Heteroleptic metal complexes of cyclopentadienyl-noncyclopentadienyl metals, preparation methods thereof, and applications in the preparation of disentangled ultrahigh molecular weight polyethylene

Abstract

The present invention provides a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, as shown in formula (I). Compared to the prior art, the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex of the present invention, shown in formula (I), contains substituted silicon groups on the cyclopentadienyl ligands and fluorine atoms on the noncyclopentadienyl ligands. The large steric interaction between the two ligands helps restrict the growth direction of the polymer chain, thereby forming a disentangled structure. Furthermore, the attraction between the substituted silicon groups and fluorine atoms on the cyclopentadienyl ligands and hydrogen significantly suppresses the β-H elimination side reaction and helps regularize the polymer chains, thereby forming a disentangled ultrahigh molecular weight polyethylene. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, a preparation method thereof, and application thereof in the preparation of disentangled ultrahigh molecular weight polyethylene. Background Art

[0002] Metallocene complexes refer to compounds in which a metal center is coordinated with one or more cyclopentadienyl groups or their derivatives; non-metallocene complexes refer to compounds in which a metal center is coordinated with a ligand that does not contain a cyclopentadienyl group; and heterometallocene-nonmetallocene complexes refer to compounds in which a central metal is coordinated with both a cyclopentadienyl group or its derivative and a non-metallocene ligand that does not contain a cyclopentadienyl group. They are very important catalysts in polymerization reactions.

[0003] Ultra-high molecular weight polyethylene (UHMWPE) has excellent mechanical properties and broad application prospects. It can be used to prepare materials such as nanobattery membranes, bulletproof helmets, and artificial joints. However, one of the biggest problems with industrialization is its high viscosity, which makes it difficult to process. Disentangled UHMWPE can greatly reduce viscosity and processing difficulty. In the early days, disentangled UHMWPE could be obtained in extremely dilute UHMWPE solutions. In recent years, by using specific low-concentration catalysts to limit active sites and thus chain growth, disentangled UHMWPE can be directly obtained through polymerization. However, research on catalysts for disentangled UHMWPE is not comprehensive enough, and the conditions are relatively harsh. For example, Chinese patent publication number CN116462787A discloses that titanium zirconium hafnium catalysts can catalyze ethylene homopolymerization to obtain disentangled UHMWPE, but the polymerization conditions are demanding, and the polymerization process requires a low temperature below 30°C.

[0004] Therefore, the development of new catalysts and new methods for preparing disentangled ultra-high molecular weight polyethylene has broad prospects and great research significance. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, a preparation method thereof, and an application in the preparation of disentangled ultra-high molecular weight polyethylene. The cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex has excellent catalytic performance and can be catalytically polymerized under mild conditions to obtain disentangled ultra-high molecular weight polyethylene.

[0006] The present invention provides a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, as shown in formula (I):

[0007]

[0008] Wherein, M is a transition metal element of Group IV;

[0009] R1, R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl;

[0010] R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, or substituted or unsubstituted C6-C20 aryl; or R6 and R7 are linked to form a ring, or R6 and R8 are linked to form a ring, or R7 and R9 are linked to form a ring;

[0011] R 10 、R 11 , R12 and R 13 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl;

[0012] R 14 、R 15 With R 16 Each is independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl;

[0013] X is selected from halogen, C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl.

[0014] Preferably, the substituents in the substituted C1-C20 alkyl, substituted C2-C20 alkenyl, substituted C6-C20 aryl and substituted C1-C20 silyl are each independently selected from one or more of halogen, C1-C5 alkyl and phenyl.

[0015] Preferably, the M is selected from titanium, zirconium or hafnium;

[0016] At least one of R1, R2, R3, R4 and R5 is fluorine.

[0017] Preferably, R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C6 alkenyl; or R6 and R7 are connected to form a five-membered ring, a six-membered ring or a condensed ring, or R6 and R8 are connected to form a five-membered ring, a six-membered ring or a condensed ring, or R7 and R9 are connected to form a five-membered ring, a six-membered ring or a condensed ring;

[0018] R 10 、R 11 、R 12 With R13 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1-C5 silyl;

[0019] R 14 、R 15 With R 16 Each is independently selected from hydrogen, and a substituted or unsubstituted C1-C5 alkyl group.

[0020] Preferably, when R6 and R7 are connected to form a ring, or R6 and R8 are connected to form a ring, or R7 and R9 are connected to form a ring, the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex is as shown in Formula (II-1) or Formula (II-2):

[0021]

[0022] Wherein, E is O, S or NR; said R is selected from C1-C5 alkyl, phenyl or substituted phenyl; the substituent in said substituted phenyl is selected from one or more C1-C5 alkyl;

[0023] The R 17 、R 18 、R 19 、R 20 、R 21 With R 22 Each is independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, and a substituted or unsubstituted C6-C20 aryl group.

[0024] Preferably, as shown in formula (III-1), formula (III-2), formula (III-3) or formula (III-4):

[0025]

[0026] wherein R1, R2 and R3 are each independently selected from H or F;

[0027] R 11 is selected from H or tert-butyl.

[0028] The present invention also provides a method for preparing a cyclopentadienyl-cyclopentadienyl heteroleptic metal complex, comprising the following steps:

[0029] S1) reacting the metallocene intermediate represented by formula (E) with the non-metallocene ligand represented by formula (F) under anhydrous and oxygen-free conditions to obtain a metallocene-non-metallocene heteroleptic metal complex represented by formula (I) wherein X is a halogen;

[0030] S2) reacting a heteroleptic metal complex of formula (I) in which X is a halogen with a lithium compound of formula (G) in the absence of water and oxygen to obtain a heteroleptic metal complex of formula (I) in which X is a C1-C5 alkyl, benzyl, amino or silyl substituted C1-C5 alkyl;

[0031]

[0032] Wherein, M is a transition metal element of Group IV;

[0033] R1, R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl;

[0034] R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, or substituted or unsubstituted C6-C20 aryl; or R6 and R7 are linked to form a ring, or R6 and R8 are linked to form a ring, or R7 and R9 are linked to form a ring;

[0035] R 10 、R 11 、R 12 With R 13 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl;

[0036] R 14 、R 15 With R 16 Each is independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl;

[0037] X is selected from halogen, C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl;

[0038] X′ and X″ are each independently selected from halogen;

[0039] R' is a C1-C5 alkyl group substituted with benzyl, amino or silyl.

[0040] The present invention also provides a catalyst composition comprising the above-mentioned cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, an organic boron salt and an alkyl aluminum.

