Phosphine-phenol half-metallocene complexes, and methods for their preparation and use - Patent Application 20070122997

Abstract

The present invention relates to the technical field of olefin polymerization catalysts and discloses a phosphine-phenol half metallocene complex, as well as a method for preparing and using the same. The structural formula of the phosphine-phenol half metallocene complex is shown in formula (I), where M is selected from Group IVB metals, Ar is selected from substituted or unsubstituted C6-C20 aryl, X is selected from halogen and C1-C10 hydrocarbyl, n is 1 or 2, and L1 is 、 The metal complex of the present invention is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl. When the complex contains the same metal and the polymerization conditions are similar, using the metal complex of the present invention as the main catalyst achieves higher polymerization activity, and the resulting polymer has a significantly narrower molecular weight distribution than the polymer obtained in the comparative example, and also has better copolymerization performance. In addition, the metal complex of the present invention still maintains higher polymerization activity even at higher polymerization temperatures. [Formula 1] JPEG2025533173000015.jpg49169

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to the technical field of olefin polymerization catalysts, and in particular to phosphine-phenol half-metallocene complexes, as well as methods for their preparation and use.

[0002] [Background technology] Polyolefin resins are widely used in industry and daily life because of their environmental friendliness compared to other resin materials. Polyethylene resins are an important polyolefin resin. Industrialized polyethylene catalysts include Ziegler-Natta catalysts (e.g., DE Pat. 889229 (1953); IT Pat. 545332 (1956) and IT Pat. 536899 (1955); Chem. Rev., 2000, 100, 1169 and related literature in the special feature), Phillips catalysts (e.g., Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327), and metallocene catalysts (e.g., W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999). Highly efficient late transition metal complex-type ethylene oligomerization and polymerization catalysts have also been rapidly developed in recent years. In 2006, the Gibson group, a group of British scientists, discovered that Group IV phenol-phosphine zirconium complexes have excellent catalytic activity for olefin polymerization, and can effectively promote the polymerization reaction of ethylene or propylene under the activation of cocatalysts such as methylaluminoxane (MAO) (Inorg. Chem, 2006, 45, 511-513, Organometallics 2008, 27, 235-245).

[0003] Currently, there is an urgent need for high-performance olefin polymerization catalysts in the production of high-end polyolefins, so the development of novel catalysts with good catalytic activity is of great importance.

[0004] Summary of the Invention The object of the present invention is to provide a phosphine-phenol half-metallocene complex, a preparation method thereof, and its use. The phosphine-phenol half-metallocene complex has good thermal stability. In particular, the metal complex can maintain a higher ethylene polymerization activity even at higher temperatures, and the resulting polymer has a narrower molecular weight distribution.

[0005] To achieve the above object, in a first aspect, the present invention provides a phosphine-phenol half metallocene complex, the structural formula of which is represented by formula (I):

[0006] [ka]

[0007] wherein M is selected from a Group IVB metal; Ar is selected from a substituted or unsubstituted C6-C20 aryl; X is selected from a halogen and a C1-C10 hydrocarbyl; n is 1 or 2; L1 is selected from a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl, a tetrahydroindenyl, and a substituted or unsubstituted fluorenyl; and R1 is OR 21 R 22 where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbyl; R 21 , R 22 and O are linked together to form a ring or ring system; and m is 0 or 1.

[0008] Preferably, the C6 to C20 aryl (including C6 to C15 aryl) is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, or biphenyl.

[0009] Preferably, for a substituted C6-C20 aryl, the substituents are selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy (preferably C1-C6 alkoxy, more preferably methoxy, ethoxy or propoxy), substituted or unsubstituted C1-C20 hydrocarbyl.

[0010] Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy.

[0011] Preferably, said halo is selected from fluoro, chloro, bromo or iodo.

[0012] Preferably, said halo includes monohalo, dihalo or perhalo, for example monofluoro, difluoro or perfluoro.

[0013] Preferably, for the substituted cyclopentadienyl, substituted indenyl, and substituted fluorenyl, the substituents are independently selected from C1 to C6 alkyl (such as methyl, ethyl, propyl, and butyl) or C6 to C15 aryl (such as phenyl, phenylmethyl, and phenylethyl).

[0014] Preferably, the C1-C10 hydrocarbyl comprises a C1-C8 hydrocarbyl (such as a C1-C6 alkyl) or a C6-C10 aralkyl, where aralkyl includes, but is not limited to, phenylmethyl, phenylethyl, phenyl n-propyl, phenyl isopropyl, phenyl n-butyl, and phenyl tert-butyl.

[0015] Preferably, the C1 to C20 hydrocarbyl comprises a C1 to C8 hydrocarbyl (such as a C1 to C6 alkyl), preferably methyl, ethyl or propyl, or a C6 to C15 aryl, preferably phenyl.

[0016] Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0017] Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0018] Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0019] In this specification, unless otherwise indicated, references to substituted states include mono- and poly-substitutions.

[0020] Unless otherwise indicated, the above radical definitions also apply to radical definitions in other preferred or related structures where the context dictates otherwise.

[0021] Preferably, the structural formula of the phosphine-phenol half metallocene complex is shown in formula (II):

[0022] [ka]

[0023] In the formula, R 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C20 hydrocarbyl. Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy, and halo-substituted C1-C6 alkoxy. Preferably, M is selected from titanium, zirconium, and hafnium.

[0024] Preferably, R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C6 hydrocarbyl, R 21 , R 22 and O are linked together to form a 5- or 6-membered ring.

[0025] Preferably, R 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl, and X is selected from halogen, C1-C8 hydrocarbyl.

[0026] Preferably, the C6-C15 aryl is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, or biphenyl.

[0027] Preferably, for substituted alkoxy, substituted C1-C10 alkyl and substituted C6-C15 aryl, the substituents are independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy.

[0028] Preferably, said halo is selected from fluoro, chloro, bromo or iodo.

[0029] Preferably, said halo includes monohalo, dihalo or perhalo.

[0030] Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0031] Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0032] Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0033] In a second aspect, the present invention provides a method for preparing the phosphine-phenol half metallocene complexes described above, the method comprising: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand of formula (V); (2) reacting the ligand with a hydrogen abstracting agent and then reacting with an M metal compound, wherein the metal M in the M metal compound is selected from Group IVB metals and the M metal compound comprises at least one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl;

[0034] [ka]

[0035] wherein Ar is defined as above.

