CN110386956B - Early transition metal compound, preparation method and intermediate thereof, and application in olefin polymerization - Google Patents

Abstract

The invention relates to the field of catalysts for olefin polymerization, in particular to an early transition metal compound, a preparation method and an intermediate thereof, and application of the early transition metal compound in olefin polymerization. The early transition metal compound is a compound represented by the formula (1). The olefin catalyzed by the early transition metal compound or the crystal thereof has high catalytic activity and excellent catalytic activity under wide polymerization reaction conditions, and the catalyst has low cost and is beneficial to industrial production.

Description

Early transition metal compound, preparation method and intermediate thereof, and application in olefin polymerization

Technical Field

The invention relates to the field of catalysts for olefin polymerization, in particular to an early transition metal compound, a preparation method and an intermediate thereof, and application of the early transition metal compound in olefin polymerization.

Background

Polyolefins are a widely used and very important class of polymeric materials, including homopolymers and copolymers of ethylene, alpha olefins. Polyolefins are important in the synthetic resin industry and are useful as films, pipes, wires and cables.

Advances in olefin polymerization catalyst technology are a direct driving force for advances in the polyolefin industry. The catalytic polymerization of olefins has been the focus of attention by researchers and manufacturers, from traditional Ziegler-Natta catalysts to single-site metallocene catalysts that appeared in the end of the 80 th century, to highly active "post-metallocene" and late transition metal catalysts at the end of the 20 th century.

The traditional Ziegler-Natta catalyst has the defects of low catalytic activity, wide molecular weight distribution and high residual catalyst content in a polymerization product obtained by solution polymerization. The discovery of group IV metallocene catalysts has better solved this problem by having a single site of activity, allowing one to obtain polymers of the desired structure by altering the structure of the catalyst as required (W.Kaminsky et al, adv.Organomet.Chem.1980, 18, 99; H.H.Brintzingger et al, Angew.Chem.int.Ed.Engl.1995, 34, 1143). In recent decades, a metal complex obtained by coordinating cyclopentadiene with a transition metal with a ligand containing a coordinating atom such as N, O, P has been actively studied as an olefin polymerization catalyst, and such a catalyst is collectively referred to as a "post-metallocene" catalyst.

Late transition metal (Fe, Co, Ni, Pd, etc.) catalysts can catalyze ethylene polymerization to obtain various polyethylene products, such as polyethylene with a highly linear to highly branched structure, polyethylene with a monomodal distribution to a broad or bimodal distribution, and copolymers of ethylene and polar monomers, polyolefin block copolymers, etc.

US006133387A discloses the use of late transition metals Fe, Co, Ni, Pd containing pyridine bisphosphine for the copolymerization of olefins, the structure of which is shown below, but the activity of the complex to catalyze ethylene polymerization is only high under specific reaction conditions (e.g. high pressure), and thus the wide application of the catalyst is not facilitated:

disclosure of Invention

The invention aims to provide a novel early transition metal compound, a preparation method and an intermediate thereof and application in olefin polymerization.

In order to achieve the above object, one aspect of the present invention provides an early transition metal compound, which is a compound represented by formula (1):

formula (1)

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

R₃is-MtX_nor-Mt (X') X_nWherein, in the step (A),

mt is a group IVB metal element;

2n X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a metal elementA ligand for element Mt.

The second aspect of the present invention provides an intermediate of the above-mentioned early transition metal compound, wherein the intermediate of the early transition metal compound is a compound represented by formula (2):

formula (2)

Each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20Alkoxy group of (2).

The third aspect of the present invention provides the crystal of the aforementioned early transition metal compound, wherein the crystal system of the crystal is a triclinic system.

The fourth aspect of the present invention provides a method for producing an early transition metal compound, the method comprising:

(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;

(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);

(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);

(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);

optionally, in the case that at least one X in the compound represented by formula (1) obtained in step (4) is a halogen, the method further comprises: (5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');

formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (a)

Formula (b)

Formula (c) R₃-X”，

Formula (d) R₅-MgX '", formula (d') R₅-Li，

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20Alkoxy group of (a);

R₃is-MtX_nor-Mt (X') X_nWherein, in the step (A),

mt is a group IVB metal element;

2n X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of a metal element Mt;

R₅is selected from C_1-10A hydrocarbon group of (a);

x "and X'" are each independently selected from halogen.

The fifth aspect of the present invention provides an early transition metal compound obtained by the above-mentioned method.

In a sixth aspect, the present invention provides use of the above-mentioned early transition metal compound or the above-mentioned crystal of the early transition metal compound for catalyzing ethylene homopolymerization and/or ethylene- α -olefin copolymerization.

In a seventh aspect, the present invention provides a catalyst composition suitable for the polymerisation of olefins, the composition comprising a procatalyst which is a compound of the aforementioned early transition metal or a crystal of a compound of the aforementioned early transition metal and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound.

The eighth aspect of the present invention provides the use of the above composition in the catalysis of ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.

The ninth aspect of the present invention provides a process for producing an olefin polymer, which comprises: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;

wherein the catalyst is the composition.

The olefin polymerization catalyzed by the early transition metal compound or the crystal thereof shows high catalytic activity, has excellent catalytic activity under wide polymerization reaction conditions, and is low in cost and beneficial to industrial production.

Drawings

FIG. 1 shows a complex structure diagram (ORTEP diagram) and corresponding atom numbers of a single crystal of a compound represented by the formula (1-Ti-1) confirmed by single crystal diffraction analysis.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In one aspect of the present invention, there is provided an early transition metal compound, which is a compound represented by formula (1):

formula (1)

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

R₃is-MtX_nor-Mt (X') X_nWherein, in the step (A),

mt is a group IVB metal element;

2n X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of the metal element Mt.

In the present invention, said C_1-20The hydrocarbon group (C) is a hydrocarbon group having 1 to 20 carbon atoms in total, and may be a linear or branched alkyl group, or a linear or branched alkenyl group having an unsaturated carbon-carbon double bond, and may be, for example, C₁、C₂、C₃、C₄、C₅、C₆、C₇、C₈、C₉、C₁₀、C₁₁、C₁₂、C₁₃、C₁₄、C₁₅、C₁₆、C₁₇、C₁₈、C₁₉Or C₂₀A hydrocarbon group of (1). For example, the C_1-20The hydrocarbon group of (A) may be C_1-20Alkyl or C_2-20Alkenyl groups of (a). For C_1-16A hydrocarbon group of_1-10A hydrocarbon group of_1-8A hydrocarbon group of_1-6The hydrocarbon group of (1) can also be explained by the above definition, and the number of carbon atoms is different, but as long as the specific hydrocarbon group within the range of the number of carbon atoms can be selected from the suitable hydrocarbon groups of the number of carbon atoms specifically enumerated above.

Said C is_1-20The alkoxy group of (A) is an alkoxy group having 1 to 20 carbon atoms in totalFor example, it may be C₁、C₂、C₃、C₄、C₅、C₆、C₇、C₈、C₉、C₁₀、C₁₁、C₁₂、C₁₃、C₁₄、C₁₅、C₁₆、C₁₇、C₁₈、C₁₉Or C₂₀Alkoxy group of (2). For C_1-16Alkoxy group of (C)_1-10Alkoxy group of (C)_1-8Alkoxy group of (C)_1-6The alkoxy group (b) may be defined as above, and the number of carbon atoms may be different, but as long as the specific alkoxy group within the range of the number of carbon atoms is selected from the suitable alkoxy groups having the number of carbon atoms specifically listed above.

Said C is_1-4The hydrocarbon group (C) means a hydrocarbon group having 1 to 4 carbon atoms in total, and may be, for example, C₁、C₂、C₃Or C₄A hydrocarbon group of (1). For example, may be C_1-4Alkyl or C_2-4Specific examples of the alkenyl group in (b) include methyl (which may be represented by Me), ethyl (which may be represented by Et), n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, allyl, and propenyl.