[0041] The present invention also provides a method for preparing disentangled ultra-high molecular weight polyethylene, comprising the following steps:

[0042] The method comprises mixing a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, an organic boron salt, an alkyl aluminum and an organic solution containing ethylene, introducing ethylene gas, and performing a polymerization reaction to obtain a disentangled ultrahigh molecular weight polyethylene.

[0043] Preferably, the viscosity-average molecular weight of the disentangled ultra-high molecular weight polyethylene is 1 to 8 million g / mol; the melting point of the disentangled ultra-high molecular weight polyethylene is 130° C. to 150° C.; and the crystallinity χ of the disentangled ultra-high molecular weight polyethylene is 60% to 90%.

[0044] The present invention provides a heteroleptic metal complex of amorphous metals, as shown in formula (I); wherein M is a Group IV transition metal element; R1, R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl; R6, R7, R8 and R9 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl; or R6 and R7 are connected to form a ring, or R6 and R8 are connected to form a ring, or R7 and R9 are connected to form a ring; R 10 、R 11 、R 12 With R 13 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 silyl; R 14 、R 15 With R 16 Each is independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group; and X is selected from halogen, a C1-C5 alkyl group, a benzyl group, an amino group, or a silyl-substituted C1-C5 alkyl group. Compared with the prior art, the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex of formula (I) provided by the present invention contains a substituted silicon group on the cyclopentadienyl ligand and a fluorine atom on the noncyclopentadienyl ligand. The large steric interaction between the two ligands helps to restrict the growth direction of the polymer chain, thereby obtaining a disentangled structure. In addition, the attraction between the substituted silicon group and the fluorine atom of the cyclopentadienyl ligand and hydrogen can greatly suppress the β-H elimination side reaction and help the polymer chains to arrange regularly, thereby obtaining a disentangled ultra-high molecular weight polyethylene.

[0045] Experimental results show that the heteroleptic titanium complex of formula (I) provided by the present invention can catalyze ethylene homopolymerization to obtain high-performance disentangled ultrahigh molecular weight polyethylene (dis-UHMWPE) with a viscosity-average molecular weight of 1 to 8 million g / mol. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the cyclopentadienyl-noncyclopentadienyl titanium complex 1 obtained in Example 1 of the present invention;

[0047] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the cyclopentadienyl-noncyclopentadienyl titanium complex 2 obtained in Example 2 of the present invention;

[0048] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the cyclopentadienyl-noncyclopentadienyl titanium complex 3 obtained in Example 3 of the present invention;

[0049] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of the cyclopentadienyl-noncyclopentadienyl titanium complex 7 obtained in Example 7 of the present invention;

[0050] Figure 5 This is a DSC test chart of the ultra-high molecular weight polyethylene obtained in Example 15 of the present invention;

[0051] Figure 6 This is a comparison of the ultra-high molecular weight polyethylene obtained in Example 20 of the present invention and the ultra-high molecular weight polyethylene prepared by catalyzing a commercial ZN catalyst and cold pressing at room temperature for 3 minutes. DETAILED DESCRIPTION

[0052] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0053] The present invention provides a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, as shown in formula (I):

[0054]

[0055] Wherein, M is a Group IV transition metal element, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf);

[0056] R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C1-C20 silyl, preferably hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C15 aryl, or substituted or unsubstituted C1-C10 silyl, more preferably hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C1-C5 silyl. ; The substituents in the substituted C1-C20 alkyl, substituted C2-C20 alkenyl, substituted C6-C20 aryl and substituted C1-C20 silyl are each independently preferably one or more of halogen, C1-C5 alkyl and phenyl, more preferably one or more of halogen, C1-C3 alkyl and phenyl; in the present invention, most preferably, R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, trimethylsilylmethyl or bistrimethylsilylmethyl; the halogen is any halogen well known to those skilled in the art without special limitation, and in the present invention, it is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine.

[0057] R6, R7, R8 and R9 are each independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, preferably hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C15 aryl, more preferably hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted substituted C6-C10 aryl; the substituents in the substituted C1-C20 alkyl, substituted C2-C20 alkenyl and substituted C6-C20 aryl are each independently one or more of halogen, C1-C5 alkyl and phenyl, more preferably one or more of halogen, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl and phenyl; the halogen is any halogen well known to those skilled in the art without special limitation, and in the present invention is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine.

[0058] Or R6 and R7 are connected to each other to form a ring, or R6 and R8 are connected to each other to form a ring, or R7 and R9 are connected to each other to form a ring; further preferably, or R6 and R7 are connected to each other to form a five-membered ring, a six-membered ring or a condensed ring, or R6 and R8 are connected to each other to form a five-membered ring, a six-membered ring or a condensed ring, or R7 and R9 are connected to each other to form a five-membered ring, a six-membered ring or a condensed ring.

[0059] More specifically, when R6 and R7 are connected to form a ring, or R6 and R8 are connected to form a ring, or R7 and R9 are connected to form a ring, the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex is as shown in Formula (II-1) or Formula (II-2):

[0060]

[0061] Wherein, E is O, S or NR; R is a C1-C5 alkyl, phenyl or substituted phenyl, preferably a methyl, ethyl, propyl, phenyl or substituted phenyl; the substituent in the substituted phenyl is preferably one or more of a C1-C5 alkyl, more preferably one or more of a methyl, ethyl and propyl.

[0062] The R 17 、R 18 、R 19 、R 20 、R 21 With R 22 Each of them is independently hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, preferably hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C15 aryl, more preferably hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C6-C10 aryl; the substituted The substituents in the C1-C20 alkyl, substituted C2-C20 alkenyl and substituted C6-C20 aryl are each independently one or more of halogen, C1-C5 alkyl and phenyl, more preferably one or more of halogen, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl and phenyl; the halogen is any halogen known to those skilled in the art without particular limitation, and in the present invention is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine; in the present invention, most preferably, the R 17 、R 18 、R 19 、R 20 、R 21 With R 22 Each is independently hydrogen, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, vinyl, propenyl, butenyl or phenyl.

[0063] R 10 、R 11 、R 12 With R 13 Each of the alkyl radicals is independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C1-C20 silyl, preferably hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C15 aryl, or substituted or unsubstituted C1-C10 silyl, more preferably hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1-C5 silyl; the substituents in the substituted C1-C20 alkyl, substituted C2-C20 alkenyl, substituted C6-C20 aryl and substituted C1-C20 silyl are each independently preferably one or more of halogen, C1-C5 alkyl and phenyl, more preferably one or more of halogen, C1-C3 alkyl and phenyl; in the present invention, most preferably, the R 10 、R 11 、R 12 With R 13 Each is independently hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, trimethylsilyl, trimethylsilylmethyl or bistrimethylsilylmethyl; the halogen is any halogen well known to those skilled in the art and is not particularly limited. In the present invention, it is preferably fluorine, chlorine, bromine or iodine, and more preferably fluorine, chlorine or bromine.