[0036] Preferably, the M metal compound is cyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trichloride, methyl-cyclopentadienyltitanium trichloride, n-butyl-cyclopentadienyltitanium trichloride, tert-butyl-cyclopentadienyltitanium trichloride, indenyltitanium trichloride, fluorenyltitanium trichloride, butyl-indenyltitanium trichloride, 1-methyl-indenyltitanium trichloride, 2-methyl-indenyltitanium trichloride. titanium trichloride, 1-phenyl-indenyl-titanium trichloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, methyl-cyclopentadienyl zirconium trichloride, 1,3-dimethyl-cyclopentadienyl-zirconium trichloride, 1,2,4-trimethyl-cyclopentadienyl-zirconium trichloride, n-butyl-cyclopentadienyl zirconium trichloride, tert-butyl-cyclopentadienyl zirconium trichloride, Indenyl zirconium trichloride, fluorenyl zirconium trichloride, butyl-indenyl-zirconium trichloride, 1-methyl-indenyl zirconium trichloride, 2-methyl-indenyl zirconium trichloride, 1-phenyl-indenyl-zirconium trichloride, cyclopentadienyl-1,2-dimethoxy-ethyl-zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, methyl-cyclopentadienyl hafnium trichloride hafnium trichloride, 1,2,3,4-tetramethyl-cyclopentadienyl-hafnium trichloride, n-butyl-cyclopentadienyl hafnium trichloride, tert-butyl-cyclopentadienyl hafnium trichloride, isobutyl-cyclopentadienyl hafnium trichloride, indenyl hafnium trichloride, fluorenyl hafnium trichloride, trihydro-indenyl-hafnium trichloride and cyclopentadienyl-1,2-dimethoxy-ethyl-hafnium trichloride.

[0037] Preferably, the hydrogen abstracting agent is selected from at least one of NaH, KH, n-butyllithium, and methyllithium.

[0038] In a third aspect, the present invention provides the use of the above-described phosphine-phenol half metallocene complexes in olefin polymerization.

[0039] In a fourth aspect, the present invention provides an olefin polymerization catalyst comprising the above-described phosphine-phenol half metallocene complex and a cocatalyst.

[0040] Preferably, the co-catalyst is an organoaluminum compound and / or an organoboron compound.

[0041] Preferably, the organoaluminum compound is selected from one or more of alkylaluminoxanes, alkylaluminums and alkylaluminum halides.

[0042] Preferably, the organoboron compound is selected from one or more of an organoboron and an organoborate.

[0043] In a fifth aspect, the present invention provides a process for olefin polymerization, comprising the step of conducting an olefin polymerization reaction in the presence of the above-described olefin polymerization catalyst.

[0044] Preferably, the olefin polymerization reaction has a temperature of -78°C to 200°C, preferably -20°C to 150°C, and a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa.

[0045] When the phosphine-phenol half metallocene complex is used as the main catalyst in an olefin polymerization catalyst, it can achieve higher activity in the olefin polymerization catalyst, and the resulting polymer has higher molecular weight, narrower molecular weight distribution, and excellent copolymerizability.

[0046] Compared with the prior art, the technical solution of the present invention has the following advantages: (1) The synthesis of the phosphine-phenol half metallocene complexes described herein can be carried out simply and easily.

[0047] (2) The phosphine-phenol half metallocene complex described herein can catalyze the polymerization of olefins (especially ethylene) with high activity, and can maintain high polymerization activity especially at higher polymerization temperatures.

[0048] (3) The described phosphine-phenol half-metallocene complexes as the main catalysts show higher performance in the copolymerization of ethylene with α-olefins or cycloolefins (such as norbornene).

[0049] Detailed Description of Specific Embodiments Specific embodiments of the present invention will now be described in detail, but it should be understood that the specific embodiments described herein are merely for the purpose of illustrating and explaining the present invention and are not intended to limit the present invention.

[0050] The range endpoints and any values ​​disclosed herein should be understood not to be limited to the exact range or value, but to encompass values ​​close to these ranges or values.For numerical ranges, the values ​​between the endpoints of each range, the values ​​between the endpoints of each range and each point value, and the values ​​between each point value can be combined with each other to obtain one or more new numerical ranges.These numerical ranges should be considered as specifically disclosed herein.

[0051] The structural formula of the phosphine-phenol half metallocene complex according to the present invention is shown in formula (I):

[0052] [ka]

[0053] In the formula, Ar is selected from substituted or unsubstituted C6 to C20 aryl, preferably substituted or unsubstituted C6 to C15 aryl, more preferably substituted or unsubstituted C6 to C8 aryl.

[0054] In a preferred embodiment, the structural formula of the phosphine-phenol half metallocene complex is shown in formula (II):

[0055] [ka]

[0056] In the formula, R 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C20 hydrocarbyl. 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted C1-C6 alkoxy or substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0057] In formula (I) and formula (II), M is selected from the group IVB metals. In preferred cases, M is selected from titanium, zirconium and hafnium.

[0058] In formula (I) and formula (II), X is selected from halogen and C1 to C10 hydrocarbyl. In preferred cases, X is selected from halogen and C1 to C8 hydrocarbyl (such as C1 to C6 alkyl).

[0059] In formula (I) and formula (II), n is 1 or 2, and the number of X groups linked to the metal M is n. In a preferred case, n is 1.

[0060] In formula (I) and formula (II), L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl. In preferred cases, the group L1 is selected from cyclopentadienyl, methylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,3,4-tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, isobutylcyclopentadienyl, indenyl, butylindenyl, 1-methylindenyl, 2-methylindenyl, 1-phenylindenyl, trihydroindenyl, and fluorenyl.

[0061] In formula (I) and formula (II), R1 is OR 21 R 22 where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbyl; R 21 , R 22 and O are linked together to form a ring or ring system. 21 and R 22 are each independently selected from substituted or unsubstituted C1-C6 hydrocarbyl, R 21 , R 22 and O are linked together to form a 5- or 6-membered ring. In more preferred instances, R is tetrahydrofuranyl (C4H8O), 2-methyltetrahydrofuranyl, 3-methyltetrahydrofuranyl, 2,5-dimethyltetrahydrofuranyl, 2,2-dimethyltetrahydrofuranyl, and the like.

[0062] In formula (I) and formula (II), m may be 0 or 1. When m is 0, it means that the group R1 is absent.

[0063] In the present invention, the term "substituted" in the phrase "substituted or unsubstituted" means including one or more substituents. The substituents herein may be independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy, and halo-substituted C1-C6 alkoxy. Preferably, halo is selected from fluoro, chloro, bromo, or iodo.

[0064] In the present invention, alkyl (such as C1-C6 alkyl or C1-C10 alkyl) may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0065] In the present invention, alkoxy (such as C1-C6 alkoxy) can be independently selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0066] In the present invention, aryl (such as C6-C8 aryl, C6-C15 aryl or C6-C20 aryl) can be independently selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl or biphenyl.

