II) (where M is Ti, R8 to R 11 is H, R7 is a methoxy group, X is -CH2C6H5, and n = 2), the complex Complex 9: Formula (II) (where M is Ti, R7, R8, R 10 , and R 11 is H, R9 is a methoxy group, X is Cl, and n = 1), the complex Complex 10: Formula (II) (where M is Ti, R7, R8, R 10 , and R 11 is H, R9 is a methoxy group, X is Cl, and n = 2), the complex Complex 11: Formula (II) (where M is Ti, R7, R8, R 10 , and R 11 is H, R9 is a methoxy group, X is a methyl group, and n = 2), the complex Complex 12: Formula (II) (where M is Ti, R7, R8, R 10 , and R 11 is H, R9 is a methoxy group, X is -CH2C6H5, and n = 2), the complex Complex 13: Formula (II) (where M is Ti, R7, R9, and R 11 is H, R8, and R 10 is -CF3, X is Cl, and n = 1), the complex Complex 14: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) Complex 15: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is a methyl group, and n=2). Complex 16: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is -CH2C6H5, and n=2). Complex 17: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is Cl, and n=1). Complex 18: Formula (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is Cl, and n=2). Complex 19: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 20: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is -CH2C6H5, and n=2). Complex 21: Equation (II) (where M is Zr, and R7~R) 11 The complex represented by (where is H, X is Cl, and n=2). Complex 22: Equation (II) (where M is Zr, and R7~R) 11 The complex represented by (where is H, X is a methyl group, and n=2). Complex 23: Equation (II) (where M is Zr, and R7~R) 11 The complex represented by (where is H, X is -CH2C6H5, and n=2). Complex 24: Equation (II) (where M is Zr, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is Cl, and n=2). Complex 25: Equation (II) (where M is Zr, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is a methyl group, and n=2). Complex 26: Equation (II) (where M is Zr, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is -CH2C6H5, and n=2). Complex 27: Equation (II) (where M is Zr, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is Cl, and n=2). Complex 28: Equation (II) (where M is Zr, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is a methyl group, and n=2). Complex 29: Equation (II) (where M is Zr, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is -CH2C6H5, and n=2). Complex 30: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) Complex 31: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is a methyl group, and n=2). Complex 32: Equation (II) (where M is Zr, R7, R9, and R11 H is R8, and R 10 The complex represented by (where is -CF3, X is -CH2C6H5, and n=2). Complex 33: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is Cl, and n=2). Complex 34: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 35: Formula (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is -CH2C6H5, and n=2). Complex 36: Equation (II) (where M is Hf, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). Complex 37: Equation (II) (where M is Hf, and R7~R 11 The complex represented by (where is H, X is a methyl group, and n=2). Complex 38: Equation (II) (where M is Hf, and R7~R 11 The complex represented by (where is H, X is -CH2C6H5, and n=2). Complex 39: Equation (II) (where M is Hf, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is Cl, and n=2). Complex 40: Equation (II) (where M is Hf, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is a methyl group, and n=2). Complex 41: Equation (II) (where M is Hf, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is -CH2C6H5, and n=2). Complex 42: Equation (II) (where M is Hf, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is Cl, and n=2). Complex 43: Equation (II) (where M is Hf, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is a methyl group, and n=2). Complex 44: Equation (II) (where M is Hf, R7, R8, R 10 , and R 11 The complex represented by (where is H, R9 is a methoxy group, X is -CH2C6H5, and n=2). Complex 45: Formula (II) (where M is Hf, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) Complex 46: Equation (II) (where M is Hf, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is a methyl group, and n=2). Complex 47: Equation (II) (where M is Hf, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is -CH2C6H5, and n=2). Complex 48: Equation (II) (where M is Hf, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is Cl, and n=2). Complex 49: Equation (II) (where M is Hf, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 50: Equation (II) (where M is Hf, R7, R9, and R 11 H is R8, and R10 The complex represented by (where is a methyl group, X is -CH2C6H5, and n=2). The method for preparing the tetrahydronaphthol-phosphine early transition metal complex of the present invention is as follows: Step (1) involves reacting the compound shown in formula (III) with the compound shown in formula (IV) to produce a ligand, The process may also include step (2) of reacting the ligand with a hydrogen extractant, then removing the hydrogen extractant, and reacting the resulting product with an M metal compound.

[0031] [ka]

[0032] (In formula (IV), Ar is selected from substituted or unsubstituted C6-C20 aryl groups, preferably substituted or unsubstituted C6-C15 aryl groups, and more preferably substituted or unsubstituted C6-C8 aryl groups.) In formula (IV), Y is a halogen, specifically, for example, chlorine or bromine, but most preferably chlorine.

[0033] In the method of the present invention, the metal M in the M metal compound is selected from group 4 metals, and is preferably Ti, Zr, or Hf.

[0034] In the method of the present invention, the specific reaction process is represented by the following reaction equation.

[0035] [ka]

[0036] (Here, the definitions of Ar, Y, M, X, and n are all the same as described above.) In a preferred embodiment, the reaction process of step (1) is represented by the following reaction equation.