Said unsubstituted C_6-16The aryl group of (2) means an aryl group having 6 to 16 carbon atoms in total, and may be a heteroaryl group or a non-heteroaryl group, and may be, for example, a phenyl group (may be represented by Ph), a naphthyl group, a biphenyl group, an anthryl group or a phenanthryl group.

Said substituted C_6-16Aryl means that the number of carbon atoms of the aromatic ring, excluding the substituents, is always from 6 to 16, and may be heteroaryl or non-heteroaryl, the substituted aryl having at least one aromatic ring H substituted by C_1-4May be substituted, for example, by C_1-4Phenyl substituted by hydrocarbon radicals of (A), C_1-4Alkyl-substituted naphthyl, by C_1-4Biphenyl substituted by hydrocarbon radicals of (A), C_1-4Or alkyl-substituted anthracenyl or by C_1-4The hydrocarbyl-substituted phenanthryl of (1).

The group IVB metal element may be Ti, Zr or Hf.

The halogen may be fluorine, chlorine, bromine or iodine.

In the present invention, the groups represented by the same symbols may be independently selected within the defined ranges, and may be the same or different, for example, although in the formula (1), the substituents at two positions are both represented by R¹Denotes, however, R at these two positions¹May be the same or different and are each at R¹Is independently selected from the definitions of (a). For example, 2n X's may be the same or different, and each is independently selected from the definition of X.

Wherein n may be 2, 3 or 4.

X 'is a ligand of the metal element Mt, such ligand may be a pi-ligand, for example X' may be a substituted or unsubstituted 1, 3-cyclobutadiene, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene ring, a substituted or unsubstituted 1,3, 5-cycloheptatriene or a substituted or unsubstituted cyclooctatetraene; wherein, for example, the substituent on these ligands may be C_1-6And halogen, and the like.

In a preferred embodiment of the invention, R¹、R²、R³And R⁴Each independently selected from H, C_1-16A hydrocarbon group of_1-16Alkoxy and halogen of (a);

mt is Ti, Zr or Hf;

2n X are each independently selected from C_1-8A hydrocarbon group of (a), fluorine, chlorine, bromine and iodine.

In another preferred embodiment of the invention, R¹、R²、R³And R⁴Each independently selected from H, C_1-10A hydrocarbon group of_1-10Alkoxy and halogen of (a);

R₁and R₂Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butylA phenyl group and a tert-butyl group;

mt is Ti, Zr or Hf;

each of the 2n xs is independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene.

In a more preferred embodiment of the invention, R¹、R²、R³And R⁴Each independently selected from H, C_1-6A hydrocarbon group of_1-6Alkoxy and halogen of (a);

R₁and R₂Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

mt is Ti, Zr or Hf;

2n X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene.

According to the invention, the early transition metal compound is preferably one of the compounds of the formula:

formula (1-Ti-1): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-2): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Ti, 2n X are Cl, and n is 3;

formula (1-Ti-3): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Ti-4): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Ti-5): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Ti, 2n xs are Br, and n is 3;

formula (1-Ti-6): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-7): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-8): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Ti, n X are Cl, and n is 3;

formula (1-Ti-9): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Ti-10): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Ti-11): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Ti, 2n xs are Br, and n is 3;

formula (1-Ti-12): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Ti, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-13): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-14): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Ti, 2n X are Cl, and n is 3;

formula (1-Ti-15): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Ti-16): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Ti-17): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_n，Mt is Ti, 2n X are Br, and n is 3;

formula (1-Ti-18): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-19): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Ti-20): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Ti, 2n X are Cl, and n is 3;

formula (1-Ti-21): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Ti-22): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Ti-23): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Ti, 2n xs are Br, and n is 3;

formula (1-Ti-24): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Ti, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-1): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-2): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Zr, 2n X are Cl, and n is 3;

formula (1-Zr-3): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are methyl, n is 2, X' is cyclopentadiene;

formula (1-Zr-4): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Zr-5): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Zr, 2n xs are Br, and n is 3;

formula (1-Zr-6): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-7): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-8): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Zr, n X are Cl, and n is 3;

formula (1-Zr-9): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are methyl, n is 2, X' is cyclopentadiene;

formula (1-Zr-10): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Zr-11): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Zr, 2n xs are Br, and n is 3;

formula (1-Zr-12): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Zr, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-13): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-14): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Zr, 2n X are Cl, and n is 3;

formula (1-Zr-15): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are methyl, n is 2, X' is cyclopentadiene;

formula (1-Zr-16):in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Zr-17): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Zr, 2n xs are Br, and n is 3;

formula (1-Zr-18): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-19): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Zr-20): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Zr, 2n X are Cl, and n is 3;

formula (1-Zr-21): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are methyl, n is 2, X' is cyclopentadiene;

formula (1-Zr-22): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Zr-23): in the formula (1), R¹、R²And R³Are all H, R⁴Are all methyl groups, and the methyl group is,R₁and R₂Are each tert-butyl, R₃is-MtX_nMt is Zr, 2n xs are Br, and n is 3;

formula (1-Zr-24): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Zr, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-1): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-2): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Hf, 2n X are Cl, and n is 3;

formula (1-Hf-3): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Hf-4): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Hf-5): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Hf, 2n xs are Br, and n is 3;

formula (1-Hf-6): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-7): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-8): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Hf, n X are Cl, and n is 3;

formula (1-Hf-9): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Hf-10): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Hf-11): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-MtX_nMt is Hf, 2n xs are Br, and n is 3;

formula (1-Hf-12): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each phenyl, R₃is-Mt (X') X_nMt is Hf, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-13): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-14): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Hf, 2n X are Cl, and n is 3;

formula (1-Hf-15): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are each methyl, n ═ 2, X' is cyclopentadiene;

formula (1-Hf-16): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Hf-17): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Hf, 2n xs are Br, and n is 3;

formula (1-Hf-18): in the formula (1), R¹、R²、R³And R⁴Are all H, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are all ethyl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-19): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Cl, n is 2, and X' is cyclopentadiene;

formula (1-Hf-20): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Hf, 2n X are Cl, and n is 3;

formula (1-Hf-21): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are each methyl, n ═ 2, and X' is a ringA pentadiene;

formula (1-Hf-22): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nMt is Hf, 2n X are Br, n is 2, and X' is cyclopentadiene;

formula (1-Hf-23): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-MtX_nMt is Hf, 2n xs are Br, and n is 3;

formula (1-Hf-24): in the formula (1), R¹、R²And R³Are all H, R⁴Are each methyl, R₁And R₂Are each tert-butyl, R₃is-Mt (X') X_nWhere Mt is Hf, 2n X are all ethyl, n ═ 2, and X' is cyclopentadiene.

In a preferred embodiment of the present invention, the early transition metal compound is one of compounds represented by the following formulae:

the second aspect of the present invention provides an intermediate of the above-mentioned early transition metal compound, wherein the intermediate of the early transition metal compound is a compound represented by formula (2):

formula (2)

Each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20Alkoxy group of (2).

The choice of the other groups in formula (2) will be made in accordance with the description of the groups of formula (1) hereinbefore, and the invention will not be described in any further detail here.

Preferably, each R₄Each independently selected from C_1-16And C is a hydrocarbon group_1-16Alkoxy group of (2).

More preferably, each R₄Each independently selected from C_1-10And C is a hydrocarbon group_1-10Alkoxy group of (2).

More preferably, each R₄Each independently selected from C_1-6And C is a hydrocarbon group_1-6Alkoxy group of (2).

Even more preferably, each R₄Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.