[0067] In the present invention, the halogens are independently selected from fluorine, chlorine, bromine and iodine.

[0068] In a further preferred embodiment, the phosphine-phenol half metallocene complex is selected from the group consisting of the following complexes: Complex 1: A complex of formula (II) where M is Ti, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 2: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 3: A complex of formula (II) in which M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 4: A complex of formula (II) in which M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 5: A complex of formula (II) in which M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 6: A complex of formula (II) where M is Ti, L is indenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 7: A complex of formula (II) in which M is Ti, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 8: A complex of formula (II) where M is Ti, L is fluorenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 9: A complex of formula (II) in which M is Ti, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 10: A complex of formula (II) where M is Ti, L1 is cyclopentadienyl, and R 11 ~R15 is H, X is methyl, n=2, m=0; Complex 11: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 12: Complex of formula (II) where M is Ti, L1=1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 13: A complex of formula (II) in which M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 14: A complex of formula (II) in which M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 15: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 16: A complex of formula (II) where M is Ti, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 17: A complex of formula (II) where M is Ti, L1 is fluorenyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 18: A complex of formula (II) in which M is Ti, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is methyl, n=2, m=0; Complex 19: A complex of formula (II) in which M is Ti, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 20: A complex of formula (II) in which M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 21: A complex of formula (II) in which M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 22: A complex of formula (II) in which M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 23: A complex of formula (II) in which M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 24: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 25: A complex of formula (II) in which M is Ti, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 26: A complex of formula (II) where M is Ti, L1 is fluorenyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 27: A complex of formula (II) in which M is Ti, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is -CH2C6H5, n=2, m=0; Complex 28: A complex of formula (II) in which M is Ti, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 29: A complex of formula (II) in which M is Ti, L1 is cyclopentadienyl, and R 11 , R 13 , R 14 and R 15 is H and R 12 is -CF3, X is Cl, n=2, m=0; Complex 30: A complex of formula (II) in which M is Ti, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 31: A complex of formula (II) where M is Ti, L1 is cyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, m=0; Complex 32: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 33: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 34: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 35: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 36: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 37: A complex of formula (II) where M is Ti, L is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 38: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, m=0; Complex 39: A complex of formula (II) where M is Ti, L1 is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 40: A complex of formula (II) where M is Ti, L1 is fluorenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 41: A complex of formula (II) where M is Ti, L1 is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 42: A complex of formula (II) in which M is Zr, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 43: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 44: A complex of formula (II) in which M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 45: A complex of formula (II) in which M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 46: A complex of formula (II) in which M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 47: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 48: A complex of formula (II) wherein M is Zr, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 49: A complex of formula (II) wherein M is Zr, L is fluorenyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 50: A complex of formula (II) wherein M is Zr, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 51: A complex of formula (II) wherein M is Zr, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 52: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 53: A complex of formula (II) in which M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 54: A complex of formula (II) in which M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 55: A complex of formula (II) in which M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 56: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 57: A complex of formula (II) wherein M is Zr, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 58: A complex of formula (II) wherein M is Zr, L is fluorenyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 59: A complex of formula (II) wherein M is Zr, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 60: A complex of formula (II) wherein M is Zr, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 61: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 62: A complex of formula (II) in which M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 63: A complex of formula (II) in which M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 64: A complex of formula (II) in which M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=1, R1 is tetrahydrofuranyl, and m=1; Complex 65: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 66: A complex of formula (II) wherein M is Zr, L1 is tetrahydroindenyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 67: A complex of formula (II) wherein M is Zr, L is fluorenyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 68: A complex of formula (II) wherein M is Zr, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is —CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 69: A complex of formula (II) wherein M is Zr, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 70: A complex of formula (II) wherein M is Zr, L1 is cyclopentadienyl, and R 11 , R 13 , R 14 and R 15 is H and R 12 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 71: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 72: A complex of formula (II) in which M is Zr, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13is methoxy, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 73: A complex of formula (II) in which M is Zr, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 74: A complex of formula (II) in which M is Zr, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is —CH 2 C 6 H 5 , n=2, R 1 is tetrahydrofuranyl, and m=1; Complex 75: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 76: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 77: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 78: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 79: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 80: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 81: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 82: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13is methoxy, X is Cl, n=2, R1 is 2-methyltetrahydrofuranyl, and m=1; Complex 83: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 84: A complex of formula (II) wherein M is Zr, L1 is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 85: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 86: A complex of formula (II) wherein M is Zr, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 87: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 88: A complex of formula (II) wherein M is Zr, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 89: A complex of formula (II) wherein M is Zr, L is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 90: A complex of formula (II) in which M is Zr, L1 is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 91: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 92: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is —CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 93: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 13 and R15 is H and R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 94: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is methyl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 95: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 96: A complex of formula (II) in which M is Zr, L1 is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1; Complex 97: A complex of formula (II) in which M is Hf, L1 is cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 98: A complex of formula (II) in which M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 99: A complex of formula (II) in which M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 ~R 15is H, X is Cl, n=2, m=0; Complex 100: A complex of formula (II) in which M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 101: A complex of formula (II) in which M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 102: A complex of formula (II) wherein M is Hf, L1 is indenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 103: A complex of formula (II) where M is Hf, L1 is fluorenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 104: A complex of formula (II) where M is Hf, L1 is phenyl-indenyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0; Complex 105: A complex of formula (II) wherein M is Hf, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 106: A complex of formula (II) wherein M is Hf, L1 is cyclopentadienyl, and R 11 , R 13 , R 14 and R 15 is H and R 12 is -CF3, X is Cl, n=2, m=0; Complex 107: A complex of formula (II) where M is Hf, L1 is cyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 108: A complex of formula (II) where M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 109: A complex of formula (II) where M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 110: A complex of formula (II) where M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 111: A complex of formula (II) where M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, m=0; Complex 112: A complex of formula (II) wherein M is Hf, L1 is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13is -CF3, X is Cl, n=2, m=0; Complex 113: A complex of formula (II) wherein M is Hf, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 114: A complex of formula (II) wherein M is Hf, L1 is indenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, m=0; Complex 115: A complex of formula (II) wherein M is Hf, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, m=0; Complex 116: A complex of formula (II) where M is Hf, L is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is -CF3, X is Cl, n=2, m=0; Complex 117: A complex of formula (II) where M is Hf, L1 is fluorenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0; Complex 118: A complex of formula (II) wherein M is Hf, L1 is fluorenyl, and R 11 , R 12 , R 14 and R 15 is H and R 13is methoxy, X is Cl, n=2, m=0.