[0037] [ka]

[0038] (Here, Y, and R7~R 11 The definitions are all the same as those described above. In a preferred embodiment, the reaction process of step (2) is represented by the following reaction equation.

[0039] [ka]

[0040] (Here, R7~R 11 The definitions of M, X, and n are all the same as described above. In a preferred embodiment, the M metal compound is one or more selected from titanium tetrachloride, tetrachlorobis(tetrahydrofuran)titanium (TiCl4(THF)2), trichlorotris(tetrahydrofuran)titanium, zirconium tetrachloride, tetrachlorobis(tetrahydrofuran)zirconium ((THF)2ZrCl4), hafnium tetrachloride, and tetrachlorobis(tetrahydrofuran)hafnium ((THF)2HfCl4).

[0041] In this invention, "THF" refers to "tetrahydrofuran".

[0042] In a preferred embodiment, in the reaction process of step (1), the compound represented by formula (III) is first mixed with the first hydrogen extractant and reacted, and then reacted with the compound represented by formula (IV).

[0043] In the method of the present invention, the reaction in step (2) is carried out in the presence of a reaction solvent. According to some embodiments of the present invention, the reaction solvent may be toluene or tetrahydrofuran, but is preferably tetrahydrofuran.

[0044] In the method of the present invention, the first hydrogen extractant used in step (1) and the hydrogen extractant used in step (2) (which may be called the second hydrogen extractant) may be the same or different, and the first hydrogen extractant and the second hydrogen extractant are each independently one or more selected from NaH, KH, n-butyllithium, and methyllithium.

[0045] In one specific embodiment, the preparation process of step (1) includes the following: Dissolve the compound represented by formula (III) in anhydrous ethyl ether in a protective gas atmosphere (e.g., nitrogen gas), add a first hydrogen extractant solution (e.g., n-butyllithium) dropwise at -78°C, and gradually allow the reaction to return to room temperature. Add a tetrahydrofuran solution of the phosphine compound represented by formula (IV) (in an ice bath) dropwise to the original reaction system, gradually raise the temperature to room temperature, stir overnight, citrate with water, extract the organic phase with ethyl ether, concentrate the obtained organic phase, deoxygenate by a refrigeration cycle, add 5 mL of concentrated hydrochloric acid in a nitrogen atmosphere and allow the reaction to proceed, and when the reaction is complete as monitored by TLC, neutralize with aqueous NaHCO3 solution, citrate with water, extract the organic phase with ethyl ether, dry over anhydrous MgSO4, filter, concentrate, and obtain the ligand represented by formula (V) by column chromatography.

[0046] In one specific embodiment, the preparation process of step (2) includes: dissolving the ligand obtained in step (1) in an organic solvent (e.g., toluene, tetrahydrofuran, etc.) in a protective gas (e.g., nitrogen gas) atmosphere, adding an excess of a second hydrogen extractant (e.g., NaH, KH, etc.), stirring at room temperature, removing the hydrogen extractant by filtration, then dissolving the M metal compound in an organic solvent (e.g., toluene, tetrahydrofuran, etc.), adding it dropwise to the original reaction system, reacting overnight, removing the solvent by aspirate, dissolving it with dichloromethane, removing the filtration cake by filtration, concentrating the filtrate, adding heptane and recrystallizing to obtain the tetrahydronaphthol-phosphine early transition metal complex of the present invention.

[0047] The present invention also provides an olefin polymerization catalyst, which contains a main catalyst and a cocatalyst. The main catalyst is the tetrahydronaphthol-phosphine early transition metal complex provided by the present invention.

[0048] In the present invention, the cocatalyst may be an organoaluminum compound and / or an organoboron compound.

[0049] In a preferred embodiment, the organoaluminum compound is an alkylaluminoxane and / or an organoaluminum compound with the general formula AlL n Z 3-n (where L is selected from hydrogen, a C1-C20 hydrocarbon group, and a C1-C20 hydrocarbyloxy group, Z is selected from halogen, 0 < n ≦ 3, and n is an integer.) and is at least one selected from organoaluminum compounds.

[0050] In a more preferred embodiment, L is selected from a C1-C20 alkyl group, a C1-C20 alkoxy group, a C7-C20 aralkyl group, and a C6-C20 aryl group.

[0051] In a more preferred embodiment, Z is selected from chlorine or bromine.

[0052] Even more preferably, the organoaluminum compound is one or more selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, chloroethylaluminum, chlorodiisobutylaluminum, ethylaluminum sesquichloride, dichloroethylaluminum, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO).

[0053] In a preferred embodiment, the organoboron compound is an aromatic hydrocarbylboron and / or an organoborate.

[0054] In a more preferred embodiment, the aromatic hydrocarbyl boron is a substituted or unsubstituted phenylborane. For example, the aromatic hydrocarbyl boron is tris(pentafluorophenyl)borane.

[0055] In a more preferred embodiment, the organic borate is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyltetrakis(pentafluorophenyl)borate.