[0064] R 14 、R 15 With R 16 Each is independently hydrogen, substituted or unsubstituted C1-C20 alkyl, preferably hydrogen, substituted or unsubstituted C1-C10 alkyl, more preferably hydrogen, substituted or unsubstituted C1-C5 alkyl, and even more preferably hydrogen, substituted or unsubstituted C1-C3 alkyl; the substituent in the substituted C1-C20 alkyl is preferably one or more of halogen, C1-C5 alkyl and phenyl, more preferably one or more of halogen, C1-C3 alkyl and phenyl; the halogen is any halogen well known to those skilled in the art and is not particularly limited. In the present invention, it is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine.

[0065] X is halogen, C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl, preferably halogen, C1-C3 alkyl, benzyl, amino or silyl-substituted C1-C3 alkyl, more preferably halogen, methyl, ethyl, propyl, benzyl, amino, trimethylsilylmethyl or trimethylsilylethyl.

[0066] According to the present invention, it is further preferred that the heteroleptic metal complex is represented by formula (III-1), formula (III-2), formula (III-3) or formula (III-4):

[0067]

[0068] wherein R1, R2 and R3 are each independently selected from H or F;

[0069] R 11 is selected from H or tert-butyl.

[0070] According to the present invention, it is further preferred that the heteroleptic metal complexes are complexes 1 to 24:

[0071] Complex 1: having the structure shown in formula (III-1), R1, R2 and R3 are F, R 11 is H;

[0072] Complex 2: has the structure shown in formula (III-1), R1 is F, R2 and R3 are H, R 11 is H;

[0073] Complex 3: has the structure shown in formula (III-1), R1, R2 and R3 are H, R 11 is H;

[0074] Complex 4: having the structure shown in formula (III-1), R1, R2 and R3 are F, R 11 is tert-butyl;

[0075] Complex 5: has the structure shown in formula (III-1), R1 is F, R2 and R3 are H, R 11 is tert-butyl;

[0076] Complex 6: has the structure shown in formula (III-1), R1, R2 and R3 are H, R 11 is tert-butyl;

[0077] Complex 7: having the structure shown in formula (III-2), R1, R2 and R3 are F, R 11 is H;

[0078] Complex 8: has the structure shown in formula (III-2), R1 is F, R2 and R3 are H, R11 is H;

[0079] Complex 9: has the structure shown in formula (III-2), R1, R2 and R3 are H, R 11 is H;

[0080] Complex 10: having the structure shown in formula (III-2), R1, R2 and R3 are F, R 11 is tert-butyl;

[0081] Complex 11: having the structure shown in formula (III-2), R1 is F, R2 and R3 are H, R 11 is tert-butyl;

[0082] Complex 12: having the structure shown in formula (III-2), R1, R2 and R3 are H, R 11 is tert-butyl;

[0083] Complex 13: having the structure shown in formula (III-3), R1, R2 and R3 are F, R 11 is H;

[0084] Complex 14: having the structure shown in formula (III-3), R1 is F, R2 and R3 are H, R 11 is H;

[0085] Complex 15: has the structure shown in formula (III-3), R1, R2 and R3 are H, R 11 is H;

[0086] Complex 16: having the structure shown in formula (III-3), R1, R2 and R3 are F, R 11 is tert-butyl;

[0087] Complex 17: having the structure shown in formula (III-3), R1 is F, R2 and R3 are H, R 11 is tert-butyl;

[0088] Complex 18: having the structure shown in formula (III-3), R1, R2 and R3 are H, R 11 is tert-butyl;

[0089] Complex 19: having the structure shown in formula (III-4), R1, R2 and R3 are F, R 11 is H;

[0090] Complex 20: having the structure shown in formula (III-4), R1 is F, R2 and R3 are H, R 11 is H;

[0091] Complex 21: having the structure shown in formula (III-4), R1, R2 and R3 are H, R 11 is H;

[0092] Complex 22: having the structure shown in formula (III-4), R1, R2 and R3 are F, R 11 is tert-butyl;

[0093] Complex 23: has the structure shown in formula (III-4), R1 is F, R2 and R3 are H, R 11 is tert-butyl;

[0094] Complex 24: having the structure shown in formula (III-4), R1, R2 and R3 are H, R 11 For tert-butyl.

[0095] The cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex of formula (I) provided by the present invention contains a substituted silicon group on the cyclopentadienyl ligand and a fluorine atom on the noncyclopentadienyl ligand. The large steric hindrance interaction between the two ligands is conducive to restricting the growth direction of the polymer chain, thereby obtaining a disentangled structure. In addition, the substituted silicon group of the cyclopentadienyl ligand and the attraction between the fluorine atom and hydrogen can greatly inhibit the β-H elimination side reaction and help the polymer chains to be regularly arranged, thereby obtaining a disentangled ultra-high molecular weight polyethylene.

[0096] The present invention also provides a method for preparing the metallocene-non-metallocene heteroleptic metal complex represented by the above formula (I), comprising the following steps: S1) reacting a metallocene intermediate represented by formula (E) with a non-metallocene ligand represented by formula (F) under anhydrous and oxygen-free conditions to obtain a metallocene-non-metallocene heteroleptic metal complex represented by formula (I) in which X is a halogen; S2) reacting the metallocene-non-metallocene heteroleptic metal complex represented by formula (I) in which X is a halogen with a lithiate represented by formula (G) under anhydrous and oxygen-free conditions to obtain a metallocene-non-metallocene heteroleptic metal complex represented by formula (I) in which X is a C1-C5 alkyl, benzyl, amino or silyl substituted C1-C5 alkyl;

[0097]

[0098] wherein M is a Group IV transition metal element; R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C1-C20 silyl; R6, R7, R8 and R9 are each independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, or substituted or unsubstituted C6-C20 aryl; or R6 and R7 are connected to form a ring, or R6 and R8 are connected to form a ring, or R7 and R9 are connected to form a ring; R10 、R 11 、R 12 With R 13 Each is independently hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C1-C20 silyl; R 14 、R 15 With R 16 Each is independently hydrogen, substituted or unsubstituted C1-C20 alkyl; X is halogen, C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl; X' and X" are each independently halogen; R' is C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl.

[0099] The present invention has no special restrictions on the sources of all raw materials, and any commercially available raw materials are sufficient; the R1 to R 16 The same as above for X, no further details will be given here.