[0069] The method for preparing the above phosphine-phenol half metallocene complex may include: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand of formula (V); (2) reacting the ligand with a hydrogen abstracting agent and then reacting with an M metal compound, wherein the metal M in the M metal compound is selected from Group IVB metals and the M metal compound comprises at least one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl;

[0070] [ka]

[0071] wherein Ar is defined as above.

[0072] In a more preferred embodiment, the reaction process of step (1) is shown in the following reaction scheme:

[0073] [ka]

[0074] In the formula, R 11 ~R 15 The definition of is the same as above.

[0075] In the methods of the present invention, the compound of formula (III) may be in the S and / or R configuration.

[0076] In the method of the present invention, preferably the transition metal M in said M metal compound is selected from titanium, zirconium and hafnium.More preferably, the M metal compound is cyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trichloride, methyl-cyclopentadienyltitanium trichloride, n-butyl-cyclopentadienyltitanium trichloride, tert-butyl-cyclopentadienyltitanium trichloride, indenyltitanium trichloride, fluorenyltitanium trichloride, butyl-indenyl-titanium trichloride, 1-methyl-indenyltitanium trichloride, 2-methyl-indenyl Titanium trichloride, 1-phenyl-indenyl-titanium trichloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, methylcyclopentadienyl zirconium trichloride, 1,3-dimethylcyclopentadienyl zirconium trichloride, 1,2,4-trimethylcyclopentadienyl zirconium trichloride, n-butylcyclopentadienyl zirconium trichloride, tert-butylcyclopentadienyl zirconium trichloride , indenyl zirconium trichloride, fluorenyl zirconium trichloride, butyl-indenyl-zirconium trichloride, 1-methyl-indenyl zirconium trichloride, 2-methyl-indenyl zirconium trichloride, 1-phenyl-indenyl-zirconium trichloride, cyclopentadienyl-1,2-dimethoxy-ethyl-zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, methyl-cyclopentadienyl hafnium trichloride hafnium trichloride, 1,2,3,4-tetramethyl-cyclopentadienyl hafnium trichloride, n-butyl-cyclopentadienyl hafnium trichloride, tert-butyl-cyclopentadienyl hafnium trichloride, isobutyl-cyclopentadienyl hafnium trichloride, indenyl hafnium trichloride, fluorenyl hafnium trichloride, trihydro-indenyl-hafnium trichloride and cyclopentadienyl-1,2-dimethoxy-ethyl-hafnium trichloride.

[0077] In the method of the present invention, in a preferred case, the reaction process of step (1) preferably comprises a step of first reacting the compound of formula (III) with a hydrogen abstracting agent, and then reacting it with the compound of formula (IV).

[0078] In step (1) and step (2), the hydrogen abstracting agents used may be the same or different and are each independently selected from at least one of NaH, KH, n-butyllithium, and methyllithium.

[0079] In a specific embodiment, the preparation process of step (1) includes the following steps: under a protective gas (such as nitrogen) atmosphere, dissolving the compound of formula (III) in anhydrous diethyl ether, adding a hydrogen abstracting agent (such as n-butyllithium) at room temperature, stirring at room temperature, adding tetrahydrofuran, and further stirring the resulting black solution containing precipitates; then adding the compound of formula (VI), stirring at room temperature, and adding aqueous NHCl solution to quench; then extracting the organic phase with ethyl acetate, drying the resulting organic phase over anhydrous sodium sulfate, and recrystallizing it with dichloromethane / hexane to obtain a yellow crystalline compound; then adding methanol and concentrated hydrochloric acid, and reacting under reflux. After the reaction is completed, the organic solvent is removed, the product is dissolved in ethyl acetate, neutralized with aqueous NaHCO, and the organic phase is extracted, followed by drying, filtration, concentration, and column chromatography to obtain the ligand of formula (VII).

[0080] In a specific embodiment, the preparation process of step (2) comprises the following steps: dissolving the ligand obtained in step (1) in tetrahydrofuran under a protective gas (such as nitrogen) atmosphere, adding an excess hydrogen abstracting agent (such as NaH or KH), stirring at room temperature, filtering to remove the hydrogen abstracting agent, adding a tetrahydrofuran solution of an M metal compound, reacting overnight at room temperature, removing the solvent by suction, dissolving in dichloromethane, filtering to remove the filter cake, concentrating the filtrate, and recrystallizing with heptane to obtain the phosphine-phenol half metallocene complex of the present invention.

[0081] The present invention also provides the use of the above-mentioned phosphine-phenol half metallocene complex in the polymerization of olefins, preferably including ethylene, α-olefins, and cycloolefins, including, but not limited to, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0082] The present invention also provides an olefin polymerization catalyst comprising the above-mentioned phosphine-phenol half metallocene complex as a main catalyst.

[0083] The olefin polymerization catalyst further comprises a co-catalyst, which is an organoaluminum compound and / or an organoboron compound.

[0084] The organoaluminum compound is an alkylaluminoxane or an organoaluminum compound of the general formula AlR n X 1 3-n The organoaluminum compounds (alkylaluminum or alkylaluminum halide) of the general formula AlR n X 1 3-n In the formula, R is H, C1 to C20 hydrocarbyl (such as C1 to C10 hydrocarbyl), or C1 to C20 hydrocarbyloxy (such as C1 to C10 hydrocarbyloxy), preferably C1 to C20 alkyl (such as C1 to C10 alkyl), C1 to C20 alkoxy (such as C1 to C10 alkoxy), C7 to C20 aralkyl (such as C7 to C15 aralkyl), or C6 to C20 aryl (such as C6 to C15 aryl), and X 1is a halogen, preferably chlorine or bromine, and 0 < n ≦ 3. Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO), but are not limited thereto. Preferably, the organoaluminum compound is methylaluminoxane (MAO).

[0085] The organoboron compound is selected from arylboron and / or borate. The arylboron is preferably substituted or unsubstituted phenylboron, more preferably tris(pentafluorophenyl)boron. The borate is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and / or triphenylmethyltetrakis(pentafluorophenyl)borate.

[0086] According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to metal M in the main catalyst is (10 to 10 7):1, for example, 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, 1000000:1, 10000000:1 and any value therebetween, preferably (10 to 100,000):1, more preferably (100 to 10,000):1. When the co-catalyst is an organic boron compound, the molar ratio of boron in the co-catalyst to the metal M in the main catalyst is (0.1 to 1000):1, for example, 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, and any value therebetween, preferably (0.1 to 500):1.

[0087] In the present invention, the olefin is a C2 to C16 olefin, preferably ethylene or an α-olefin having 3 to 16 carbon atoms.

[0088] The present invention also provides a method for polymerizing an olefin, which comprises carrying out an olefin polymerization reaction in the presence of the above-mentioned olefin polymerization catalyst. The olefin polymerization reaction may be homopolymerization or copolymerization.