[0056] In a preferred embodiment, when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to metal M in the main catalyst is 10 to 10 7 The molar ratio is 1, preferably 10 to 100000:1, more preferably 100 to 10000:1, and specifically the molar ratio may be 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1, or any value in between.

[0057] In a preferred embodiment, when the co-catalyst is an organoboron compound, the molar ratio of boron in the co-catalyst to metal M in the main catalyst is 0.1 to 1000:1, preferably 0.1 to 500:1. Specifically, the molar ratio may be 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, or any value in between.

[0058] In the present invention, the olefin may be a C2-C16 olefin.

[0059] In the present invention, the olefin may be at least one of ethylene, α-olefin, and cycloolefin.

[0060] In a preferred embodiment, the olefin may be ethylene and / or an α-olefin having 3 to 16 carbon atoms.

[0061] The present invention also provides an olefin polymerization method, which comprises the step of carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst of the present invention.

[0062] In the olefin polymerization method of the present invention, the temperature of the olefin polymerization reaction may be -78°C to 200°C, but more preferably -20°C to 150°C. Since the main catalyst of the olefin polymerization catalyst used is the tetrahydronaphthol-phosphine pre-transition metal complex of the present invention, the olefin polymerization method of the present invention is particularly suitable for olefin polymerization reactions at high temperatures. In some embodiments, the temperature of the olefin polymerization reaction is 80 to 100°C.

[0063] In the olefin polymerization method of the present invention, the polymerization pressure of the olefin polymerization reaction may be 0.01 to 10 MPa, but is preferably 0.01 to 5 MPa.

[0064] In the olefin polymerization method of the present invention, the polymerization reaction time for the olefin polymerization reaction may be 5 to 60 minutes.

[0065] In the present invention, the olefin polymerization reaction may be homopolymerization or copolymerization.

[0066] In this invention, "polymerization pressure" refers to the ethylene pressure in the polymerization system and is expressed as absolute pressure.

[0067] In the olefin polymerization method of the present invention, the olefin is a C2-C16 olefin.

[0068] According to one embodiment of the present invention, the olefin is ethylene.

[0069] According to one embodiment of the present invention, the olefin is at least one of ethylene, propylene, α-olefin, and cycloolefin.

[0070] According to some embodiments of the present invention, the olefin polymerization reaction is carried out in a solvent using an olefin monomer, and the polymerization solvent is one or more selected from alkanes, aromatic hydrocarbons, and halogenated hydrocarbons.

[0071] According to some specific embodiments of the present invention, the polymerization solvent is one or more selected from hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, chlorobenzene, and dichloroethane, and preferably one or more of hexane, toluene, and heptane.

[0072] According to some embodiments of the present invention, the process for catalyzing ethylene homopolymerization with an olefin polymerization catalyst having a tetrahydronaphthol-phosphine early transition metal complex as the main catalyst is as follows. A high-pressure solution polymerization reaction is carried out in an inert solvent using ethylene and an olefin polymerization catalyst. After the reaction is completed, the polymer is precipitated with a precipitating agent, and then filtered and dried.

[0073] In a preferred embodiment, the inert solvent is at least one of toluene, xylene, and decalin, and the precipitating agent is at least one of methanol, ethanol, and acetone.

[0074] In the present invention, when catalyzing ethylene homopolymerization with an olefin polymerization catalyst having a tetrahydronaphthol-phosphine early transition metal complex as the main catalyst, the homopolymerization activity is excellent in stability and reaches up to 5.6×10 7 g / (mol·h), and even reaches 10 6 g / (mol·h) under the polymerization conditions of 80°C.

[0075] According to some embodiments of the present invention, a specific reaction process in which an olefin polymerization catalyst mainly catalyzes the direct coordination copolymerization of ethylene and a copolymer monomer (α-olefin and / or cycloolefin) using a tetrahydronaphthol-phosphine pre-transition metal complex is as follows: Ethylene, the copolymer monomer, and the olefin polymerization catalyst are subjected to a solution polymerization reaction in an inert solvent; after the reaction is complete, the polymer is precipitated with a precipitating agent, and then filtered and dried.

[0076] In preferred embodiments, the inert solvent is at least one of toluene, xylene, and decalin, and the precipitating agent is methanol, ethanol, or acetone.

[0077] In this invention, the olefin polymerization catalyst, primarily using a tetrahydronaphthol-phosphine-pre-transition metal complex, exhibits a maximum activity of 1.56 × 10⁻¹⁶ for catalyzing direct coordination copolymerization between ethylene and copolymer monomers (α-olefins and / or cycloolefins). 6 The concentration reaches g / (mol·h), and the insertion rate of copolymer monomers and the molecular weight of the copolymer are relatively high.

[0078] In one specific embodiment, the copolymer monomer is a long-chain α-olefin and norbornene.

[0079] In preferred embodiments, the molar ratio of the copolymer monomer to the olefin polymerization catalyst is 0 to 1000:1, specifically 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, or 1000:1.