[0100] In the present invention, the metallocene intermediate represented by formula (E) can be prepared according to existing methods well known to those skilled in the art without any special limitations. In the present invention, the following steps are preferably followed: A1) reacting the metallocene ligand represented by formula (A) with trimethylhalosilane represented by formula (B) under anhydrous and oxygen-free conditions to obtain a silyl-substituted metallocene ligand represented by formula (C); A2) reacting the silyl-substituted metallocene ligand represented by formula (C) with a metal halide represented by formula (D) under anhydrous and oxygen-free conditions to obtain the metallocene intermediate represented by formula (E).

[0101]

[0102] Formula (D)

[0103] In the present invention, taking M as Ti and X″ as Cl as an example, when the cyclopentadienyl ring of the metallocene intermediate shown in formula (E) is a tetramethylcyclopentadienyl group substituted with a trimethylsilyl group, it can be prepared according to the following process:

[0104]

[0105] In the present invention, taking M as Ti and X″ as Cl as an example, when the cyclopentadienyl ring of the titanocene metal intermediate represented by formula (E) is a thiophene-fused trimethylsilylcyclopentadienyl ligand, it can be prepared according to the following process:

[0106]

[0107] Under anhydrous and oxygen-free conditions, the metallocene intermediate represented by formula (E) is reacted with the non-metallocene ligand represented by formula (F) to obtain a metallocene-nonmetallocene heteroleptic metal complex represented by formula (I) in which X is a halogen; in the present invention, the non-metallocene ligand represented by formula (F) is preferably reacted before sodium hydride in an organic solvent to obtain the corresponding sodium salt, and then the sodium salt is reacted with the metallocene intermediate represented by formula (E); the anhydrous and oxygen-free conditions are preferably provided by a protective atmosphere; the protective atmosphere can be any protective atmosphere well known to those skilled in the art and is not particularly limited. In the present invention, nitrogen and / or argon are preferably used; the organic solvent can be any organic solvent well known to those skilled in the art and is not particularly limited. In the present invention, tetrahydrofuran and / or toluene are preferably used; after the reaction, the reaction is preferably concentrated and recrystallized to obtain a metallocene-nonmetallocene heteroleptic metal complex represented by formula (I) in which X is a halogen.

[0108] Under anhydrous and oxygen-free conditions, a cyclopentadienol-noncyclopentadienol heteroleptic metal complex represented by formula (I) in which X is a halogen is reacted with a lithium compound represented by formula (G) to obtain a cyclopentadienol-noncyclopentadienol heteroleptic metal complex represented by formula (I) in which X is a C1-C5 alkyl group, benzyl group, amino group or silyl group substituted C1-C5 alkyl group; the anhydrous and oxygen-free conditions are preferably provided by a protective atmosphere; the protective atmosphere can be any protective atmosphere well known to those skilled in the art and is not particularly limited. In the present invention, nitrogen and / or argon are preferably used; the organic solvent can be any organic solvent well known to those skilled in the art and is not particularly limited. In the present invention, tetrahydrofuran and / or toluene are preferably used; after the reaction, the reaction mixture is preferably concentrated and recrystallized to obtain a cyclopentadienol-noncyclopentadienol heteroleptic metal complex represented by formula (I) in which X is a C1-C5 alkyl group, benzyl group, amino group or silyl group substituted C1-C5 alkyl group.

[0109] The present invention also provides a catalyst composition comprising the above-mentioned cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, an organic boron salt and an alkyl aluminum.

[0110] The catalyst composition provided by the present invention uses an organic boron salt as an activator, which is an ionic compound or a neutral compound containing boron.

[0111] The cationic portion of the organic boron salt is preferably one or more of a carbon cation, an oxonium ion, an ammonium cation and a phosphonium cation; the carbon cation is preferably a (triphenyl)carbon cation and / or a tri(substituted phenyl)carbon cation; the tri(substituted phenyl)carbon cation is preferably one or more of a tri(methylphenyl)carbon cation, a tri(dimethylphenyl)carbon cation and a tri(trimethylphenyl)carbon cation; the ammonium cation is preferably one or more of a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation and a tributylammonium cation; the phosphonium cation is preferably one or more of a triphenylphosphonium cation, a trimethylphenylphosphonium cation and a tri(xylyl)phosphonium cation.

[0112] The anion portion of the organic boron salt is preferably a tetravalent boron anion; the tetravalent boron anion is any tetravalent boron anion well known to those skilled in the art, and is not particularly limited. In the present invention, it is preferably one or more of tetrakis(phenyl)boron anion, tetrakis(monofluorophenyl)boron anion, tetrakis(difluorophenyl)boron anion, tetrakis(tetrafluoro-methyl-phenyl)boron anion and tetrakis(pentafluorophenyl)boron anion.

[0113] The organic boron salt in the present invention can be a combination product of any of the above-mentioned cationic moieties and anionic moieties or a neutral compound containing boron, preferably one or more of [Ph3C][B(C6F5)4], [PhMe2NH][B(C6F5)4] and B(C6F5)3.

[0114] In the catalyst composition provided by the present invention, the molar ratio of the organic boron salt to the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex represented by formula (I) is preferably (0.5-10):1, more preferably (1-5):1, and even more preferably (1-3):1.

[0115] According to the present invention, the alkyl aluminum is a co-catalyst, which can be any alkyl aluminum well known to those skilled in the art without any special limitation. In the present invention, it is preferably one or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum and diethylbenzylaluminum.

[0116] In the catalyst composition provided by the present invention, the molar ratio of the aluminum element in the alkyl aluminum to the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex represented by formula (I) is preferably (1-200):1, more preferably (1-100):1, and even more preferably (1-20):1.

[0117] The catalyst composition provided by the present invention can be used for the polymerization reaction of olefins; the olefins are preferably one or more of α-olefins, cyclic olefins, styrene and substituted styrenes; the α-olefins are preferably C2-C20 olefins, more preferably C2-C10 olefins, more preferably C2-C6 olefins, more preferably C2-C4 olefins, and most preferably ethylene and / or propylene; the cyclic olefins are preferably C5-C20 cyclic olefins, more preferably C5-C12 cyclic olefins, and more preferably one or more of norbornene (NB)-type cyclic olefins, dicyclopentadiene (DCPD) and cyclohexadiene.

[0118] The catalyst composition provided by the present invention exhibits the characteristics of high activity, high molecular weight, low entanglement and the like in catalyzing the polymerization reaction of ethylene and α-olefins.

[0119] The present invention also provides a method for preparing disentangled ultra-high molecular weight polyethylene, comprising the following steps: mixing the above-mentioned cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, organic boron salt, alkyl aluminum and an organic solution containing ethylene, and introducing ethylene gas to carry out a polymerization reaction to obtain disentangled ultra-high molecular weight polyethylene.