The specific selection of the intermediate of the above-mentioned early transition metal compound represented by the formula (2) can be selected in accordance with the specific examples of the early transition metal compound described above.

In a preferred embodiment of the present invention, the intermediate represented by formula (2) is one of the compounds represented by the following formulae:

the third aspect of the present invention provides the crystal of the aforementioned early transition metal compound, wherein the crystal system of the crystal is a triclinic system.

Specifically, the crystal system of the single crystal of the early transition metal compound represented by the above formula (1-Ti-1) is a triclinic crystal system, the space group is P-1, and the unit cell parameters:

α＝86.02°(3)，β＝89.96°(3)，γ＝61.44°(3)，Z＝2，ρ_calc＝1.4082g/cm³。

the single crystal of the present invention will have higher catalytic activity than that of the mixed crystal or non-single crystal form of the early transition metal compound.

The fourth aspect of the present invention provides a method for producing an early transition metal compound, the method comprising:

(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;

(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);

(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);

(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);

optionally, in the case that at least one X in the compound represented by formula (1) obtained in step (4) is a halogen, the method further comprises: (5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');

formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (a)

Formula (b)

Formula (c) R₃-X”，

Formula (d) R₅-MgX '", formula (d') R₅-Li，

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20Alkoxy group of (a);

R₃is-MtX_nor-Mt (X') X_nWherein, in the step (A),

mt is a group IVB metal element;

2n X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of a metal element Mt;

R₅is selected from C_1-10A hydrocarbon group of (a);

x "and X'" are each independently selected from halogen.

According to the invention, the above groups can be selected according to the description hereinbefore, which is not repeated here.

Preferably, R¹、R²、R³And R⁴Each independently selected from H, C_1-16A hydrocarbon group of_1-16Alkoxy and halogen of (a);

each R is₄Each independently selected from C_1-16And C is a hydrocarbon group_1-16Alkoxy group of (a);

mt is Ti, Zr or Hf;

2n X are each independently selected from C_1-8A hydrocarbon group of (a), fluorine, chlorine, bromine and iodine;

R₅is selected from C_1-8A hydrocarbon group of (1).

More preferably, R¹、R²、R³And R⁴Each independently selected from H, C_1-10A hydrocarbon group of_1-10Alkoxy and halogen of (a);

R₁and R₂Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

each R is₄Each independently selected from C_1-10And C is a hydrocarbon group_1-10Alkoxy group of (a);

mt is Ti, Zr or Hf;

each of the 2n xs is independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene;

R₅selected from methyl, ethyl, n-propyl or isopropyl.

Even more preferably, R¹、R²、R³And R⁴Each independently selected from H, C_1-6A hydrocarbon group of_1-6Alkoxy and halogen of (a);

R₁and R₂Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

each R is₄Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy;

mt is Ti, Zr or Hf;

2n X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene;

R₅selected from methyl or ethyl;

x "and X'" are each independently selected from the group consisting of fluorine, chlorine, bromine, and iodine.

In the above production method, the compound for reaction may be one or more of the compounds represented by the above formulae, and the compound represented by the formula (1) thus produced may be one of the compounds represented by the formula (1), or a mixture of a plurality of compounds represented by the formula (1), and this is within the scope of the present invention.

Wherein, the specific examples of the compound represented by the formula (3) may be selected from one or more of the compounds represented by the following formulae:

formula (3-1)

Formula (3-1)

Formula (3-3)

Formula (3-4)

Specific examples of the compound represented by the formula (4) may be selected from one or more compounds represented by the following formulae:

formula (4-1)

(also known as diphenyl ether);

formula (4-2)

Specific examples of the compound represented by the formula (a) may be selected from one or more compounds represented by the following formulae:

formula (a-1): in the formula (a), R₁And R₂Are each phenyl, X₃Is chlorine (also known as diphenyl phosphine chloride);

formula (a-2): in the formula (a), R₁And R₂Are each tert-butyl, X₃Is chlorine;

formula (a-3): in the formula (a), R₁And R₂Are each phenyl, X₃Is H;

formula (a-4): in the formula (a), R₁And R₂Are each tert-butyl, X₃Is H;

formula (a-5): in the formula (a), R₁And R₂Are each phenyl, X₃Is bromine;

formula (a-2): in the formula (a), R₁And R₂Are each tert-butyl, X₃Is bromine.

Specific examples of the compound represented by the formula (b) may be selected from one or more compounds represented by the following formulae:

formula (b-1): in the formula (b), R₄Are both methyl (also known as azidotrimethylsilane);

formula (b-2): in the formula (b), R₄Are all ethyl;

formula (b-3): in the formula (b), R₄Are both methoxy;

formula (b-2): in the formula (b), R₄Are all ethoxy groups.

Specific examples of the compound represented by the formula (c) may be selected from one or more compounds represented by the following formulae:

formula (c-Ti-1): in the formula (c), X' is Cl, R₃is-Mt (X') X_nWhere Mt is Ti, n X are Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpTiCl)₃)；

Formula (c-Ti-2): in the formula (c), X' is Cl, R₃is-MtX_nWhere Mt is Ti, n X are Cl, and n is 3 (which may also be represented by TiCl)₄)；

Formula (c-Ti-3): in the formula (c), X' is Br, R₃is-Mt (X') X_nMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;

formula (c-Ti-4): in the formula (c), X' is Br, R₃is-MtX_nMt is Ti, n X are Br, and n is 3;

formula (c-Zr-1): in the formula (c), X' is chlorine, R₃is-Mt (X') X_nWhere Mt is Zr, n X are each Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpZrCl)₃)；

Formula (c-Zr-2): in the formula (c), X' is chlorine, R₃is-MtX_nWhere Mt is Zr, n X are Cl, and n is 3 (may also be represented as ZrCl)₄)；

Formula (c-Zr-3): in the formula (c), X' is Br, R₃is-Mt (X') X_nMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;

formula (c-Zr-4): in the formula (c), X' is Br, R₃is-MtX_nMt is Zr, n X are Br, and n is 3;

formula (c-Hf-1): in the formula (c), X' is chlorine, R₃is-Mt (X') X_nWhere Mt is Hf, n X are Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpHfCl)₃)；

Formula (c-Hf-2): in the formula (c), X' is chlorine, R₃is-MtX_nWhere Mt is Hf, n X are Cl, and n is 3 (may also be represented as HfCl)₄)；

Formula (c-Hf-3): in the formula (c), X' is Br, R₃is-Mt (X') X_nMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;

formula (c-Hf-4): in the formula (c), X' is Br, R₃is-MtX_nWhere Mt is Hf, n X are Br, and n is 3.

Specific examples of the compound represented by the formula (d) may be selected from one or more compounds represented by the following formulae:

formula (d-1): in the formula (d), R₅Is methyl, X' "is Br (also denoted MeMgBr);

formula (d-2): in the formula (d), R₅Is a firstX' "is Cl (also can be represented by MeMgCl);

formula (d-3): in the formula (d), R₅Is ethyl, X' "is Br (also denoted by EtMgBr);

formula (d-4): in the formula (d), R₅For ethyl, X' "is Cl (also denoted by EtMgCl).

Specific examples of the compound represented by the formula (d') may be selected from one or more compounds represented by the following formulae:

formula (d' -1): in the formula (d'), R₅Is methyl;

formula (d' -2): in the formula (d'), R₅Is ethyl.

According to the present invention, the compound represented by formula (4) will be caused to form a lithium salt, i.e., X represented by formula (4), by the first substitution reaction of step (1)₁And X₂A lithium salt is formed at the group. Wherein the organolithium reagent may be selected from a plurality of organolithium compounds, preferably the organolithium reagent is of formula R₆-one or more of the compounds represented by Li, wherein R₆Is C_1-8Alkyl group of (1). More preferably, the organolithium reagent is one or more of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.