[0080] In the olefin polymerization method of the present invention, the amount of olefin polymerization catalyst used is 5 to 30 μmol, and specifically, for example, it may be 5 μmol, 10 μmol, 15 μmol, 20 μmol, 25 μmol, or 30 μmol.

[0081] In the present invention, alkyl groups refer to linear alkyl groups, branched alkyl groups, or cycloalkyl groups, and include, but are not limited to, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, s-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, isopentyl groups, tert-pentyl groups, neopentyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups, n-decyl groups, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, 4-methylcyclohexyl groups, 4-ethylcyclohexyl groups, 4-n-propylcyclohexyl groups, and 4-n-butylcyclohexyl groups.

[0082] In this invention, the alkenyl group is a linear alkenyl group, a branched alkenyl group, or a cycloalkenyl group, and includes, but is not limited to, an ethylene group, an allyl group, or a butenyl group.

[0083] In the present invention, examples of aralkyl groups include, but are not limited to, phenylmethyl, phenylethyl, phenyl n-propyl, phenylisopropyl, phenyl n-butyl, and phenyl t-butyl groups.

[0084] In the present invention, examples of alkaryl groups include, but are not limited to, toluene, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and t-butylphenyl groups.

[0085] The tetrahydronaphthol-phosphine transition metal complex of the present invention, its preparation method, and its use will be further described below with reference to examples. The examples are carried out based on the technical solutions of the present invention and show detailed embodiments and specific operating processes, but the scope of protection of the present invention is not limited to the following examples.

[0086] Unless otherwise specified, the experimental methods in the following examples are all conventional methods in the relevant art. Unless otherwise specified, the experimental materials used in the following examples are all commercially available.

[0087] The analytical characterization equipment and measurement methods used in the following examples and comparative examples are as follows. (1) Nuclear magnetic resonance spectrometer: Avance III HD 500 (500 MHz), using tetramethylsilane (TMS) as the internal standard. (2) Molecular weight and molecular weight distribution of polymers PDI (PDI = M w / M n ): Measured at 150°C using a PL-GPC220 chromatograph with trichlorobenzene as the solvent (standard sample: PS, flow rate: 1.0 mL / min, chromatography column: 3×PLgel 10 μm M1×ED-B, 300×7.5 nm). (3) Method for measuring activity: The polymer was washed with hydrochloric acid and ethanol solutions, vacuum dried, and then weighed. Method for calculating polymerization activity: Polymer weight (g) / Metal (mol) × 60 / Polymerization time (min). (4) Analysis of copolymer monomer content of polymers: 1 1H NMR and 13 Measurements were performed using 13C NMR spectroscopy. A 400MHz Bruker Avance 400 nuclear magnetic resonance spectrometer was used with a 10mm PASEX13 probe to dissolve polymer samples in 1,2,4-trichlorobenzene at 120°C, and then analyzed and measured.

[0088] Example 1 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). In a nitrogen atmosphere, the compound represented by formula (III) (2.32 g, 10 mmol) was dissolved in anhydrous ethyl ether (20 mL), and n-butyllithium solution (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78 °C. The reaction was gradually restored to room temperature, and stirring was continued for 12 h to obtain a white precipitate. Diphenylphosphine chloride (PPh2Cl) (11 mmol, 2.42 g) was uniformly dispersed in 10 mL of ethyl ether, and it was added dropwise to the original reaction system under an ice-water bath. The temperature was slowly raised to room temperature and stirred overnight. It was quenched with water, and the organic phase was extracted with ethyl ether. The obtained organic phase was concentrated, deoxygenated by a freezing cycle, 5 mL of concentrated hydrochloric acid was added in a nitrogen atmosphere, and the reaction was carried out for 5 h. As a result of monitoring by TLC, when the reaction was completed, an aqueous solution of NaHCO3 was added for neutralization, quenched with water, the organic phase was extracted with ethyl ether, dried over anhydrous MgSO4, filtered, concentrated, and the ligand L1 was obtained by column chromatography with a yield of 33%. 1 H NMR (500 MHz, CDCl3, TMS): δ 11.30 (s, 1H), 7.72 - 7.67 (m, 4H), 7.58 - 7.55 (m, 2H), 7.49 - 7.46 (m, 4H), 6.74 - 6.70 (m, 1H), 6.58 - 6.55 (m, 1H), 2.74 - 2.68 (m, 4H), 1.83 - 1.74 (m, 4H). 13 C NMR (126 MHz, CDCl3) δ 161.96, 161.94, 144.03, 144.01, 132.69, 132.32, 132.30, 132.04, 131.96, 131.85, 128.65, 128.55, 128.17, 128.09, 127.01, 126.95, 119.89, 119.79, 106.84, 105.99, 77.27, 77.02, 76.76, 30.04, 22.78, 22.54, 22.48. 31 P NMR (202 MHz, CDCl3) δ 39.67。

[0089] Under a nitrogen atmosphere, ligand L1 (0.66 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of TiCl4(THF)2 (0.334 g, 1 mmol) in tetrahydrofuran was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 2 in 77% yield. Elemental analysis was performed. 44 H 40 Cl2O2P2Ti (781.52): Theoretical calculation: C, 67.62; H, 5.16; Measured values: C, 67.43; H, 5.33.