[0120] The catalyst composition is composed of the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, the organic boron salt and the alkyl aluminum. The types and proportions of the components are the same as those described above and will not be repeated here.

[0121] In the present invention, it is preferred to first perform an activation reaction on the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex, the organic boron salt and the alkyl aluminum in an organic solvent. It is more preferred to first perform an activation reaction on the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex and the alkyl aluminum in an organic solvent and then add the organic boron salt to obtain an activated catalyst composition. The organic solvent is any organic solvent well known to those skilled in the art and is not particularly limited. In the present invention, toluene is preferred. The activation reaction time is preferably 0.5 to 10 minutes, more preferably 1 to 5 minutes.

[0122] The activated catalyst composition is mixed with an organic solution containing ethylene, and ethylene gas is introduced to carry out a polymerization reaction; the organic solvent of the organic solution containing ethylene is preferably hexane; the concentration of the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex in the polymerization system is preferably 0.01 to 1 mmol / L, more preferably 0.01 to 0.8 mmol / L; the ethylene pressure in the polymerization system is preferably 2 to 10 bar, more preferably 4 to 8 bar, and even more preferably 4 to 6 bar; the polymerization reaction temperature is preferably 20° C. to 60° C., more preferably 25° C. to 40° C.; and the polymerization reaction time is preferably 5 to 100 min, more preferably 5 to 60 min.

[0123] After the polymerization reaction, the reaction is preferably terminated using a hydrochloric acid-ethanol solution; the volume ratio of hydrochloric acid to ethanol in the hydrochloric acid-ethanol solution is preferably 1:(5-15), more preferably 1:(8-12), and even more preferably 1:10; the mass concentration of the hydrochloric acid is preferably 20%-40%, more preferably 30%-40%, and even more preferably 35%-37%.

[0124] After the reaction is terminated, the reaction solution is preferably precipitated in ethanol and filtered to obtain disentangled ultrahigh molecular weight polyethylene.

[0125] The viscosity-average molecular weight of the disentangled ultra-high molecular weight polyethylene is preferably 200,000 to 8 million g / mol, more preferably 270,000 to 8 million g / mol, even more preferably 900,000 to 8 million g / mol, and most preferably 1 to 8 million g / mol; the melting point of the disentangled ultra-high molecular weight polyethylene is preferably 130°C to 150°C; the crystallinity of the disentangled ultra-high molecular weight polyethylene is preferably 60% to 90%.

[0126] To further illustrate the present invention, the following describes in detail a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex provided by the present invention, a preparation method thereof, and an application thereof in the preparation of disentangled ultrahigh molecular weight polyethylene in combination with examples.

[0127] The reagents used in the following examples are all commercially available; the mass concentration of hydrochloric acid used in the examples is 37%; the viscosity-average molecular weight in the examples and comparative examples is determined by utilizing the property that the viscosity of a dilute polymer solution is positively correlated with the molecular weight. A dilute decalin solution of ultra-high molecular weight polyethylene is prepared, and the difference between its viscosity and that of the standard solvent decalin is measured using a viscometer to calculate the viscosity-average molecular weight of the ultra-high molecular weight polyethylene; the crystallinity in the examples and comparative examples is tested using DSC.

[0128] Example 1

[0129] Under nitrogen protection, 0.34 g (1 mmol) of salicylaldimine ligand 1a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.45 g (yield 69%) of red solid complex 1, molecular formula C 29 H 33 Cl2F5NOSiTi, the reaction formula is as follows:

[0130]

[0131] The complex 1 obtained in Example 1 was analyzed by nuclear magnetic resonance to obtain its hydrogen nuclear magnetic resonance spectrum, as shown in FIG. Figure 1 The results of nuclear magnetic resonance are as follows: 1 H NMR (500MHz, Benzene-d6): δ9.57 (s, 1H), 8.40 (dd, J=7.8, 1.8Hz, 1H), 7.26 (dd, J=7.8, 1.8Hz, 1H), 6.84 (t, J = 7.7Hz, 1H), 2.14 (s, 6H), 1.50 (s, 6H), 1.32 (s, 9H), 0.33 (s, 9H).

[0132] The complex 1 obtained in Example 1 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 53.25 (53.31); H 5.01 (5.09); N 2.16 (2.14). The elemental analysis results were consistent with the theoretical values.

[0133] Example 2

[0134] Under nitrogen protection, 0.31 g (1 mmol) of salicylaldehyde imine ligand 2a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.32 g (yield 51%) of red solid complex 2, molecular formula C 29 H 35 Cl2F3NOSiTi, the reaction formula is as follows:

[0135]

[0136] The complex 2 obtained in Example 2 was analyzed by nuclear magnetic resonance to obtain its hydrogen nuclear magnetic resonance spectrum, as shown in FIG. Figure 2 The results of nuclear magnetic resonance are as follows: 1 H NMR (500MHz, Benzene-d6): δ9.59 (d, J=1.8Hz, 1H), 8.45 (dd, J=7.8, 1.8Hz, 1H), 7.24 (dd, J=7.8, 1.8Hz, 1 H),6.84(td,J=7.7,0.8Hz,1H),6.39--6.30(m,2H),2.17(s,6H),1.54(s,6H),1.35(s,9H),0.36(s,9H).

[0137] The complex 2 obtained in Example 2 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 56.35 (56.41); H 5.46 (5.71); N 2.12 (2.27). The elemental analysis results were consistent with the theoretical values.

[0138] Example 3

[0139] Under nitrogen protection, 0.29 g (1 mmol) of salicylaldehyde imine ligand 3a was dissolved in 5 mL of tetrahydrofuran, 0.024 g (1 mmol) of sodium hydride was slowly added, and the reaction was carried out for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran, and the reaction was carried out for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.08 g (yield 15%) of red solid complex 3, molecular formula C 29 H 36 Cl2F2NOSiTi, the reaction formula is as follows:

[0140]

[0141]

[0142] The complex 3 obtained in Example 3 was analyzed by nuclear magnetic resonance to obtain its hydrogen nuclear magnetic resonance spectrum, as shown in FIG. Figure 3 The results of nuclear magnetic resonance are as follows: 1 H NMR (500MHz, Benzene-d6): δ9.65 (d, J=1.8Hz, 1H), 8.49 (dd, J=7.8, 1.8Hz, 1H), 7.24 (dd, J=7.7, 1.8Hz, 1H), 6.84 (td, J=7 .7,0.8Hz,1H),6.67--6.63(m,2H),6.49(ddd,J=8.4,5.8,2.8Hz,1H),2.18(s,6H),1.57(s,6H),1.35(s,9H),0.35(s,9H).