According to the present invention, the amount of the organolithium reagent may vary within a wide range as long as the compound represented by formula (4) can be sufficiently formed into the corresponding lithium salt, and preferably, the molar ratio of the compound represented by formula (4) to the organolithium reagent is 1: 1.8 to 3, preferably 1: 2-2.5.

According to the present invention, the solvent used in the first substitution reaction may be various solvents having good solubility for the compound represented by formula (4), for example, one or more selected from toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, chloroform, tetrachloromethane, and tetrahydrofuran. The amount of the solvent to be used may be varied within a wide range, and for example, the amount of the solvent to be used is 10 to 200mL relative to 10mmol of the compound represented by the formula (4).

According to the present invention, preferably, the conditions of the first substitution reaction include: the reaction is carried out for 0.5 to 2 hours at the temperature of between 90 ℃ below zero and 50 ℃ below zero, and then for 10 to 24 hours at the temperature of between 10 and 40 ℃. More preferably, the conditions of the first substitution reaction include: the reaction is carried out for 0.5 to 1.5 hours at the temperature of between 80 ℃ below zero and 70 ℃ below zero, and then the reaction is carried out for 12 to 20 hours at the temperature of between 20 and 30 ℃. The first substitution reaction may be carried out by mixing the compound represented by the formula (4) with a solvent, then introducing an organolithium reagent at-90 ℃ to-50 ℃ (preferably-80 ℃ to-70 ℃) (for example, in the form of dropwise addition).

According to the invention, the compound shown in the formula (3) is formed in the step (2) through a second substitution reaction, wherein the substitution product obtained in the step (1) can be extracted to perform the second substitution reaction with the compound shown in the formula (a), but preferably the substitution product obtained in the step (1) is not extracted, and the compound shown in the formula (a) is directly introduced into the system of the first substitution reaction to perform the second substitution reaction. Wherein the amount of the compound represented by formula (a) may be varied within a wide range as long as the compound represented by formula (3) can be obtained, and preferably, the molar ratio of the compound represented by formula (4) to the compound represented by formula (a) is 1: 1.8 to 3, preferably 1: 2-2.5.

According to the present invention, the compound represented by the formula (a) may be provided as a pure compound, but in order to promote the second substitution reaction to proceed more sufficiently, the compound represented by the formula (a) is provided as a solution thereof, and the solvent used may be, for example, one or more of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane, and tetrahydrofuran, and may be used in an amount such that the concentration of the solution of the compound represented by the formula (a) is, for example, 0.5 to 10 mmol/mL.

According to the present invention, preferably, the conditions of the second substitution reaction include: the temperature is 10-40 ℃ and the time is 10-24 h. More preferably, the conditions of the second substitution reaction include: the temperature is 20-30 ℃ and the time is 12-20 h. Wherein, the operation process of the step (2) may include: under the ice-bath condition, the compound solution shown in the formula (a) is introduced into the system of the first substitution reaction (for example, in a dropwise manner), and then the reaction is carried out under the conditions of the second substitution reaction.

According to the present invention, in order to extract the compound represented by the formula (3), the compound represented by the formula (3) can be obtained by removing the solvent (for example, by rotary evaporation) after the completion of the second substitution reaction, washing (for example, washing with acetone), and then drying.

According to the present invention, the compound represented by formula (2) can be obtained by reacting the compound represented by formula (3) with the azidosilane compound represented by formula (b) via the Staudinger reaction of step (3). The amount ratio of the compound represented by the formula (3) to the azidosilane compound represented by the formula (b) may be varied within a wide range, and in order to allow the compound represented by the formula (3) to react more sufficiently, it is preferable that the molar ratio of the compound represented by the formula (3) to the azidosilane compound represented by the formula (b) is 1: 1.8 to 5, preferably 1: 2-4.

According to the invention, the reaction can be carried out in the presence of one or more organic solvents selected from the group consisting of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane and tetrahydrofuran, which can be used in a wide range, for example in an amount of 10 to 200mL, relative to 10mmol of the compound of formula (3).

According to the present invention, preferably, the conditions of the staudinger reaction include: the temperature is 80-150 ℃ and the time is 5-20 h. More preferably, the conditions of the staudinger reaction include: the temperature is 100 ℃ and 140 ℃, and the time is 8-14 h. In order to extract the compound represented by the formula (2), the solvent may be removed (for example, by rotary evaporation) after the reaction is completed, and the compound represented by the formula (2) may be obtained.

According to the present invention, the compound represented by the formula (2) and the compound represented by the formula (c) are subjected to a third substitution reaction to obtain the compound represented by the formula (1). Preferably, the molar ratio of the compound represented by the formula (2) to the compound represented by the formula (c) is 1: 1.8 to 4, preferably 1: 2-3. Wherein, the compound shown in the formula (c) can be provided in the form of a solution thereof, and the solvent used can be one or more of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, chloroform, tetrachloromethane and tetrahydrofuran, and the concentration thereof can be 0.05 to 1mmol/mL, for example.

According to the invention, the reaction of step (4) can also be carried out in the presence of one or more organic solvents selected from the group consisting of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane and tetrahydrofuran, in an amount which can vary within wide limits, for example in an amount of 10 to 500mL, relative to 10mmol of the compound of formula (2).

According to the present invention, preferably, the conditions of the third substitution reaction include: the temperature is 80-150 ℃ and the time is 8-20 h. More preferably, the conditions of the third substitution reaction include: the temperature is 100-140 ℃, and the time is 10-15 h. After the third substitution reaction is completed, the solvent may be removed (for example, by rotary evaporation), washed (for example, with n-pentane), and then dried to obtain the compound represented by formula (1).

According to the invention, the preparation of the compound of formula (1) wherein X is a hydrocarbon group can also be carried out in other ways, for which purpose the process can optionally further comprise: in the case where at least one X in the compound represented by the formula (1) obtained in the step (4) is a halogen, the method further comprises: (5) carrying out a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d'); thus, the halogen X in the compound represented by the formula (1) as a reactant can be substituted with a hydrocarbon group.

According to the present invention, in the case of including step (5), the compound represented by formula (1) and the grignard reagent or alkyllithium are used in a molar ratio of 1: 1.8 to 8, preferably 1: 2-6. Wherein, the Grignard reagent or alkyl lithium can be provided in the form of a solution thereof, and the solvent generally used can be, for example, one or more of diethyl ether, tetrahydrofuran, n-hexane, n-pentane, etc., and the concentration thereof can be, for example, 0.5 to 5 mmol/mL.

According to the present invention, the fourth substitution reaction is carried out in the presence of an organic solvent, which may be one or more selected from the group consisting of diethyl ether, tetrahydrofuran, n-hexane, n-pentane, etc., in an amount varying over a wide range, for example, 100-2000mL relative to 10mmol of the compound represented by formula (1) as a reactant.

According to the present invention, preferably, the conditions of the fourth substitution reaction include: the temperature is 80-150 ℃ and the time is 8-20 h. More preferably, the conditions of the fourth substitution reaction include: the temperature is 100 ℃ and 140 ℃, and the time is 10-18 h. After the fourth substitution reaction is completed, the solvent may be removed (for example, by rotary evaporation), washed (for example, with n-pentane), and dried to obtain the compound represented by formula (1) as a product.

According to the present invention, in order to obtain a single crystal of the compound represented by formula (1), the crude product of the compound represented by formula (1) obtained by the above-mentioned method may be dissolved in a mixed solvent of dichloromethane/toluene (volume ratio is preferably 1: 0.5-2), the dissolving process is preferably performed in an inert atmosphere (e.g., nitrogen atmosphere, argon atmosphere, etc.), and then the resulting solution is allowed to stand and subjected to a solvent volatilization treatment (preferably performed in a vacuum drier), whereby a single crystal of the compound represented by formula (1) can be obtained.