[0090] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 was added, and methylaluminoxane (6.5mL, 10 mmol) was added. The reaction was carried out at 30°C, maintaining an ethylene pressure of 1.0 atm, and vigorously stirred for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0091] Example 2 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 was added, and methylaluminoxane (6.5mL, 10 mmol) was added. The reaction was carried out at 30°C, maintaining an ethylene pressure of 10 atm, and vigorously stirred for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0092] Example 3 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 was added, and methylaluminoxane (6.5mL, 10 mmol) was added. The reaction was carried out at 80°C, maintaining an ethylene pressure of 10 atm, and vigorously stirred for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0093] Example 4 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 was added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted at 100°C while maintaining an ethylene pressure of 10 atm and stirring vigorously for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0094] Example 5 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 and 10mL of 1-octene were added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0095] Example 6 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 and 10mL of 1-octene were added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted at 70°C while maintaining an ethylene pressure of 1.0 atm and stirring vigorously for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0096] Example 7 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 and 0.5g of norbornene were added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted by vigorously stirring for 10 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0097] Example 8 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 and 0.5g of norbornene were added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted at 50°C while maintaining an ethylene pressure of 1.0 atm and stirring vigorously for 10 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0098] Example 9 Complex 2: Equation (II) (where M is Ti, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, 7.8mg (10μmol) of complex 2 and 0.5g of norbornene were added, and methylaluminoxane (6.5mL, 10 mmol) was added. The mixture was reacted at 70°C while maintaining an ethylene pressure of 1.0atm and stirring vigorously for 10 minutes. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0099] Example 10 Complex 21: Equation (II) (where M is Zr, and R7~R) 11 The complex represented by (where is H, X is Cl, and n=2). Ligand L1 was prepared according to the method of Example 1.

[0100] Under a nitrogen atmosphere, ligand L1 (0.66 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of (THF)2ZrCl4 (0.38 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 21 in 71% yield. Elemental analysis measurement C 44 H 40 Cl2O2P2Zr (824.87): Theoretical calculation: C, 64.07; H, 4.89; Measured values: C, 63.79; H, 4.95.

[0101] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (6.5mL, 10 mmol) and complex 21 (8.2 mg, 10 μmol) were added, and the mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0102] Example 11 Complex 36: Equation (II) (where M is Hf, and R7~R 11 The complex represented by (where is H, X is Cl, and n=2). Ligand L1 was prepared according to the method of Example 1.

[0103] Under a nitrogen atmosphere, ligand L1 (0.66 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of (THF)2HfCl4 (0.46 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 36 in 76% yield. Elemental analysis measurement C 44 H 40 Cl2O2P2Hf(912.14): Theoretical calculation: C, 57.94; H, 4.42; Measured values: C, 57.78; H, 4.31.

[0104] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (6.5mL, 10 mmol) and complex 36 (9.1 mg, 10 μmol) were added, and the mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0105] Example 12 Complex 14: Equation (II) (where M is Ti, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) Under a nitrogen atmosphere, dissolve the compound represented by formula (III) (2.32 g, 10 mmol) in anhydrous ethyl ether (20 mL), add n-butyllithium solution (2.7 M, 4.0 mL, 11 mmol) dropwise at -78°C, and gradually allow the reaction to return to room temperature. Continue stirring for 12 hours to obtain a white precipitate. Disperse bis(3,5-bis(trifluoromethyl)phenyl)chlorophosphine (PPh2(CF3)4Cl) (11 mmol, 5.42 g) uniformly in 10 mL of ethyl ether, and under an ice bath, The reaction system was added dropwise, the temperature was slowly raised to room temperature, stirred overnight, citrated with water, the organic phase was extracted with ethyl ether, the obtained organic phase was concentrated, deoxygenated by a refrigeration cycle, and the reaction was carried out for 5 hours with 5 mL of concentrated hydrochloric acid in a nitrogen atmosphere. After monitoring by TLC, when the reaction was complete, aqueous NaHCO3 solution was added to neutralize the reaction, citrated with water, the organic phase was extracted with ethyl ether, dried over anhydrous MgSO4, filtered, concentrated, and ligand L2 was obtained in 31% yield by column chromatography. 1 H NMR (500 MHz, CDCl3, TMS): δ 10.48 (s, 0.9H), 8.13-8.11 (d, J =13.0 Hz, 6H), 6.70-6.66 (m, 2H), 2.78-2.76 (t, J = 5.5 Hz, 2H), 2.71-2.68 (t, J = 6.0 Hz, 2H), 1.84-1.79 (m, 4H). 13 C NMR (126 MHz, CDCl3) δ 162.14, 146.44, 135.07, 134.24, 133.39, 133.28, 133.00, 132.90, 132.73, 132.63, 132.46, 132.36, 131.80, 131.78, 131.71, 131.68, 128.33, 128.26, 126.92, 126.89, 126.86, 126.84, 126.82, 126.74, 123.64, 121.46, 121.36, 121.25, 77.28, 77.02, 76.77, 30.14, 22.75, 22.26, 22.20. 31 P NMR (202 MHz, CDCl3) δ 34.86.