[0089] The olefin polymerization reaction may be carried out at a temperature of -78°C to 200°C, preferably -20°C to 150°C, and at a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa. Here, the term "pressure" refers to the ethylene pressure in the polymerization system, and is expressed in absolute pressure.

[0090] In the olefin polymerization method according to the present invention, the olefin is a C2 to C16 α-olefin.

[0091] According to one embodiment of the present invention, the olefin comprises ethylene.

[0092] According to one embodiment of the present invention, the olefins include ethylene, propylene, α-olefins and cycloolefins.

[0093] According to one embodiment of the present invention, the olefin polymerization reaction is carried out in a solvent with an olefin monomer, and the polymerization solvent is selected from one or more of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons. Specifically, the polymerization solvent is selected from one or more of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, chlorobenzene, and dichloroethane, and preferably selected from one or more of hexane, toluene, and heptane.

[0094] In the present invention, alkyl means straight chain alkyl, branched alkyl, or cyclic alkyl, including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0095] In the present invention, examples of aryl include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0096] In the present invention, alkenyl means straight chain alkenyl, branched alkenyl or cycloalkenyl, including, but not limited to, vinyl, allyl, butenyl.

[0097] In the present invention, examples of aralkyl include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-tert-butyl.

[0098] In the present invention, examples of alkaryl include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0099] The phosphine-phenol half metallocene complex of the present invention, as well as its preparation method and use, will be further illustrated by the following examples.This example is carried out on the premise of the technical solution of the present invention, and provides detailed embodiments and specific operation processes.However, the protection scope of the present invention is not limited to the following examples.

[0100] The experimental methods in the following examples are conventional in the art unless otherwise specified. The experimental materials used in the following examples are commercially available unless otherwise specified.

[0101] The analytical characterization equipment and test methods used in the following examples and comparative examples are as follows: (1) Nuclear magnetic resonance spectrometer: Bruker DMX 300 (300 MHz), tetramethylsilane (TMS) as an internal standard.

[0102] (2) Molecular weight and molecular weight distribution (PDI) of polymer (PDI = Mw / Mn): Measurement is carried out using a PL-GPC220 chromatograph with trichlorobenzene as the solvent at 150°C (standard: PS, flow rate: 1.0 mL / min, chromatography column: 3 x PLgel 10 μm M1 x ED-B, 300 x 7.5 nm).

[0103] (3) Activity measurement method: The polymer is washed with a hydrochloric acid-ethanol solution, dried in vacuum, and then weighed. The polymerization activity is calculated by polymer weight (g) / metal (mol) × 60 / polymerization time (min).

[0104] (4) Analysis of polymer comonomer content: Polymer samples were dissolved in 1,2,4-trichlorobenzene at 120°C and analyzed on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer using a 10 mm PASEX 13 probe. 1 H NMR, 13 Analyze by C NMR spectroscopy.

[0105] Example 1 Complex 43: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0106] Under a nitrogen atmosphere, compound of formula (III) (11.23 g, 30 mmol, S-configuration) was dissolved in anhydrous diethyl ether (150 mL). n-Butyllithium solution (2.7 M, 33.3 mL, 90 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. Tetrahydrofuran (150 mL) was added, and the resulting black solution containing a precipitate was stirred for an additional hour. Diphenylphosphine chloride (PPh2Cl) (90 mmol, 16.7 mL) was added at 0 °C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a yellow crystalline compound (15.54 g). Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed as monitored by thin layer chromatography (TLC), the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO3 solution. The organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and then separated by column chromatography (dichloromethane as solvent) to obtain ligand L1 in 67% yield. 1H NMR (400MHz, CDCl3): δ=5.41(s,2H),7.13~7.15(m,2H),7.24~7.29(m,4H),7.38~7.45(m,22H),7.62~7.64(m,2H). 31 P NMR (162 MHz, CDCl3): δ = -17.19 (s). High-resolution mass spectrometry: calculated: 654.19, tested: 655.20.

[0107] Under a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienyl zirconium trichloride (0.666 g, 2 mmol) in tetrahydrofuran (-78 °C) was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the yellow complex 43 in 77% yield. 1 H NMR (400MHz, CDCl3): δ=2.00(m,30H),3.63(m,8H),1.97(m,8H),6.63~7.56(m,22H),7.58~7.80(m,6H),7.95~8.10(m,2H). Elemental analysis test C 72 H 76 Cl4O4P2Zr2: Theoretical: C, 62.14; H, 5.51; Tested: C, 62.32; H, 5.62.

[0108] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 6.9 mg (5 μmol) of complex 43 were added. The reaction was carried out at 75°C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0109] Example 2 Complex 43: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0110] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously for 6 hours at 130°C, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 6.9 mg (5 μmol) of complex 43 were added. The reaction was carried out at 100°C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The results are shown in Table 1. After drying, the polymer was weighed and the polymerization activity was measured. The weight average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0111] Example 3 Complex 43: A complex of formula (II) in which M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0112] A 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 10 mL of 1-octene, and 6.9 mg (5 μmol) of complex 43 were added. The reaction was carried out at 75 °C for 10 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain a polymer. The polymer was dried and weighed, and the polymerization activity was measured. The weight average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0113] Example 4 Complex 2: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0114] Ligand L1 was prepared by the method of Example 1.

[0115] Under a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienyltitanium trichloride (0.578 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the orange complex 2 in 79% yield. 1 H NMR (300MHz, CDCl3): δ=2.28(s,30H),7.13~7.16(m,2H),7.27~7.30(m,4H),7.38~7.48(m,22H),7.61~7.64(m,2H). Elemental analysis test C 64 H 60Cl4O2P2Ti2: Theoretical: C, 66.23; H, 5.21; Tested: C, 66.41; H, 5.52.

[0116] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 5.8 mg (5 μmol) of complex 2 were added. The reaction was carried out at 30°C for 10 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. After drying, the polymer was weighed and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0117] Example 5 Complex 2: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0118] A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene was charged to the polymerization kettle, and triisobutylaluminum (0.2 mL, 1 mol / L), triphenylmethyltetra(pentafluorophenyl)borate (2 mL, 2 mmol / L), 2.5 g of norbornene, and 1.2 mg (1 μmol) of Complex 2 were added. The reaction was carried out at 25 °C for 10 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain the polymer. After drying, the polymer was weighed and its polymerization activity was measured. The weight average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0119] Example 6 Complex 2: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0120] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 5.8 mg (5 μmol) of complex 2 were added. The reaction was carried out at 75°C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. After drying, the polymer was weighed and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0121] Example 7 Complex 2: A complex of formula (II) where M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0122] A 1-L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 10 mL of 1-octene, and 5.8 mg (5 μmol) of complex 2 were added. The reaction was carried out at 75 °C for 30 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain polyethylene. The polymer was dried and weighed, and the polymerization activity was measured. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0123] Example 8 Complex 98: A complex of formula (II) in which M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0124] Ligand L1 was prepared by the method of Example 1.