The fifth aspect of the present invention provides an early transition metal compound obtained by the above-mentioned method.

The early transition metal compound produced by the above-mentioned production method of the present invention may be understood as a crude product of an early transition metal compound, a mixture of a plurality of early transition metal compounds, a single crystal of an early transition metal compound, a mixture of a plurality of single crystals of early transition metal compounds, or the like, and these are within the scope of the present invention.

In a sixth aspect, the present invention provides use of the above-mentioned early transition metal compound or the above-mentioned crystal of the early transition metal compound for catalyzing ethylene homopolymerization and/or ethylene- α -olefin copolymerization.

The alpha-olefin herein may be an alpha-olefin conventionally used in the art for copolymerization with ethylene, and may be, for example, one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene.

In a seventh aspect, the present invention provides a catalyst composition suitable for the polymerisation of olefins, the composition comprising a procatalyst which is a compound of the aforementioned early transition metal or a crystal of a compound of the aforementioned early transition metal and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound. It is to be understood that the procatalyst is one or more of the aforementioned early transition metal compounds or one or more of the aforementioned crystals of early transition metal compounds, including of course any combination thereof. Where the activator contains an organoboron compound, it is also understood that the activator contains one or more of organoboron compounds.

According to the invention, in the case where the activator is one or more of aluminum-containing compounds, the composition preferably contains the main catalyst in terms of the metal element Mt and the aluminum-containing compound in terms of the aluminum element in a molar ratio of 1: 50-3000, preferably 1: 100-1000, more preferably 1: 100-500, for example, 1: 100-200, 1: 300-500.

According to the present invention, in the case where the activator is an aluminum-containing compound and an organoboron compound, in the composition, preferably, the main catalyst in terms of a metal element Mt, the aluminum-containing compound in terms of an aluminum element, and the organoboron compound in terms of a boron element are contained in a molar ratio of 1: 0.1-500: 0.5 to 5, preferably 1: 0.2-100: 1-3, for example 1: 0.2-1: 1-2, 1: 2-10: 1-3, 1: 15-30: 1-3, 1: 50-80: 1-3.

According to the present invention, the aluminum-containing compound as an activator may be selected from a wide range and may be one or more of an alkylaluminum compound and an alkylaluminoxane compound, and preferably, the aluminum-containing compound is a mixture of an alkylaluminum compound and an alkylaluminoxane compound or an alkylaluminoxane compound.

Preferably, the alkylaluminoxane compound may be represented by formula (e),

wherein R is₃₁At least one group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl; t is an integer of 5 to 30. More preferably, in formula (3), R₃₁Is at least one group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl and tert-butyl. Further preferably, in formula (3), R₃₁Is at least one group selected from methyl, ethyl and isobutyl. Particularly preferably, the alkylaluminoxane compound is Methylaluminoxane (MAO) and/or isobutylaluminoxane, i.e., R₃₁Is methyl or isobutyl.

Preferably, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride. Particularly preferably, the alkyl aluminum compound is triisobutylaluminum.

According to the invention, preferably, the organoboron compound is selected from tris (pentafluorophenyl) boron (B (C)₆F₅)₃) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate ([ HNMe)₂Ph][B(C₆F₅)₄]) And triphenylcarbenium tetrakis (pentafluorophenyl) borate ([ Ph)₃C][B(C₆F₅)₄]) One or more of (a).

The composition of the present invention may also contain other necessary additives as long as these additives do not affect the catalytic effect of the composition. For example, the composition may contain an impurity scavenger.

The eighth aspect of the present invention provides the use of the above composition in the catalysis of ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.

In this application of the present invention, the order of addition and the method of addition of the components forming the catalyst composition suitable for olefin polymerization are not particularly limited, and the procatalyst, the activator and the optionally contained additive may be mixed in advance and then added to the polymerization reaction, or the procatalyst, the activator and the optionally contained additive may be added separately to the polymerization reaction. According to a preferred embodiment: the activator and the additive which is optionally contained are added into the reaction system, then the olefin monomer is introduced, and then the main catalyst is added.

Wherein the alpha olefin is as described above, and the invention is not repeated herein.

The ninth aspect of the present invention provides a process for producing an olefin polymer, which comprises: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;

wherein the catalyst is the composition.

According to the present invention, preferably, the polymerization conditions include: the temperature is-50 ℃ to 200 ℃, and the pressure is 0.1MPa to 5 MPa. More preferably, the polymerization conditions include: the temperature is 20-100 deg.C, and the pressure is 0.1-2MPa (such as 0.1-0.5 MPa). The pressure is a gauge pressure.

The polymerization reaction of the present invention may be carried out by solution polymerization or bulk polymerization. The polymerization reaction of the present invention may be a solution polymerization reaction, and it will be apparent to those skilled in the art that the solvent used therein should be liquid under the polymerization conditions and not participate in the polymerization reaction nor react with the polymer obtained by the reaction, i.e., the solvent is inert. Such solvents will be readily apparent to those of ordinary skill in the polymerization art and can be readily selected. Nevertheless, for the present invention, specific examples of the organic solvent may be, for example, one or more of benzene, toluene, ethylbenzene, xylene, n-pentane, n-hexane, n-heptane, n-octane, and cyclohexane, preferably n-hexane, n-octane, or n-heptane, and more preferably n-hexane is used as the solvent in the homopolymerization reaction of the present invention. For the polymerization according to the invention, the solvent is used in such an amount that the concentration of the polymer is in the range from 5 to 30% by weight, preferably from 8 to 10% by weight.

According to the present invention, the above polymerization process is preferably carried out under protection of an inert atmosphere, for example, one or more of nitrogen, helium, argon, etc. may be used to provide such an inert atmosphere.

In the polymerization reaction of the present invention, a terminator may be used to terminate the polymerization reaction after the completion of the polymerization reaction. The terminating agents used for this step are conventional to those skilled in the art. Commonly used terminating agents include deionized water, alcohols, acids, and the like. In the present invention, the terminator to be preferably used is one or more of isopropyl alcohol, methanol, water and the like.

Preferably, the olefin monomer is one or more of ethylene, an α -olefin and a cyclic olefin. Preferably, the α -olefin is one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene, and the cyclic olefin is one or more of cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene.

The above catalyst of the present invention is particularly suitable for homopolymerization of ethylene and copolymerization of ethylene-alpha olefin (particularly copolymerization of ethylene-propylene in a molar ratio of 1: 0.5-5).

More specifically, the above-mentioned production process enables to produce an olefin polymer with higher catalytic efficiency, for example, up to 10, using the composition of the present invention as a catalyst⁶g_{Polymer and method of making same}/mol_MetalH. The catalyst of the present invention can prepare high density polyethylene with higher molecular weight and higher linearity degree and ethylene-propylene elastomer with high molecular weight under lower pressure.

The present invention will be described in detail below by way of examples.

In the following examples:

the various starting materials used are all commercially available, unless otherwise specified.

The weight average molecular weight of the polymers described below was determined by Waters150 Gel Permeation Chromatography (GPC) and was determined at 135 ℃ with 1,2, 4-trichlorobenzene as the mobile phase.

Catalytic efficiency is the mass of polymer obtained per mole of Mt per unit time, in g_{Polymer and method of making same}/mol_MetalH represents.

¹H NMR spectrometer model Bruker Ascend 400M of Bruker corporation was used

The single crystal diffraction analysis was performed using a Bruker APEX II model X-ray single crystal diffractometer from Bruker.

Example 1

This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.