[0143] The complex 3 obtained in Example 3 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 58.46 (58.11); H 5.87 (6.05); N 2.15 (2.34). The elemental analysis results were consistent with the theoretical values.

[0144] Example 4

[0145] Under nitrogen protection, 0.40 g (1 mmol) of salicylaldehyde imine ligand 4a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.32 g (yield 45%) of red solid complex 4, molecular formula C 33 H 41 Cl2F5NOSiTi, the reaction formula is as follows:

[0146]

[0147] The complex 4 obtained in Example 4 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 55.57 (55.86); H 5.67 (5.82); N 2.04 (1.97). The elemental analysis results were consistent with the theoretical values.

[0148] Example 5

[0149] Under nitrogen protection, 0.36 g (1 mmol) of salicylaldimine ligand 5a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.38 g (yield 56%) of red solid complex 5, molecular formula C 33 H 43 Cl2F3NOSiTi, the reaction formula is as follows:

[0150]

[0151] The complex 5 obtained in Example 5 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 59.03 (58.85); H 6.32 (6.44); N 2.01 (2.08). The elemental analysis results were consistent with the theoretical values.

[0152] Example 6

[0153] Under nitrogen protection, 0.34 g (1 mmol) of salicylaldehyde imine ligand 6a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.35 g (1 mmol) of trimethylsilyltetramethylcyclopentadienyltitanium trichloride intermediate 1b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.30 g (yield 46%) of red solid complex 6, molecular formula C 33 H 44 Cl2F2NOSiTi, the reaction formula is as follows:

[0154]

[0155] The complex 6 obtained in Example 6 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 59.98 (60.46); H 6.54 (6.77); N 2.35 (2.14). The elemental analysis results were consistent with the theoretical values.

[0156] Example 7

[0157] Under nitrogen protection, 0.34 g (1 mmol) of salicylaldimine ligand 1a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.40 g (yield 58%) of red solid complex 7, molecular formula C 30 H 32 Cl2F5NOSSiTi, the reaction formula is as follows:

[0158]

[0159] The complex 7 obtained in Example 7 was analyzed by nuclear magnetic resonance to obtain its hydrogen nuclear magnetic resonance spectrum, as shown in FIG. Figure 4 The results of nuclear magnetic resonance are as follows: 1 H NMR (500MHz, Benzene-d6): δ7.63(s,1H),7.38(d,J=7.7Hz,1H),7.08–-6.99(m,1H),6.83(dd,J=17.3,8.0Hz,1H),6.63(dt, J=26.5,7.8Hz,1H),2.06(d,J=50.4Hz,2H),1.54(d,J=10.4Hz,9H),1.42–-1.31(m,9H),0.28(d,J=10.6Hz,2H),0.13(s,2H).

[0160] The complex 7 obtained in Example 7 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 51.88 (51.73); H 4.95 (4.63); N 2.16 (2.01). The elemental analysis results were consistent with the theoretical values.

[0161] Example 8

[0162] Under nitrogen protection, 0.31 g (1 mmol) of salicylaldehyde imine ligand 2a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.25 g (yield 38%) of red solid complex 8, molecular formula C 30 H 34Cl2F3NOSSiTi, the reaction formula is as follows:

[0163]

[0164]

[0165] The complex 8 obtained in Example 8 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 54.32 (54.55); H 5.46 (5.19); N 2.33 (2.12). The elemental analysis results were consistent with the theoretical values.

[0166] Example 9

[0167] Under nitrogen protection, 0.29 g (1 mmol) of salicylaldehyde imine ligand 3a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.38 g (yield 59%) of red solid complex 9, molecular formula C 30 H 35 Cl2F2NOSSiTi, the reaction formula is as follows:

[0168]

[0169] The complex 9 obtained in Example 9 was analyzed by elemental analysis, and the elemental analysis results showed that the measured values ​​(theoretical values) were: C 56.41 (56.08); H 5.16 (5.49); N 2.02 (2.18). The elemental analysis results were consistent with the theoretical values.

[0170] Example 10

[0171] Under nitrogen protection, 0.40 g (1 mmol) of salicylaldehyde imine ligand 4a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.32 g (yield 43%) of red solid complex 10, molecular formula C 34 H 40 Cl2F5NOSSiTi, the reaction formula is as follows:

[0172]

[0173] Elemental analysis: Measured value (theoretical value) %: C 54.67 (54.26); H 5.01 (5.36); N 1.99 (1.86). The elemental analysis results are consistent with the theoretical values.

[0174] Example 11

[0175] Under nitrogen protection, 0.36 g (1 mmol) of salicylaldimine ligand 5a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.35 g (yield 35%) of red solid complex 11, molecular formula C 34 H 42 Cl2F3NOSSiTi, the reaction formula is as follows:

[0176]

[0177] Elemental analysis: Measured value (theoretical value) %: C 57.21 (56.99); H 5.84 (5.91); N 2.12 (1.95). The elemental analysis results are consistent with the theoretical values.

[0178] Example 12

[0179] Under nitrogen protection, 0.34 g (1 mmol) of salicylaldehyde imine ligand 6a was dissolved in 5 mL of tetrahydrofuran, and 0.024 g (1 mmol) of sodium hydride was slowly added. The reaction was continued for 12 h. The filtrate was filtered to obtain a solution of 0.39 g (1 mmol) of thiophene-fused trimethylsilylcyclopentadienyl titanium trichloride intermediate 2b in tetrahydrofuran. The reaction was continued for 12 h. The reaction solution was concentrated and recrystallized to obtain 0.35 g (yield 51%) of red solid complex 12, molecular formula C 34 H 43 Cl2F2NOSSiTi, the reaction formula is as follows:

[0180]

[0181] Elemental analysis: Measured value (theoretical value) %: C 58.21 (58.45); H 6.34 (6.20); N 1.95 (2.00). The elemental analysis results are consistent with the theoretical values.

[0182] Example 13

[0183] Under nitrogen protection, 0.65 g (1 mmol) of complex 1 was dissolved in 20 mL of toluene, and 0.19 g (2 mmol) of trimethylsilylmethylene lithium was slowly added. The reaction was continued for 12 h, and the filtrate was filtered to obtain the filtrate. The reaction solution was concentrated and recrystallized to obtain 0.31 g (yield 41%) of complex 13 as a red solid, with the molecular formula C 37 H 56 F5NOSi3Ti, the reaction formula is as follows:

[0184]

[0185] Elemental analysis: Measured value (theoretical value) %: C 58.09 (58.63); H 6.98 (7.45); N 1.43 (1.85). The elemental analysis results are consistent with the theoretical values.