[0125] Ligand L1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran under a nitrogen atmosphere, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienylhafnium trichloride (0.840 g, 2 mmol) in tetrahydrofuran (-78 °C) was added dropwise and allowed to react at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give white complex 98 in 80% yield. 1 H NMR (300MHz, CDCl3): δ=1.93~2.06(m,30H),7.05~7.07(m,2H),7.17~7.21(m,4H),7.28~7.37(m,22H),7.53~7.55(m,2H). Elemental analysis test C 64 H 60 Cl4Hf2O2P2: Theoretical: C, 54.06; H, 4.25; Tested: C, 54.27; H, 4.46.

[0126] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 7.1 mg (5 μmol) of complex 98 were added. The reaction was carried out at 75°C for 10 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. After drying, the polymer was weighed and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0127] Example 9 Complex 98: A complex of formula (II) in which M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 ~R 15 is H, X is Cl, n=2, m=0.

[0128] A 1-L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 10 mL of 1-octene, and 7.1 mg (5 μmol) of complex 98 were added. The reaction was carried out at 75°C for 10 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain a polymer. After drying, the polymer was weighed and its polymerization activity was measured. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the obtained polymer are shown in Table 1.

[0129] Example 10 Complex 78: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0130] Under a nitrogen atmosphere, the compound of formula (III) (3.74 g, 10 mmol, R-configuration) was dissolved in anhydrous diethyl ether (120 mL). n-Butyllithium solution (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. Tetrahydrofuran (120 mL) was added, and the resulting black solution containing a precipitate was stirred for an additional hour. Bis(3,5-di(trifluoromethyl)phenyl)phosphine chloride (30 mmol, 14.78 g) was added at 0°C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed as monitored by TLC, the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and then separated by column chromatography (dichloromethane as solvent) to obtain ligand L2 in 40% yield. 1 H NMR(400MHz,DMSO)δ9.10(s,2H),8.17(s,2H),8.13(s,2H),8.08(dd,J=13.3,6.5Hz,8 H),7.81(d,J=7.6Hz,2H),7.56(d,J=8.4Hz,2H),7.27(dd,4H),6.90(d,J=8.2Hz,2H). High-resolution mass spectrometry test: Theoretical calculation value: 1198.09, Test value: 1198.95. 31 P NMR (162MHz, DMSO): δ=-8.37(s). 1 H NMR(400MHz,CDCl3)δ5.14(s,2H),7.08~7.11(m,2H),7.41~7.46(m,4H),7.63( d, 2H), 7.78~7.81 (m, 2H), 7.84 (d, 4H), 7.86 (d, 4H), 7.91 (s, 2H), 7.94 (s, 2H).

[0131] Under a nitrogen atmosphere, ligand L2 (1.20 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienyl zirconium trichloride (0.666 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the yellow complex 78 in 77% yield. Elemental Analysis Test C 80 H 68 Cl4F 24 O4P2Zr2: Theoretical calculation: C, 49.64; H, 3.54; Tested values: C, 49.84; H, 3.61.

[0132] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 9.6 mg (5 μmol) of complex 78 were added. The reaction was carried out at 75°C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0133] Example 11 Complex 36: A complex of formula (II) where M is Ti, L1 is indenyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is -CF3, X is Cl, n=2, m=0.

[0134] Ligand L2 was prepared by the method of Example 10.

[0135] Under a nitrogen atmosphere, ligand L2 (1.20 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of indenyltitanium trichloride (0.539 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the red complex 36 in 75% yield. Elemental Analysis Test C 70 H 36 Cl4F 24 O2P2Ti2: Theoretical calculation: C, 50.51; H, 2.18; Tested values: C, 50.68; H, 2.32.

[0136] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 8.3 mg (5 μmol) of complex 36 were added. The reaction was carried out at 30°C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0137] Example 12 Complex 71: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 12 , R 14 and R 15 is H and R 13 is methoxy, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0138] Under a nitrogen atmosphere, compound (III) (3.74 g, 10 mmol, S-configuration) was dissolved in anhydrous diethyl ether (120 mL). n-Butyllithium solution (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. Tetrahydrofuran (120 mL) was added, and the resulting black solution containing a precipitate was stirred for an additional hour. Di(4-methoxy)phosphine chloride (30 mmol, 8.42 g) was added at 0°C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed as monitored by TLC, the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and then separated by column chromatography (dichloromethane as solvent) to give ligand L3 in 56% yield.

[0139] Under a nitrogen atmosphere, ligand L3 (0.774 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienyl zirconium trichloride (0.666 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the yellow complex 71 in 78% yield. Elemental Analysis Test C 76 H 84 Cl4O8P2Zr2: Theoretical: C, 60.38; H, 5.60; Tested: C, 60.44; H, 5.67.

[0140] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 7.6 mg (5 μmol) of complex 71 were added. The reaction was carried out at 75°C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0141] Example 13 Complex 79: A complex of formula (II) where M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 15 is H and R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuranyl, and m=1.

[0142] Under a nitrogen atmosphere, the compound of formula (III) (3.74 g, 10 mmol, R-configuration) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium (2.5 M, 12 mL, 30 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. Tetrahydrofuran (120 mL) was added, and the resulting black solution containing a precipitate was stirred for an additional hour. Di(3,5-dimethylphenyl)phosphine chloride (30 mmol, 8.30 g) was added at 0°C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH₄Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed as monitored by TLC, the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and then separated by column chromatography (dichloromethane as solvent) to give ligand L4 in 58% yield. 1 H NMR (400MHz, CDCl3) δ: 2.28 (s, 24H), 5.43 (s, 2H), 6.96~7.05 (m, 12H), 7.17 (m, 2H), 7.24 ~ 7.29 (m, 4H), 7.43 (d, 2H), 7.65 (m, 2H). High-resolution mass spectrometry test: Theoretical calculation value: 766.31, Test value: 767.32. 31 P NMR(162MHz, CDCl3)δ=-15.4(s).

[0143] Under a nitrogen atmosphere, ligand L4 (0.77 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of pentamethylcyclopentadienyl zirconium trichloride (0.666 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was allowed to proceed at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give the yellow complex 79 in 78% yield. Elemental Analysis Test C 80 H92 Cl4O4P2Zr2: Theoretical: C, 63.90; H, 6.17; Tested: C, 64.94; H, 6.37.

