Olefin polymerization reaction catalyst component, olefin prepolymerization reaction or polymerization reaction catalyst, and olefin prepolymerization reaction or polymerization reaction method

Abstract

The invention relates to an olefin polymerization reaction catalyst component, an olefin prepolymerization reaction or polymerization reaction catalyst and an olefin prepolymerization reaction or polymerization reaction method, and belongs to the field of olefin polymerization catalysts. The solid catalyst component for olefin polymerization comprises magnesium, titanium, halogen and internal electron donor compounds, wherein the internal electron donor compounds comprise a first internal electron donor compound as shown in a formula (I) and a second internal electron donor compound as shown in a formula (II). When the catalyst containing the solid catalyst component provided by the invention is used for olefin polymerization reaction, the polymerization activity is excellent, and the obtained polymer is higher in melt index, wider in molecular weight distribution and higher in isotactic index.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization catalysts, specifically relating to olefin polymerization reaction catalyst components, olefin prepolymerization reaction or polymerization reaction catalysts, and olefin prepolymerization reaction or polymerization reaction methods. Background Technology

[0002] Ziegler-Natta catalysts, based on magnesium, titanium, halogens, and internal electron donors, are widely used in the industrial production of polypropylene. For polypropylene Ziegler-Natta catalysts, internal electron donor compounds are essential components. The type and content of internal electron donors play a crucial role in regulating catalyst activity, orientation ability, kinetic behavior, hydrogen sensitivity, molecular weight distribution, and copolymerization performance. To date, the research and development of novel internal electron donor compounds has been a key focus in the development of polypropylene catalysts, and advancements in internal electron donor technology can drive the continuous upgrading of polypropylene catalysts. With the development of Ziegler-Natta catalysts, numerous internal electron donor compounds have been synthesized and reported. For example, patent document CN85100997A uses di-n-butyl phthalate or diisobutyl phthalate as internal electron donor compounds; patent document CN1453298A uses glycol ester compounds; patent document CN1313869A uses succinate compounds; and patent document CN1015062B uses diether compounds as internal electron donors. However, catalysts prepared using reported internal electron donor compounds have some drawbacks. For example, when glycol esters are used as internal electron donors in Ziegler-Natta catalysts, the resulting polymers have a low melt index, which is not conducive to the processing and application of the polymers.

[0003] Therefore, the current problem is the need to research and develop Ziegler-Natta catalysts that can overcome the shortcomings of existing technologies. Summary of the Invention

[0004] To address the problems existing in the prior art, the inventors discovered through extensive experiments that a polymer compound with a specific structure as shown in formula (I) and a glycol ester compound, used as an internal electron donor, can be applied to the preparation of Ziegler-Natta catalyst components to obtain a catalyst with excellent overall performance. When this catalyst is used for propylene polymerization, it exhibits high polymerization activity, a high melt index, and a wide molecular weight distribution in the resulting polymer.

[0005] According to a first aspect of the present invention, the present invention provides an olefin polymerization catalyst component comprising magnesium, titanium and an internal electron donor, the internal electron donor comprising a first internal electron donor compound represented by formula (I) and a second internal electron donor compound represented by formula (II);

[0006]

[0007] In equation (I), 3 ≤ n ≤ 1000;

[0008] R1, R2, and R3 can be optionally keyed together to form a ring;

[0009] R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen and C. 1- C 12 Straight-chain or branched alkyl groups I, C3-C 12 Cyclic hydrocarbon group I, C2-C 12 Alkenyl I, C2-C 12 alkynyl group I, C6-C 20 Aryl I, C7-C 20 Hydrocarbon aryl I, C7-C 20 Aromatic group I, C6-C 20 heteroaryl I, C4-C 20 Heterocyclic group I, halogen atom;

[0010] The C 1- C 12 Straight-chain or branched alkyl groups I, C3-C 12 Cyclic hydrocarbon group I, C2-C 12 Alkenyl I, C2-C 12 alkynyl group I, C6-C 20 Aryl I, C7-C 20 Hydrocarbon aryl I, C7-C 20 Aromatic group I, C6-C 20 heteroaryl I, C4-C 20 The hydrogen atom on heterocyclic group I may optionally be replaced by one or more substituents X1;

[0011] R4 is one of the structures shown in equations (III), (IV), and (V):

[0012]

[0013] R5, R6, and R7 may be the same or different, and each is independently selected from hydrogen and C. 1- C 12 Straight-chain or branched alkyl II, C3-C 12 Cyclic hydrocarbon group II, C2-C 12 Alkenyl II, C2-C 12 Alkyne II, C6-C20 Aryl II, C7-C 20 Hydrocarbon aryl II, C7-C 20 Aromatic group II, C6-C 20 heteroaryl II, C4-C 20 Heterocyclic group II, halogen atom;