[0186] Example 14

[0187] Under anhydrous and oxygen-free conditions, 5 μmol of complex 1 was reacted with 100 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 5 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 150 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 40°C under 4 bar ethylene pressure for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 3.30 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =780×10 4 g / mol, T m =145℃.

[0188] Example 15

[0189] Under anhydrous and oxygen-free conditions, 5 μmol of complex 1 was reacted with 100 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 5 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 150 mL of hexane solvent and ethylene atmosphere. After the reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 4.14 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =710×10 4 g / mol, T m =141℃.

[0190] The ultra-high molecular weight polyethylene obtained in Example 15 was analyzed by differential scanning calorimetry, and its DSC test graph was obtained as follows: Figure 5 As shown. Figure 5 It can be seen that the melting point measured during the second heating process is lower than that during the first heating process, indicating that the sample changes from a low entanglement state to an entangled state at high temperature. The melting point of the first heating process is higher than that of the second heating process, indicating that the disentanglement degree of polyethylene decreases and the crystallinity decreases after heating.

[0191] Example 16

[0192] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was reacted with 600 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 5 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 600 mL of hexane solvent and ethylene atmosphere. After the reaction was carried out at 4 bar ethylene pressure and 40°C for 2 hours, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 13.20 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =610×10 4 g / mol, T m =143℃.

[0193] Example 17

[0194] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 150 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 40°C under 4 bar ethylene pressure for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 2.30 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =651×10 4 g / mol, T m =143℃.

[0195] Example 18

[0196] Under anhydrous and oxygen-free conditions, 2 μmol of complex 1 was reacted with 40 μmol of Al iBu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 2 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 150 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 40°C under 4 bar ethylene pressure for 1 hour. After that, ethanol acidified with hydrochloric acid was added to terminate the polymerization reaction, producing 0.53 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =684×10 4 g / mol, T m =145℃.

[0197] Example 19

[0198] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 150 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 6 bar ethylene pressure and 40°C for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 1.54 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =480×10 4 g / mol, T m =147℃.

[0199] Example 20

[0200] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 40°C under 4 bar ethylene pressure for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.40 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =618×10 4 g / mol, T m =137℃.

[0201] The ultra-high molecular weight polyethylene obtained in Example 20 was cold-pressed at room temperature for 3 minutes. Figure 6 As shown. Figure 6It can be seen that the ultra-high molecular weight polyethylene of the present invention exhibits a completely different behavior from commercial ultra-high molecular weight polyethylene after cold pressing at room temperature, and is transparent. This is one of the characteristics of disentangled ultra-high molecular weight polyethylene, and transparency indicates a low degree of entanglement.

[0202] Example 21

[0203] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and a temperature of 25°C for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.10 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =91×10 4 g / mol, T m =135℃.

[0204] Example 22

[0205] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 60°C for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.14 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =27×10 4 g / mol, T m =129℃.

[0206] Example 23

[0207] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 and 5000 μmol of MAO were reacted in 2 mL of toluene at room temperature for 5 minutes. The toluene solution of the catalyst composition was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 40°C under 4 bar ethylene pressure for 1 hour. The polymerization reaction was terminated by adding a hydrochloric acid-ethanol solution in a volume ratio of 1:10 to produce 0.04 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =338×10 4 g / mol, Tm =136℃.

[0208] Example 24

[0209] Under anhydrous and oxygen-free conditions, 10 μmol of complex 1 and 5000 μmol of MAO were reacted in 2 mL of toluene at room temperature for 5 minutes. The toluene solution of the catalyst composition was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 4 bar ethylene pressure and 25°C for 1 hour. The polymerization reaction was terminated by adding a hydrochloric acid-ethanol solution in a volume ratio of 1:10 to produce 0.03 g of ultra-high molecular weight polyethylene. Its viscosity-average molecular weight M v =105×10 4 g / mol, T m =134℃.

[0210] Example 25

[0211] Under anhydrous and oxygen-free conditions, 10 μmol of complex 2 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, followed by the addition of 10 μmol of [Ph3C][B(C6F5)4] to form a 2 mL catalyst solution. This toluene solution was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 40°C under 4 bar ethylene pressure for 1 hour. The polymerization was terminated by the addition of a 1:10 by volume hydrochloric acid-ethanol solution, yielding 0.11 g of ultrahigh molecular weight polyethylene.

[0212] Example 26

[0213] Under anhydrous and oxygen-free conditions, 10 μmol of complex 3 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, followed by the addition of 10 μmol of [Ph3C][B(C6F5)4] to prepare a 2 mL catalyst solution. This toluene solution was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 40°C under 4 bar ethylene pressure for 1 hour. The polymerization was terminated by the addition of a 1:10 by volume hydrochloric acid-ethanol solution, yielding 0.05 g of ultra-high molecular weight polyethylene.

[0214] Example 27

[0215] Under anhydrous and oxygen-free conditions, 10 μmol of complex 4 was reacted with 200 μmol of Al iBu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.25 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =357×10 4 g / mol.

[0216] Example 28

[0217] Under anhydrous and oxygen-free conditions, 10 μmol of complex 5 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, followed by the addition of 10 μmol of [Ph3C][B(C6F5)4] to prepare a 2 mL catalyst solution. This toluene solution was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 40°C under 4 bar ethylene pressure for 1 hour, and then terminated by the addition of a 1:10 by volume hydrochloric acid-ethanol solution to produce 0.10 g of ultra-high molecular weight polyethylene.

[0218] Example 29

[0219] Under anhydrous and oxygen-free conditions, 10 μmol of complex 6 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, followed by the addition of 10 μmol of [Ph3C][B(C6F5)4] to prepare a 2 mL catalyst solution. This toluene solution was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was continued at 40°C under 4 bar ethylene pressure for 1 hour. The polymerization was terminated by the addition of a 1:10 by volume hydrochloric acid-ethanol solution, yielding 0.05 g of ultra-high molecular weight polyethylene.

[0220] Example 30

[0221] Under anhydrous and oxygen-free conditions, 10 μmol of complex 7 was reacted with 200 μmol of Al iBu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.45 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =486×10 4 g / mol.

[0222] Example 31

[0223] Under anhydrous and oxygen-free conditions, 10 μmol of complex 7 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 150 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 5.03 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =412×10 4 g / mol.

[0224] Example 32

[0225] Under anhydrous and oxygen-free conditions, 10 μmol of complex 13 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.33 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =257×10 4 g / mol.