[0144] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 7.5 mg (5 μmol) of complex 79 were added. The reaction was carried out at 75°C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0145] Comparative Example 1 A 1-L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 7.2 mg (10 μmol) of Complex A (see Dalton Trans., 2014, 43, 222-230 for its synthesis process) were added. The reaction was carried out at 75 °C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0146] [ka]

[0147] Comparative Example 2 A 1-L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol) and 5.2 mg (10 μmol) of Complex B (for its synthesis, see JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1585-1594) were added. The reaction was carried out at 30 °C for 10 minutes with vigorous stirring, while maintaining the ethylene pressure at 4.0 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0148] [ka]

[0149] [Table 1]

[0150] As can be seen from the data in Table 1, when the complexes contain the same metals and the polymerization conditions are similar, using the metal complexes of the present invention as the main catalyst achieves higher polymerization activity, and the resulting polymers have significantly narrower molecular weight distributions than the polymers obtained in the comparative examples, and also have better copolymerization performance. Moreover, the metal complexes of the present invention still maintain higher polymerization activity even at higher polymerization temperatures.

[0151] Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited thereto. Within the technical spirit of the present invention, many simple modifications can be made to the technical solutions of the present invention, including various technical features combined in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosure of the present invention, and all fall within the scope of the present invention.

Claims

1. It has a structural formula shown in formula (I): 【Chemical 1】 wherein M is selected from a Group IVB metal; Ar is selected from a substituted or unsubstituted C6-C20 aryl; X is selected from a halogen, a C1-C10 hydrocarbyl; n is 1 or 2; and L １ is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl, and R １ is OR ２１ R ２２ where R ２１ and R ２２ are each independently selected from substituted or unsubstituted C1-C10 hydrocarbyl; R ２１ , R ２２ and O are linked together to form a ring or ring system, and m is 0 or 1; Preferably, the C6-C20 aryl is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, or biphenyl; Preferably, for the substituted C6-C20 aryl, the substituents are selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted C1-C20 hydrocarbyl, preferably, the alkoxy is C1-C6 alkoxy; Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy; Preferably, said halo is selected from fluoro, chloro, bromo, or iodo; Preferably, the C1-C10 hydrocarbyl is selected from C1-C8 hydrocarbyl, more preferably C1-C8 alkyl, and / or Preferably, the C1-C20 hydrocarbyl is selected from C1-C6 alkyl; Preferably, the phosphine-phenol half metallocene complex is characterized in that, for the substituted cyclopentadienyl, substituted indenyl, and substituted fluorenyl, the substituents are independently selected from C1 to C6 alkyl or C6 to C15 aryl.

2. It has a structural formula shown in formula (II): 【Chemistry 2】 In the formula, R １１ ~R １５ are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C20 hydrocarbyl, preferably for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents thereof are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy, and halo-substituted C1-C6 alkoxy.

3. 3. The phosphine-phenol half metallocene complex according to claim 1, wherein M is selected from titanium, zirconium and hafnium.

4. R ２１ and R ２２ are each independently selected from substituted or unsubstituted C1-C6 hydrocarbyl; R ２１ , R ２２ 3. The phosphine-phenol half metallocene complex according to claim 1, wherein O and O are linked together to form a 5- or 6-membered ring.

5. R １１ ~R １５ are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl; X is selected from halogen, C1-C8 hydrocarbyl; Preferably, for substituted alkoxy, substituted C1-C10 alkyl and substituted C6-C15 aryl, the substituents are independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy; Preferably, said C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; Preferably, said C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy; The phosphine-phenol half metallocene complex according to claim 2, characterized in that the halogen is preferably selected from fluorine, chlorine, bromine and iodine.