Preparation was carried out according to the above reaction formula, specifically:

(1) diluting diphenyl ether (0.02mol) in hexane (50mL), dropwise adding n-BuLi (42mmol) in hexane (after the addition within about 5 min) at-78 ℃, reacting for 1h, then raising the temperature to room temperature (about 25 ℃), and continuing to stir for reacting for 16 h;

(2) then, under the ice-water bath, 15mL of diphenyl phosphine chloride (42mmol) n-hexane solution is dripped into the reaction system in the step (1) (after the addition is completed within about 5 min), and then the stirring reaction is continued at room temperature (about 25 ℃) for 16 h; the solvent was removed by rotary evaporation to give a pale yellow viscous oil, which was washed with acetone and dried in vacuo to give 9.4g of a white powder, i.e., a compound represented by the formula (3-1): the yield thereof was found to be 87%,¹H NMR(400MHz,C₆D₆)δ:7.41-7.26(m,8H,o-PPh₂),7.08-6.93(m,14H,m-PPh₂,p-PPh₂,phenylate),6.91-6.87(t,J＝8Hz,2H,phenylate),6.72-6.66(m,4H,phenylate)ppm。

(3) the compound represented by the formula (3-1) (2mmol) was dissolved in 10mL of toluene, and then azide was added dropwise under magnetic stirringTrimethylsilane (6mmol) (added over about 3 min), then heated to 110 ℃ for 10h reflux; after the reaction was completed, the reaction mixture was rotary evaporated under reduced pressure and then dried by suction to obtain 1.38g of a white solid, i.e., a compound represented by the formula (2-1): the yield thereof was found to be 97%.¹H NMR(400MHz,C₆D₆)δ:8.22(ddd,J＝14.3,7.6,1.4Hz,2H,phenylate),7.57(ddd,J＝24.2,12.8,7.1Hz,8H,o-PPh₂),7.05–6.81(m,14H,m-PPh₂,p-PPh₂,phenylate),6.73(t,J＝7.5Hz,2H,phenylate),5.80(dd,J＝7.9,5.2Hz,2H,phenylate),0.31(s,18H,SiMe₃)ppm.

(4) The compound of formula (2-1) (1mmol) was dissolved in 10mL of toluene and 5mL of CpTiCl was added dropwise with magnetic stirring₃(2mmol) of a toluene solution, and then heating to 110 ℃ for refluxing for 12 h; after the reaction is finished, the solvent toluene is removed by reduced pressure rotary evaporation to obtain a light yellow crude product, the crude product is washed 3 times by using n-pentane, and the product is dried in vacuum to obtain 0.86g, namely the compound shown in the formula (1-Ti-1): the yield thereof was found to be 92%.¹H NMR(400MHz,CD₂Cl₂)δ:8.16(ddd,J＝14.5,7.4,1.8Hz,2H,phenylate),7.68–7.56(m,2H,phenylate),7.54–7.40(m,14H,m-PPh₂,p-PPh₂,phenylate),7.38(dd,J＝16.6,9.3Hz,2H,phenylate),7.28-7.15(m,8H,o-PPh₂),6.08(s,8H,cp),5.87(t,J＝6.9Hz,2H,phenylate)ppm.

Preparing a single crystal: dissolving the compound (about 0.1mmol) shown in the formula (1-Ti-1) obtained in the step (4) in 5mL of dichloromethane/toluene mixed solvent (volume ratio is 1: 1) under the protection of nitrogen, placing the mixture in a vacuum drier for slowly volatilizing solvent to obtain a corresponding compound single crystal shown in the formula (1-Ti-1), and analyzing through single crystal diffraction to confirm that the structure is shown in figure 1, the crystal system is a triclinic crystal system, the space group is P-1, and the unit cell parameters are:

α＝86.02°(3)，β＝89.96°(3)，γ＝61.44°(3)，Z＝2，ρ_calc＝1.4082g/cm³。

example 2

This example illustrates the early transition metal compounds of the present invention, their preparation and intermediates.

The method of embodiment 1, except that in step (4): the compound represented by the formula (2-1) (1mmol) was dissolved in 10mL of toluene, and 5mL of TiCl was added dropwise with magnetic stirring₄(2mmol) of a toluene solution, and then heating to 110 ℃ for refluxing for 12 h; after the reaction is finished, the solvent toluene is removed by reduced pressure rotary evaporation, the crude product is washed for 3 times by pentane, and the product is obtained by vacuum drying¹The compound represented by the formula (1-Ti-2) was identified by H NMR.

Example 3

This example illustrates the early transition metal compounds of the present invention, their preparation and intermediates.

The method of example 1, except that an equimolar amount of CpZrCl was used in step (4)₃In place of CpTiCl₃To give the corresponding product, via¹The compound represented by the formula (1-Zr-1) was identified by H NMR.

Example 4

This example illustrates the early transition metal compounds of the present invention, their preparation and intermediates.

The method of example 1, except that an equimolar amount of CpHfCl was used in step (4)₃In place of CpTiCl₃To give the corresponding product, via¹The compound represented by the formula (1-Hf-1) was identified by H NMR.

Example 5

This example illustrates the early transition metal compounds of the present invention, their preparation and intermediates.

The method of embodiment 1, except that the example further comprises:

(5) dissolving a compound (0.3mmol) shown in a formula (1-Ti-1) in 25mL of diethyl ether, dropwise adding 1.5mmol of MeMgBr in diethyl ether (0.5mL) under magnetic stirring (after the addition is finished within about 5 min), and then heating to 110 ℃ for refluxing for 15 h; after the reaction is finished, removing the solvent by rotary evaporation, washing the crude product with pentane, drying in vacuum to obtain a corresponding product, and purifying by vacuum distillation¹The compound represented by the formula (1-Ti-3) was identified by H NMR.

Example 6

This example illustrates the early transition metal compounds of the present invention, their preparation and intermediates.

The method of example 5, except that an equimolar amount of CpZrCl was used in step (4)₃In place of CpTiCl₃Thus obtaining the corresponding product after step (5) by¹The compound represented by the formula (1-Zr-3) was identified by H NMR.

Comparative example 1

Preparation was carried out according to the above reaction formula, specifically:

(1) to a stirred solution of diphenylphosphine (PHPh) in THF (100mL) at-78 deg.C₂) (0.02mol) was added n-BuLi (12.5mL of 1.6M n-hexane solution) to give a deep red solution, which was stirred at 25 ℃ for 8 h;

(2) then, 20mL of a THF solution of 2, 6-dibromopyridine (0.01mol) was added dropwise to the above solution, and the mixture was stirred for 8 hours, followed by removal of the solvent by vacuum suction to obtain a ligand represented by the formula (B1).

The yield is 78 percent;¹H NMR(400MHz,C₆D₆)δ:7.44(m,8H,o-PPh₂),7.02(m,12H,m-PPh₂,p-PPh₂),6.94(d,J＝8.4Hz,2H,py),6.73(m,1H,py)。

(3) reacting trimethyl azide silane N₃SiMe₃(0.02mol) was slowly added to a solution of the ligand represented by the formula (B1) (0.01mol) and 20mL of toluene, and the reaction mixture was heated under reflux for 12 h. When the vacuum is applied to remove the solvent and the excess TMSN₃Then, a white solid, i.e., the ligand represented by formula (B2), was obtained.

The yield is 86%;¹H NMR(400MHz,CDCl₃)δ:8.45-8.37(m,2H,py),8.05-7.97(m,1H,py),7.51–7.43(m,12H,m-PPh₂,p-PPh₂),7.27–7.22(m,8H,o-PPh₂),0.01(s,18H,-SiMe₃).

(4) dissolving the ligand (5mmol) shown in the formula (B2) in 10mL of toluene, stirring uniformly, adding 5mL of toluene solution containing cyclopentadienyl titanium trichloride (10mmol), heating to 110 ℃, reacting for 12h, cooling to 25 ℃, and removing the solvent to obtain the product, namely the compound shown in the formula (1B).