[0106] Under a nitrogen atmosphere, ligand L2 (1.21 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of TiCl4(THF)2 (0.334 g, 1 mmol) in tetrahydrofuran was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 14 in 75% yield. Elemental analysis was performed. 52 H 32 Cl2F 24 O2P2Ti (1325.50): Theoretical calculation: C, 47.12; H, 2.43; Measured value: C, 47.01; H, 2.30.

[0107] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (3.3mL, 5 mmol) and complex 14 (6.6 mg, 5 μmol) were added, and the mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0108] Example 13 Complex 30: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) Ligand L2 was prepared according to the method of Example 10.

[0109] Under a nitrogen atmosphere, ligand L2 (1.21 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of (THF)2ZrCl4 (0.38 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 30 in 71% yield. Elemental analysis measurement C 52 H 32 Cl2F 24 O2P2Zr (1368.86): Theoretical calculation: C, 45.63; H, 2.36; Measured value: C, 45.42; H, 2.30.

[0110] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (3.3mL, 5 mmol) and complex 30 (6.8 mg, 5 μmol) were added, and the mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0111] Example 14 Complex 30: Equation (II) (where M is Zr, R7, R9, and R 11 H is R8, and R 10 The complex represented by (where is -CF3, X is Cl, and n=2) A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (3.3mL, 5 mmol) and complex 30 (6.8 mg, 5 μmol) were added, and the mixture was reacted at 80°C while maintaining an ethylene pressure of 1.0 atm and stirring vigorously for 30 minutes. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0112] Example 15 Complex 24: Equation (II) (where M is Zr, and R8~R) 11 The complex represented by (where is H, R7 is a methoxy group, X is Cl, and n=2). Under a nitrogen atmosphere, the compound represented by formula (III) (2.32 g, 10 mmol) is dissolved in 20 mL of anhydrous ethyl ether, and n-butyllithium solution (2.7 M, 4.0 mL, 11 mmol) is added dropwise at -78°C, allowing the reaction to gradually return to room temperature. Stirring is continued for 12 hours to obtain a white precipitate. Bis(4-methoxy)chlorophosphine (PPh2(OMe)2Cl) (11 mmol, 3.08 g) is uniformly dispersed in 10 mL of ethyl ether and added dropwise to the original reaction system under an ice bath. The mixture was slowly heated to room temperature, stirred overnight, citrated with water, the organic phase was extracted with ethyl ether, the resulting organic phase was concentrated, deoxygenated by a refrigeration cycle, and the mixture was reacted for 5 hours with 5 mL of concentrated hydrochloric acid under a nitrogen atmosphere. After monitoring by TLC, when the reaction was complete, aqueous NaHCO3 solution was added to neutralize the mixture, citrated with water, the organic phase was extracted with ethyl ether, dried over anhydrous MgSO4, filtered, concentrated, and ligand L3 was obtained in 28% yield by column chromatography. Elemental analysis measurement C 24 H 25 O3P (392.43): Theoretical calculation: C, 73.46; H, 6.42; Measured values: C, 73.15; H, 6.78.

[0113] Under a nitrogen atmosphere, ligand L3 (0.78 g, 2 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of (THF)2ZrCl4 (0.38 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was reacted overnight at room temperature, the solvent was removed by aspirate, and dichloromethane (30 mL) was added to dissolve the mixture. The filtration cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 24 in 77% yield. Elemental analysis was performed. 48 H 48 Cl2O6P2Zr (944.98): Theoretical calculation: C, 61.01; H, 5.12; Measured values: C, 61.25; H, 5.32.

[0114] A 1L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 500mL of toluene was poured into the polymerization vessel, methylaluminoxane (3.3mL, 5 mmol) and complex 24 (4.7 mg, 5 μmol) were added, and the mixture was reacted by vigorously stirring for 30 minutes at 30°C while maintaining an ethylene pressure of 1.0 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0115] Comparative Example 1 A 1 L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours, and while still hot, it was vacuum-suctioned and purged three times with N2 gas. 500 mL of toluene was poured into the polymerization vessel, and methyl aluminoxane (6.5 mL, 10 mmol) and 8.3 mg (10 μmol) of complex A (synthesis is described in Inorg. Chem. 2006, 45, 511-513) were added. The reaction was carried out at 80°C, maintaining an ethylene pressure of 1.0 atm, and vigorously stirred for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene, and the polymer was dried and weighed to measure its polymerization activity. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0116] [ka]