[0226] Example 33

[0227] Under anhydrous and oxygen-free conditions, 10 μmol of complex 13 was reacted with 200 μmol of Al iBu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 150 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 4.01 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =214×10 4 g / mol.

[0228] Example 34

[0229] Under anhydrous and oxygen-free conditions, 10 μmol of complex 19 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 10 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.42 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =342×10 4 g / mol.

[0230] Example 35

[0231] Under anhydrous and oxygen-free conditions, 10 μmol of complex 19 was reacted with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol [Ph3C] [B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction bottle containing 150 mL of toluene solvent and ethylene atmosphere. The reaction was carried out at 4 bar ethylene pressure and 40°C for 1 hour, and then a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 4.87 g of ultra-high molecular weight polyethylene with a viscosity-average molecular weight of M v =297×10 4 g / mol.

[0232] Comparative Example 1

[0233] To further demonstrate the role of trimethylsilyl groups in heteroleptic metallocyclopentadienyl-cyclopentadienyl complexes, the present invention synthesized a similarly structured heteroleptic metallocyclopentadienyl-cyclopentadienyl catalyst without trimethylsilyl groups and conducted a comparative experiment under the same conditions. Comparative complex 1' was synthesized according to the method described in Journal of Organometallic Chemistry, 2003, 665, 135-149.

[0234]

[0235] According to the reaction conditions of Example 19, 10 μmol of comparative complex 1′ was mixed with 200 μmol of Al i Bu3 was reacted in 1 mL of toluene at room temperature for 5 minutes, and then 10 μmol of [Ph3C][B(C6F5)4] was added to prepare a catalyst composition solution (2 mL). The catalyst composition toluene solution was then injected into a reaction flask containing 10 mL of toluene solvent and an ethylene atmosphere. The reaction was carried out at 40°C under 4 bar ethylene pressure for 1 hour. After that, a hydrochloric acid-ethanol solution with a volume ratio of 1:10 was added to terminate the polymerization reaction, producing 0.13 g of polyethylene. Its viscosity-average molecular weight M v =150×10 4 g / mol, T m =137℃.

[0236] Table 1 shows the reaction parameters of the above examples and comparative examples and the performance test results of the obtained ultra-high molecular weight polyethylene.

[0237] Table 1 Reaction parameters and results of Examples 14 to 35 and Comparative Example 1

[0238]

[0239]

[0240] As can be seen from the above embodiments and comparative examples, the present invention provides a cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex for olefin polymerization, having a structure of formula (I); compared with the corresponding cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex not containing a trimethylsilyl group, the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex of the present invention exhibits ultrahigh molecular weight and low entanglement when catalyzing ethylene polymerization to obtain polyethylene.

[0241] The preferred embodiments of the present invention disclosed above are merely intended to help illustrate the present invention, but the present invention is not limited thereto. Those skilled in the art will appreciate that, within the scope of the technical concept of the present invention, the technical solutions of the present invention may be modified, or some of the technical features may be combined in any other manner. Such modifications or combinations do not deviate from the essence of the corresponding technical solutions from the spirit and scope of the various technical solutions of the present invention, and should be regarded as the contents disclosed by the present invention and fall within the scope of protection of the present invention.

Claims

1. A heteroleptic metal complex comprising: As shown in formula (I): Formula (I); Wherein, M is a transition metal element of Group IV; R1, R2 and R3 are each independently selected from hydrogen or fluorine; R4 and R5 are selected from fluorine; R6, R7, R8 and R9 are selected from methyl groups; or R6 and R8 are connected to each other to form a ring; R 10 、R 11 、R 12 With R 13 Each is independently selected from hydrogen or tert-butyl, and at least one is tert-butyl; R 14 、R 15 With R 16 selected from methyl; X is selected from halogen, C1~C5 alkyl, benzyl, amino or silyl-substituted C1~C5 alkyl; When R6 and R8 are connected to form a ring, the heteroleptic metal complex is as shown in Formula (II-1) or Formula (II-2): Formula (II-1) Formula (II-2) Where, E is S; The R 17 、R 18 、R 19 、R 20 、R 21 With R 22 Each is independently selected from hydrogen, substituted or unsubstituted C1~C20 alkyl, substituted or unsubstituted C2~C20 alkenyl, substituted or unsubstituted C6~C20 aryl; The substituents in the substituted C1-C20 alkyl group, the substituted C2-C20 alkenyl group, the substituted C6-C20 aryl group and the substituted C1-C20 silyl group are each independently selected from one or more of halogen, C1-C5 alkyl group and phenyl group.

2. The heteroleptic metal complex according to claim 1, characterized in that The M is selected from titanium, zirconium or hafnium.

3. The heteroleptic metal complex according to claim 1, wherein As shown in formula (III-1), formula (III-2), formula (III-3) or formula (III-4): Formula (III-1) Formula (III-2) Formula (III-3) Formula (III-4) wherein R1, R2 and R3 are each independently selected from H or F; R 11 is selected from H or tert-butyl.

4. A method for preparing the heteroleptic metal complex of claim 1, characterized in that: The following steps are involved: S1) reacting a metallocene intermediate represented by formula (E) with a non-metallocene ligand represented by formula (F) under anhydrous and oxygen-free conditions to obtain a metallocene-non-metallocene heteroleptic metal complex represented by formula (I) wherein X is a halogen; S2) reacting a heteroleptic metal complex of formula (I) in which X is a halogen with a lithium compound of formula (G) in the absence of water and oxygen to obtain a heteroleptic metal complex of formula (I) in which X is a C1-C5 alkyl, benzyl, amino or silyl substituted C1-C5 alkyl; Formula (E) Formula (F) Formula (I) Formula (G) X″ is selected from halogen; R' is selected from C1-C5 alkyl, benzyl, amino or silyl-substituted C1-C5 alkyl.

5. A catalyst composition, characterized in that The invention comprises the heteroleptic metal complex of any one of claims 1 to 3, an organic boron salt and an alkyl aluminum.

6. A method for preparing disentangled ultra-high molecular weight polyethylene, characterized in that: The following steps are involved: The cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex according to any one of claims 1 to 3, an organic boron salt, an alkyl aluminum and an organic solution containing ethylene are mixed, and ethylene gas is introduced to carry out a polymerization reaction to obtain a disentangled ultrahigh molecular weight polyethylene.

7. The preparation method according to claim 6, characterized in that The viscosity-average molecular weight of the disentangled ultra-high molecular weight polyethylene is 1 to 8 million g / mol; the melting point of the disentangled ultra-high molecular weight polyethylene is 130° C. to 150° C.; and the crystallinity χ of the disentangled ultra-high molecular weight polyethylene is 60% to 90%.

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