Polymerization example 1

This example illustrates the preparation of an ethylene homopolymer according to the invention.

2mL of MAO in toluene (purchased from Albemarle, the same shall apply hereinafter) was added to 200mL of toluene under nitrogen protection at 50 ℃ so that the Al content was 10mmol, and ethylene gas (volume flow rate: 50L/h) was continuously introduced while maintaining a gauge pressure of 0.1MPa, and then the compound represented by the formula (1-Ti-1) (0.02mmol) obtained in step (4) of example 1 was added and polymerization was carried out for 15min, and the supply of monomers was stopped. The reaction was terminated with isopropanol, the resulting polymer was freed of solvent and oven dried.

The results are shown in table 1.

Polymerization example 2

This example illustrates the preparation of an ethylene homopolymer according to the invention.

According to the method described in polymerization example 1, except that the compound represented by the formula (1-Ti-1) was used in an amount of 0.03mmol, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization examples 3 to 8

This example illustrates the preparation of an ethylene homopolymer according to the invention.

The process of polymerization example 1, except that:

polymerization example 3 in which the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 was replaced with an equimolar amount of single crystal of the compound represented by the formula (1-Ti-1) gave the corresponding polymer, and the results are shown in Table 1.

Polymerization example 4 in place of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, an equimolar amount of the compound represented by the formula (1-Ti-2) obtained in the step (4) of example 2 was used to obtain a corresponding polymer, and the results are shown in Table 1.

Polymerization example 5 in which the compound represented by the formula (1-Zr-1) obtained in the step (4) of example 3 was used in an equimolar amount instead of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization example 6 was conducted using an equimolar amount of the compound represented by the formula (1-Hf-1) obtained in the step (4) of example 4 in place of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1 to obtain a corresponding polymer, and the results are shown in Table 1.

Polymerization example 7 in which the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 was replaced with an equimolar amount of the compound represented by the formula (1-Ti-3) obtained in step (5) of example 5, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization example 8 in which the compound represented by the formula (1-Zr-3) obtained in the step (5) of example 6 was used in an equimolar amount instead of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization example 9

This example is intended to illustrate the preparation of the ethylene-propylene copolymer of the present invention.

2mL of MAO in toluene was added to 200mL of toluene under nitrogen protection at 50 ℃ so that the Al content was 10mmol, and an ethylene/propylene/hydrogen mixed gas (molar ratio 1: 2: 0.05, volume flow rate 50L/h) was continuously introduced while maintaining a gauge pressure of 0.5MPa, and then the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 (0.02mmol) was added and polymerization was carried out for 15min, and the supply of monomers was stopped. The reaction was terminated with isopropanol and an antioxidant lrganox 1520 (from BASF, same below; used in such an amount that the content of the antioxidant in the polymer was 0.2% by weight) was added. The resulting polymer was freed of the solvent and oven dried.

The results are shown in table 1.

Polymerization example 10

This example is intended to illustrate the preparation of the ethylene-propylene copolymer of the present invention.

According to the procedure as described in polymerization example 9, except that the compound represented by the formula (1-Zr-1) obtained in the step (4) of example 3 was used in an equimolar amount instead of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization example 11

This example is intended to illustrate the preparation of the ethylene-propylene copolymer of the present invention.

0.4mL of MAO in toluene was added to 200mL of toluene under nitrogen protection at 70 deg.C (so that the Al content was 2mmol), and an ethylene/propylene/hydrogen mixture (molar ratio 1: 2: 0.01, volume flow rate 50L/h) was continuously introduced while maintaining the gauge pressure at 0.5MPa, and [ CPh ] was added₃][B(C₆F₅)₄]A toluene solution of an organoboron compound (used in such an amount that the molar ratio B/Mt is 1/1) was added, and then a compound represented by the formula (1-Ti-3) (0.02mmol) was subjected to polymerization for 15min, and the supply of the monomer was stopped. The reaction was terminated with isopropanol and an antioxidant lrganox 1520 (from BASF, same below; used in such an amount that the content of the antioxidant in the polymer was 0.2% by weight) was added. The resulting polymer was freed of the solvent and oven dried.

The results are shown in table 1.

Polymerization example 12

This example is intended to illustrate the preparation of the ethylene-propylene copolymer of the present invention.

According to the procedure as described in polymerization example 11, except that the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 was replaced with an equimolar amount of the compound represented by the formula (1-Zr-3) obtained in step (5) of example 6, the corresponding polymer was obtained, and the results are shown in Table 1.

Polymerization comparative example 1

According to the method described in polymerization example 1, except that 0.04mmol of ZrCp are used₂Cl₂The complexes were substituted for the compound represented by the formula (1-Ti-1), and the remainder was the same as in polymerization example 1, to give corresponding polymers, the results of which are shown in Table 1.

Polymerization comparative example 2

According to the method described in polymerization example 11, except that 0.04mmol of ZrCp are used₂Me₂The complex was substituted for the compound represented by the formula (1-Ti-3), and the remainder was the same as in polymerization example 11, to obtain a corresponding polymer, the results of which are shown in Table 1.

Polymerization comparative example 3

According to the method described in polymerization example 1, except that this comparative example uses an equimolar amount of C₂H₄{Ph₂PNTiCl₂Cp*}₂The complexes were substituted for the compound represented by the formula (1-Ti-1), and the remainder was the same as in polymerization example 1, to give corresponding polymers, the results of which are shown in Table 1.

Comparative example 4 polymerization

The same procedure as in polymerization example 1 was conducted except that this comparative example used an equimolar amount of the compound represented by the formula (1B) obtained in comparative example 1 in place of the compound represented by the formula (1-Ti-1) to obtain the corresponding polymer, and the results are shown in Table 1.

TABLE 1

As can be seen from the data of Table 1, the olefin catalyzed by the early transition metal compound or the crystal thereof of the present invention has high catalytic activity as will be shown, and has excellent catalytic activity under a wide range of polymerization reaction conditions; in particular, the single crystal catalytic activity of the early transition metal compound of the present invention is higher.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (44)

1. An early transition metal compound, characterized in that the early transition metal compound is a compound represented by the formula (1):

formula (1)

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

R₃is-MtX_nor-Mt (X') X_n-1Wherein, in the step (A),

mt is a group IVB metal element;

2n or 2(n-1) X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of the element Mt; x' is a ligand of a metal element Mt and is selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene and substituted or unsubstituted fluorene, and a substituent on the substituted cyclopentadiene, the substituted indene and the substituted fluorene is C_1-6And halogen.

2. The early transition metal compound of claim 1, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-16A hydrocarbon group of_1-16Alkoxy and halogen of (a);

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from C_1-8Linear or branched alkyl, fluorine, chlorine, bromine and iodine.

3. The early transition metal compound of claim 2, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-10A hydrocarbon group of_1-10Alkoxy and halogen of；

R₁And R₂Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo and iodo.

4. The early transition metal compound of claim 3, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-6A hydrocarbon group of_1-6Alkoxy and halogen of (a);

R₁and R₂Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo.

5. The early transition metal compound according to any one of claims 1 to 4, wherein the early transition metal compound is one of compounds represented by the following formulae;

6. the intermediate of a transition metal compound according to any one of claims 1 to 5, wherein the intermediate of a transition metal compound is a compound represented by formula (2):

formula (2)

Each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20And the other substituents are as defined in any one of claims 1 to 5.

7. An intermediate according to claim 6, wherein each R is₄Each independently selected from C_1-16And C is a hydrocarbon group_1-16Alkoxy group of (2).