6. The phosphine-phenol half metallocene complex according to any one of claims 1 to 4, characterized in that it is selected from the group consisting of the following complexes: Complex 1: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 2: A complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 3: A complex of formula (II) where M is Ti and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 4: A complex of formula (II) where M is Ti and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 5: A complex of formula (II) where M is Ti and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 6: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 7: A complex of formula (II) where M is Ti and L １ is tetrahydroindenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 8: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 9: A complex of formula (II) where M is Ti and L １ is phenyl-indenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 10: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 11: A complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 12: A complex of formula (II) where M is Ti and L １ = 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 13: A complex of formula (II) where M is Ti and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 14: A complex of formula (II) where M is Ti and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 15: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 16: A complex of formula (II) where M is Ti and L １ is tetrahydroindenyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 17: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 18: Complex of formula (II) where M is Ti and L １ is phenyl-indenyl, and R １１ ~R １５ is H, X is methyl, n=2, m=0; Complex 19: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 20: Complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 21: A complex of formula (II) where M is Ti and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 22: A complex of formula (II) where M is Ti and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 23: A complex of formula (II) where M is Ti and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 24: Complex of formula (II) where M is Ti and L １ is indenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 25: A complex of formula (II) where M is Ti and L １ is tetrahydroindenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 26: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 27: A complex of formula (II) where M is Ti and L １ is phenyl-indenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and m=0; Complex 28: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 29: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ , R １３ , R １４ and R １５ is H and R １２ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 30: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 31: A complex of formula (II) where M is Ti and L １ is cyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, m=0; Complex 32: A complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 33: A complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 34: A complex of formula (II) where M is Ti and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 35: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 36: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 37: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 38: A complex of formula (II) where M is Ti and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, m=0; Complex 39: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 40: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 41: A complex of formula (II) where M is Ti and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 42: A complex of formula (II) in which M is Zr and L １ is cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 43: A complex of formula (II) in which M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 44: A complex of formula (II) where M is Zr and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 45: A complex of formula (II) where M is Zr and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 46: A complex of formula (II) where M is Zr and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 47: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 48: A complex of formula (II) in which M is Zr and L １ is tetrahydroindenyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 49: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 50: A complex of formula (II) in which M is Zr and L １ is phenyl-indenyl, and R １１ ~R １５ is H, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 51: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 52: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 53: A complex of formula (II) in which M is Zr and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 54: A complex of formula (II) where M is Zr and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 55: A complex of formula (II) where M is Zr and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 56: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 57: A complex of formula (II) where M is Zr and L １ is tetrahydroindenyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 58: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 59: A complex of formula (II) where M is Zr and L １ is phenyl-indenyl, and R １１ ~R １５ is H, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 60: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 61: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 62: A complex of formula (II) where M is Zr and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 63: A complex of formula (II) where M is Zr and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 64: A complex of formula (II) where M is Zr and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=1 and R １ is tetrahydrofuranyl and m=1; Complex 65: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 66: A complex of formula (II) where M is Zr and L １ is tetrahydroindenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 67: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 68: A complex of formula (II) where M is Zr and L １ is phenyl-indenyl, and R １１ ~R １５ is H and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 69: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 70: A complex of formula (II) in which M is Zr and L １ is cyclopentadienyl, and R １１ , R １３ , R １４ and R １５ is H and R １２ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 71: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 72: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 73: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 74: A complex of formula (II) where M is Zr and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy and X is —CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 75: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 76: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 77: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ and X is -CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 78: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 79: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 80: A complex of formula (II) in which M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 81: A complex of formula (II) in which M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ and X is -CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 82: A complex of formula (II) where M is Zr and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and R １ is 2-methyltetrahydrofuranyl and m=1; Complex 83: A complex of formula (II) in which M is Zr and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 84: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 85: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ and X is -CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 86: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 87: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 88: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 89: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ and X is -CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 90: A complex of formula (II) where M is Zr and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 91: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 92: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 93: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 94: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ X is methyl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 95: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ and X is -CH ２ C ６ H ５ where n=2 and R １ is tetrahydrofuranyl and m=1; Complex 96: A complex of formula (II) where M is Zr and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and R １ is tetrahydrofuranyl and m=1; Complex 97: A complex of formula (II) where M is Hf and L １ is cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 98: A complex of formula (II) where M is Hf and L １ is pentamethylcyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 99: A complex of formula (II) where M is Hf and L １ is 1-methyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 100: A complex of formula (II) where M is Hf and L １ is 1-n-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 101: A complex of formula (II) where M is Hf and L １ is 1-tert-butyl-2,4-cyclopentadienyl, and R １１ ~R １５ is H, X is Cl, n=2, and m=0; Complex 102: A complex of formula (II) where M is Hf and L １ is indenyl, and R １１ ~R １５ is H, X is Cl, n=2, and m=0; Complex 103: A complex of formula (II) where M is Hf and L １ is fluorenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 104: A complex of formula (II) where M is Hf and L １ is phenyl-indenyl, and R １１ ~R １５ is H, X is Cl, n=2, m=0; Complex 105: A complex of formula (II) where M is Hf and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 106: A complex of formula (II) where M is Hf and L １ is cyclopentadienyl, and R １１ , R １３ , R １４ and R １５ is H and R １２ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 107: A complex of formula (II) where M is Hf and L １ is cyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 108: A complex of formula (II) where M is Hf and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 109: A complex of formula (II) where M is Hf and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 110: A complex of formula (II) where M is Hf and L １ is pentamethylcyclopentadienyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 111: A complex of formula (II) where M is Hf and L １ is pentamethylcyclopentadienyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, m=0; Complex 112: A complex of formula (II) where M is Hf and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, and m=0; Complex 113: A complex of formula (II) where M is Hf and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 114: A complex of formula (II) where M is Hf and L １ is indenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, m=0; Complex 115: A complex of formula (II) where M is Hf and L １ is indenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ is methyl, X is Cl, n=2, m=0; Complex 116: A complex of formula (II) where M is Hf and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 117: A complex of formula (II) where M is Hf and L １ is fluorenyl, and R １１ , R １３ and R １５ is H and R １２ and R １４ Ha-CF ３ wherein X is Cl, n=2, m=0; Complex 118: A complex of formula (II) where M is Hf and L １ is fluorenyl, and R １１ , R １２ , R １４ and R １５ is H and R １３ is methoxy, X is Cl, n=2, and m=0.

7. A method for preparing the phosphine-phenol half metallocene complex according to any one of claims 1 to 6, characterized in that the method comprises the following steps: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand of formula (V); (2) reacting the ligand with a hydrogen abstracting agent and then reacting with an M metal compound, wherein the metal M in the M metal compound is selected from Group IVB metals and the M metal compound comprises at least one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl; 【Chemistry 3】 In the formula, the definition of Ar is the same as in claims 1, 2 and 6.

8. The M metal compound is cyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trichloride, methyl-cyclopentadienyltitanium trichloride, n-butyl-cyclopentadienyltitanium trichloride, tert-butyl-cyclopentadienyltitanium trichloride, indenyltitanium trichloride, fluorenyltitanium trichloride, butyl-indenyl-titanium trichloride, 1-methyl-indenyltitanium trichloride, 2-methyl-indenyltitanium trichloride , 1-phenyl-indenyl-titanium trichloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, methyl-cyclopentadienyl zirconium trichloride, 1,3-dimethyl-cyclopentadienyl-zirconium trichloride, 1,2,4-trimethyl-cyclopentadienyl-zirconium trichloride, n-butyl-cyclopentadienyl zirconium trichloride, tert-butyl-cyclopentadienyl zirconium trichloride, indenyl zirconium trichloride Chloride, fluorenyl zirconium trichloride, butyl-indenyl-zirconium trichloride, 1-methyl-indenyl zirconium trichloride, 2-methyl-indenyl zirconium trichloride, 1-phenyl-indenyl-zirconium trichloride, cyclopentadienyl-1,2-dimethoxy-ethyl-zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, methyl-cyclopentadienyl hafnium trichloride, 1,2,3,4-tetramethyl 8. The method of claim 7, wherein the hafnium trichloride is selected from at least one of butyl-cyclopentadienyl-hafnium trichloride, n-butyl-cyclopentadienyl hafnium trichloride, tert-butyl-cyclopentadienyl hafnium trichloride, isobutyl-cyclopentadienyl hafnium trichloride, indenyl hafnium trichloride, fluorenyl hafnium trichloride, trihydro-indenyl-hafnium trichloride and cyclopentadienyl-1,2-dimethoxy-ethyl-hafnium trichloride.

9. 8. The method of claim 7, wherein the hydrogen abstracting agent is selected from at least one of NaH, KH, n-butyllithium, and methyllithium.

10. Use of the phosphine-phenol half metallocene complex according to any one of claims 1 to 6 in olefin polymerization.

11. An olefin polymerization catalyst comprising the phosphine-phenol half metallocene complex according to any one of claims 1 to 6 and a cocatalyst.

12. the co-catalyst is an organoaluminum compound and / or an organoboron compound; Preferably, the organoaluminum compound is selected from one or more of alkylaluminoxanes, alkylaluminums and alkylaluminum halides; 12. The olefin polymerization catalyst according to claim 11, wherein the organoboron compound is preferably selected from one or more of organoborons and organoborates.

13. 13. The method of claim 12, further comprising: carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst according to claim 11. Preferably, the olefin polymerization reaction can be carried out at a temperature of -78°C to 200°C, preferably -20°C to 150°C, and at a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa.

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