[0117] Comparative Example 2 A 100 mL glass polymerization vessel with mechanical stirring function was dried continuously at 130 °C for 6 hours. While still hot, it was vacuum-suctioned and purged three times with N2 gas. 50 mL of toluene was poured into the polymerization vessel, and methyl aluminoxane (6.5 mL, 10 mmol), norbornene (0.5 g), and complex A (3.3 mg, 4.0 μmol) were added. The reaction was carried out at 70 °C, maintaining an ethylene pressure of 1.0 atm, and vigorously stirred for 10 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymer was dried, weighed, and its polymerization activity was measured. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0118] Comparative Example 3 A 1 L stainless steel polymerization vessel with mechanical stirring function was dried continuously at 130°C for 6 hours, and while still hot, it was vacuum-suctioned and purged three times with N2 gas. 500 mL of hexane was poured into the polymerization vessel, followed by methylaluminoxane (6.5 mL, 10 mmol) and complex B 8.3 mg (10 μmol) (synthesis is described in Inorg. Chem. 2006, 45, 511-513). The reaction was carried out at 80°C, maintaining an ethylene pressure of 1.0 atm, and vigorously stirred for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene, and the polymer was dried and weighed to measure its polymerization activity. The weight-uniform molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0119] [ka]

[0120] [Table 1]

[0121] From the data in Table 1, it was found that when the tetrahydronaphthol-phosphine early transition metal complex of the present invention was used as the main catalyst, it exhibited higher homopolymerization / copolymerization activity under similar polymerization conditions, and the resulting polymers had significantly improved molecular weight and a narrower molecular weight distribution. Specifically, comparing Examples 1-4 and 12 with Comparative Example 1, when Ti was used as the coordination metal in all cases, the complex of the present invention showed significantly high homopolymerization activity, and the prepared olefin polymers had significantly high molecular weight and a narrow molecular weight distribution. Comparing Examples 10 and 13-15 with Comparative Example 3, when Zr was used as the coordination metal, the complex of the present invention showed significantly high homopolymerization activity, and the prepared olefin polymers had significantly high molecular weight and a narrow molecular weight distribution. Comparing Examples 5-9 with Comparative Example 2, the complex according to the present invention showed significantly high olefin copolymerization activity, and the prepared polymers had high molecular weight and a narrow molecular weight distribution.

[0122] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, several simple modifications can be made to the technical solution of the present invention, including combining each technical feature in any other suitable manner, and these simple modifications and combinations should also be considered as part of the disclosure of the present invention and all fall within the scope of protection of the present invention.

Claims

1. A tetrahydronaphthol-phosphine early transition metal complex characterized by having a structural formula represented by formula (I). 【Chemistry 1】 (Here, M is selected from Group 4 metals, Ar is selected from substituted or unsubstituted C6-C20 aryl groups, X is selected from halogens and C1-C10 hydrocarbon groups, and n is 1 or 2.)

2. The tetrahydronaphthol-phosphine pre-transition metal complex according to claim 1, characterized in that its structural formula is represented by formula (II). 【Chemistry 2】 (Here, R ７ ~R １１ Each of these is independently selected from hydrogen, halogen, hydroxyl group, and substituted or unsubstituted C1-C20 hydrocarbon group.

3. R ７ ~R １１ The tetrahydronaphthol-phosphine pre-transition metal complex according to claim 2, characterized in that each of the members is independently selected from hydrogen, halogen, hydroxyl group, substituted or unsubstituted C1-C10 alkyl group, and substituted or unsubstituted C6-C15 aryl group.

4. The tetrahydronaphthol-phosphine pre-transition metal complex according to any one of claims 1 to 3, characterized in that M is Ti, Zr, or Hf.

5. The tetrahydronaphthol-phosphine pre-transition metal complex according to any one of claims 1 to 4, characterized in that X is a halogen or a C1-C8 hydrocarbon group.