8. An intermediate according to claim 7, wherein each R is₄Each independently selected from C_1-10And C is a hydrocarbon group_1-10Alkoxy group of (2).

9. An intermediate according to claim 8, wherein each R is₄Each independently selected from C_1-6And C is a hydrocarbon group_1-6Alkoxy group of (2).

10. An intermediate according to claim 9, wherein each R is₄Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.

11. The crystal of an early transition metal compound according to any one of claims 1 to 5, wherein the crystal system of the crystal is a triclinic system.

12. A process for preparing an early transition metal compound according to any of claims 1 to 5, which comprises:

(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;

(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);

(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);

(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);

optionally, in the case that at least one X in the compound represented by formula (1) obtained in step (4) is a halogen, the method further comprises: 5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');

formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (a)

Formula (b)

Formula (c) R₃-X”，

Formula (d) R₅-MgX '", formula (d') R₅-Li，

Wherein R is¹、R²、R³And R⁴Each independently selected from H, C_1-20A hydrocarbon group of_1-20Alkoxy and halogen of (a);

R₁and R₂Each independently selected from H, C_1-4And substituted or unsubstituted C_6-12Aryl of (a), the substituted C_6-12The substituents on the aryl group of (A) are selected from C_1-4A hydrocarbon group of (a);

each R is₄Each independently selected from C_1-20And C is a hydrocarbon group_1-20Alkoxy group of (a);

R₃is-MtX_nor-Mt (X') X_n-1Wherein, in the step (A),

mt is a group IVB metal element;

2n or 2(n-1) X are each independently selected from C_1-10And halogen, and n ═ n '-1, n' is the valence of the element Mt; x' is a ligand of a metal element Mt and is selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene and substituted or unsubstituted fluorene, and a substituent on the substituted cyclopentadiene, the substituted indene and the substituted fluorene is C_1-6One or more of hydrocarbyl and halogen;

R₅is selected from C_1-10A hydrocarbon group of (a);

x "and X'" are each independently selected from halogen;

X₁and X₂Is H, X₃H, Cl or Br.

13. The method of claim 12, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-16A hydrocarbon group of_1-16Alkoxy and halogen of (a);

each R is₄Each independently selected from C_1-16And C is a hydrocarbon group_1-16Alkoxy group of (a);

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from C_1-8Linear or branched alkyl groups of (a), fluorine, chlorine, bromine and iodine;

R₅is selected from C_1-8A hydrocarbon group of (1).

14. According to the claimsThe method of claim 13, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-10A hydrocarbon group of_1-10Alkoxy and halogen of (a);

R₁and R₂Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

each R is₄Each independently selected from C_1-10And C is a hydrocarbon group_1-10Alkoxy group of (a);

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo;

R₅selected from methyl, ethyl, n-propyl or isopropyl.

15. The method of claim 14, wherein R¹、R²、R³And R⁴Each independently selected from H, C_1-6A hydrocarbon group of_1-6Alkoxy and halogen of (a);

R₁and R₂Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;

each R is₄Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy;

mt is Ti, Zr or Hf;

2n or 2(n-1) X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo;

R₅is selected from methylOr an ethyl group;

x "and X'" are each independently selected from the group consisting of fluorine, chlorine, bromine, and iodine.

16. The process of any one of claims 12-15, wherein the organolithium reagent is of formula R₆-one or more of the compounds represented by Li, wherein R₆Is C1-C8 alkyl.

17. The process of claim 16, wherein the organolithium reagent is one or more of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.

18. The method of claim 16, wherein the compound of formula (4) and the organolithium reagent are used in a molar ratio of 1: 1.8-3.

19. The method of claim 18, wherein the compound of formula (4) and the organolithium reagent are used in a molar ratio of 1: 2-2.5.

20. The process according to any one of claims 12 to 15, wherein the compound of formula (4) and the compound of formula (a) are used in a molar ratio of 1: 1.8-3.

21. The method according to claim 20, wherein the compound of formula (4) and the compound of formula (a) are used in a molar ratio of 1: 2-2.5.

22. The method according to claim 20, wherein the molar ratio of the compound represented by formula (3) to the azidosilane compound represented by formula (b) is 1: 1.8-5.

23. The method according to claim 22, wherein the molar ratio of the compound represented by formula (3) to the azidosilane compound represented by formula (b) is 1: 2-4.

24. The method according to claim 20, wherein the compound of formula (2) and the compound of formula (c) are used in a molar ratio of 1: 1.8-4.

25. The method according to claim 24, wherein the compound of formula (2) and the compound of formula (c) are used in a molar ratio of 1: 2-3.

26. The method of any one of claims 12-15, wherein the conditions of the first substitution reaction comprise: the reaction is carried out for 0.5 to 2 hours at the temperature of between 90 ℃ below zero and 50 ℃ below zero, and then for 10 to 24 hours at the temperature of between 10 and 40 ℃.

27. The method of claim 26, wherein the conditions of the second substitution reaction comprise: the temperature is 10-40 ℃ and the time is 10-24 h.

28. The method of claim 26, wherein the conditions of the staudinger reaction comprise: the temperature is 80-150 ℃ and the time is 5-20 h.

29. The method of claim 26, wherein the conditions of the third substitution reaction comprise: the temperature is 80-150 ℃ and the time is 8-20 h.

30. The method according to any one of claims 12 to 15, wherein the compound represented by formula (1) and the grignard reagent or the alkyllithium are used in a molar ratio of 1: 1.8-8.

31. The method according to claim 30, wherein the compound represented by formula (1) and the grignard reagent or alkyl lithium are used in a molar ratio of 1: 2-6.

32. The method of claim 30, wherein the conditions of the fourth substitution reaction comprise: the temperature is 80-150 ℃ and the time is 8-20 h.

33. An early transition metal compound produced by the process of any one of claims 12 to 32.

34. Use of the early transition metal compound according to any one of claims 1 to 5 and 33 or the crystal of the early transition metal compound according to claim 11 for catalyzing ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.

35. A catalyst composition for the polymerisation of olefins comprising a procatalyst which is an early transition metal compound according to any one of claims 1 to 5 and 33 or a crystal of an early transition metal compound according to claim 11 and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound.

36. The composition according to claim 35, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 50-3000 parts of;

in the case where the activator is an aluminum-containing compound and an organoboron compound, the composition contains the main catalyst in terms of metal element Mt, the aluminum-containing compound in terms of aluminum element, and the organoboron compound in terms of boron element in a molar ratio of 1: 0.1-500: 0.5-5.

37. The composition of claim 36, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 100-;

in the case where the activator is an aluminum-containing compound and an organoboron compound, the composition contains the main catalyst in terms of metal element Mt, the aluminum-containing compound in terms of aluminum element, and the organoboron compound in terms of boron element in a molar ratio of 1: 0.2-100: 1-3.

38. The composition according to claim 37, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 100-500.

39. The composition of any of claims 35-38, wherein the aluminum-containing compound is a mixture of an alkylaluminum compound and an alkylaluminoxane compound or an alkylaluminoxane compound.

40. The composition according to claim 39, wherein the alkylaluminoxane compound is methylaluminoxane and/or isobutylaluminoxane and the alkylaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.

41. A composition as claimed in claim 39 wherein the organoboron compound is selected from one or more of tris (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylcarbonium tetrakis (pentafluorophenyl) borate.

42. Use of a composition according to any one of claims 35 to 41 for catalysing ethylene homopolymerisation and/or ethylene-alpha olefin copolymerisation.

43. A process for producing an olefin polymer, the process comprising: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;

wherein the catalyst is the composition of any one of claims 35-41.

44. The method of claim 43, wherein the polymerization conditions comprise: the temperature is-50 ℃ to 200 ℃, and the pressure is 0.1MPa to 5 MPa.

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