6. A tetrahydronaphthol-phosphine pre-transition metal complex according to any one of claims 1 to 5, characterized by being selected from the group consisting of the following complexes. Complex 1: Formula (II) (where M is Ti and R) ７ ~R １１ The complex represented by (where is H, X is Cl, and n=1). Complex 2: Formula (II) (where M is Ti and R) ７ ~R １１ The complex represented by (where is H, X is Cl, and n=2). Complex 3: a complex represented by formula (II) (where M is Ti, R ７ ~R １１ is H, X is a methyl group, and n = 2) Complex 4: Equation (II) (where M is Ti and R ７ ~R １１ H is H, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 5: Formula (II) (where M is Ti and R) ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is Cl, and n=1). Complex 6: Formula (II) (where M is Ti and R ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 7: Equation (II) (where M is Ti and R) ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 8: Formula (II) (where M is Ti and R ８ ~R １１ H is R ７ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 9: Formula (II) (where M is Ti and R) ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is Cl, and n=1). Complex 10: Formula (II) (where M is Ti and R) ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 11: Formula (II) (where M is Ti and R) ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 12: Formula (II) (where M is Ti and R) ７ , R ８ , R １０ , and R １１ H is R ９ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 13: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is Cl and n=1). Complex 14: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is Cl and n=2) Complex 15: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is a methyl group and n=2). Complex 16: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ Therefore, X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 17: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is Cl, and n=1). Complex 18: a complex represented by formula (II) (where M is Ti, R ７ , R ９ , and R １１ are H, R ８ , and R １０ are methyl groups, X is Cl, and n = 2). Complex 19: Formula (II) (where M is Ti and R) ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 20: Formula (II) (where M is Ti, R ７ , R ９ , and R １１ is H, R ８ , and R １０ is a methyl group, X is -CH ２ C ６ H ５ and n = 2), a complex represented by Complex 21: Formula (II) (where M is Zr and R ７ ~R １１ The complex represented by (where is H, X is Cl, and n=2). Complex 22: Formula (II) (where M is Zr and R ７ ~R １１ The complex represented by (where is H, X is a methyl group, and n=2). Complex 23: Formula (II) (where M is Zr and R ７ ~R １１ H is H, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 24: Formula (II) (where M is Zr and R ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 25: Formula (II) (where M is Zr and R ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 26: Formula (II) (where M is Zr and R ８ ~R １１ H is R ７ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 27: Formula (II) (where M is Zr and R ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 28: Formula (II) (where M is Zr and R ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 29: Formula (II) (where M is Zr and R) ７ , R ８ , R １０ , and R １１ H is R ９ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 30: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is Cl and n=2) Complex 31: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is a methyl group and n=2). Complex 32: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ Therefore, X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 33: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is Cl, and n=2). Complex 34: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 35: Formula (II) (where M is Zr and R ７ , R ９ , and R １１ H is R ８ , and R １０ is a methyl group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 36: Formula (II) (where M is Hf and R) ７ ~R １１ The complex represented by (where is H, X is Cl, and n=2). Complex 37: Formula (II) (where M is Hf and R) ７ ~R １１ The complex represented by (where is H, X is a methyl group, and n=2). Complex 38: Formula (II) (where M is Hf and R) ７ ~R １１ H is H, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 39: Formula (II) (where M is Hf and R) ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 40: Formula (II) (where M is Hf and R) ８ ~R １１ H is R ７ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 41: Formula (II) (where M is Hf and R) ８ ~R １１ H is R ７ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 42: Formula (II) (where M is Hf and R ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is Cl, and n=2). Complex 43: Formula (II) (where M is Hf and R) ７ , R ８ , R １０ , and R １１ H is R ９ The complex represented by (where is a methoxy group, X is a methyl group, and n=2). Complex 44: Formula (II) (where M is Hf and R) ７ , R ８ , R １０ , and R １１ H is R ９ is a methoxy group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 45: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is Cl and n=2) Complex 46: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ The complex represented by (where X is a methyl group and n=2). Complex 47: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ Ha-CF ３ Therefore, X is -CH ２ C ６ H ５ The complex represented by (where n=2) Complex 48: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is Cl, and n=2). Complex 49: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ The complex represented by (where is a methyl group, X is a methyl group, and n=2). Complex 50: Formula (II) (where M is Hf and R) ７ , R ９ , and R １１ H is R ８ , and R １０ is a methyl group, and X is -CH ２ C ６ H ５ The complex represented by (where n=2)

7. A method for preparing a tetrahydronaphthol-phosphine early transition metal complex, wherein the method is: Step (1) involves reacting a compound represented by formula (III) with a compound represented by formula (IV) to produce a ligand, The process includes step (2) of reacting the ligand with a hydrogen extractant, then removing the hydrogen extractant, and reacting the resulting product with an M metal compound. The method is characterized in that the metal M in the aforementioned M metal compound is selected from Group 4 metals. 【Transformation 3】 (Here, in formula (IV), Ar is selected from substituted or unsubstituted C6-C20 aryl groups, and Y is a halogen.)

8. The method according to claim 7, characterized in that the hydrogen extractant is at least one selected from NaH, KH, n-butyllithium, and methyllithium.

9. The method according to 7, characterized in that the M metal compound is at least one selected from titanium tetrachloride, tetrachlorobis(tetrahydrofuran)titanium, trichlorotris(tetrahydrofuran)titanium, zirconium tetrachloride, tetrachlorobis(tetrahydrofuran)zirconium, hafnium tetrachloride, and tetrachlorobis(tetrahydrofuran)hafnium.

10. An olefin polymerization catalyst comprising a main catalyst and a co-catalyst, wherein the main catalyst is a tetrahydronaphthol-phosphine pre-transition metal complex as described in any one of claims 1 to 6.

11. The olefin polymerization catalyst according to claim 10, characterized in that the co-catalyst is an organoaluminum compound and / or an organoboron compound.

12. The aforementioned organoaluminum compounds include alkylaluminoxanes and those with the general formula Al ｎ Z ３－ｎ The olefin polymerization catalyst according to claim 11, characterized in that it is at least one organoaluminum compound (wherein L is selected from hydrogen, C1-C20 hydrocarbon groups, and C1-C20 hydrocarbyloxy groups, Z is selected from halogens, 0 < n ≤ 3, and n is an integer).

13. The olefin polymerization catalyst according to claim 11, characterized in that the organoboron compound is aromatic hydrocarbylboron and / or an organoborate.

14. A method for olefin polymerization, The method is characterized by comprising the step of carrying out an olefin polymerization reaction in the presence of an olefin polymerization catalyst according to any one of claims 10 to 13.

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