[0014] The C 1- C 12 Straight-chain or branched alkyl II, C3-C 12 Cyclic hydrocarbon group II, C2-C 12 Alkenyl II, C2-C 12 Alkyne II, C6-C 20 Aryl II, C7-C 20 Hydrocarbon aryl II, C7-C 20 Aromatic group II, C6-C 20 heteroaryl II, C4-C 20 The hydrogen atom on heterocyclic group II may optionally be replaced by one or more substituents X2;

[0015] The substituents X1 and X2 are independently selected from C1-C6 straight-chain or branched alkyl groups (e.g., methyl, ethyl n-propyl, or isopropyl), C3-C... 10 Cycloalkyl (e.g., cyclopentyl or cyclohexyl), hydroxyl, amino, C1-C6 alkoxy (e.g., methoxy, ethoxy, n-propoxy or isopropoxy), C1-C6 alkyl-substituted amino (e.g., -NHCH3 or -N(CH3)2), halogen atom (e.g., fluorine atom, chlorine atom, bromine atom or iodine atom), cyano;

[0016] In formula (II),

[0017] R8 and R9 can be optionally bonded into a ring, that is, R8 and R9 can be either not cyclic or connected to each other to form a ring. R8 and R9 may be the same or different, and each can be independently selected from hydrogen, halogen, or C1-C. 10 Alkyl I, C3-C 10 Cycloalkyl I, C6-C 10 Aryl I, C7-C 10 aryl hydrocarbons (I or C7-C) 10 Aromatic group I;

[0018] R 10 and R 11 Whether they are the same or different, they are each independently selected from halogens, C1-C. 10 Alkyl II, C3-C 10 Cycloalkyl II, C6-C 10 aryl II, C7-C 10 Hydrocarbon aryl II or C7-C 10 Aromatic group II; the C1-C10 Alkyl II, C3-C 10 Cycloalkyl II, C6-C 10 Aryl II, C7-C 10 Hydrocarbon aryl II or C7-C 10 The hydrogen atom on the aryl group II may optionally be replaced by an alkyl group or a halogen;

[0019] R 12 and R 13 Whether they are the same or different, they are each independently selected from C3-C. 20 cycloalkyl, C6-C 20 Aryl III, C7-C 20 aryl hydrocarbons (III or C7-C) 20 Aromatic group III; the C3-C 20 cycloalkyl, C6-C 20 Aryl III, C7-C 20 aryl hydrocarbons (III or C7-C) 20 The hydrogen atom on the aryl group III can optionally be replaced by an alkyl group or a halogen, and R 12 and R 13 Cannot be C3-C at the same time 20 Cycloalkyl.

[0020] In this invention, the term "cycloalkyl" refers to cycloalkyl, cycloalkenyl, or cycloynyl, and also includes cycloalkyl groups linked by alkyl groups, such as methylcyclohexyl.

[0021] The "hydroaryl" in this invention refers to alkylaryl, olefinic, or alkynylaryl.

[0022] The "aromatic group" mentioned in this invention is an aralkyl group, an arene group, or an arynyl group.

[0023] The "heteroaryl" described in this invention refers to an aryl group containing heteroatoms. Preferably, the heteroaryl group contains 1-3 heteroatoms; preferably, the heteroatoms are selected from at least one of N, O, and S; preferably, the heteroaryl group has a five-, six-, or seven-membered skeleton. Specifically, heteroaryl groups include, but are not limited to: pyridyl, pyrimidinyl, pyrazinyl, furanyl, and thiopheneyl.

[0024] The "heterocyclic group" described in this invention is a cycloalkyl group containing heteroatoms. Preferably, the heterocyclic group contains 1-3 heteroatoms; preferably, the heteroatoms are selected from at least one of N, O, and S; preferably, the heteroaryl group has a ternary, quaternary, pentaneary, hexanal, or heptaneary skeleton. Specifically, the heterocyclic group includes, but is not limited to: ethylene oxide, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl.

[0025] In a preferred embodiment, 3 ≤ n ≤ 100; more preferably 4 ≤ n ≤ 20.

[0026] In a preferred embodiment, R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen, C1-C8 straight-chain or branched alkyl groups, and C5-C6... 10 Cycloalkyl group I, C2-C8 alkenyl group I, C2-C8 alkynyl group I, C6-C 14 Aryl I, C7-C 15 Hydrocarbon aryl I, C7-C 15 Aromatic group I, C6-C 15 heteroaryl I, C4-C 15 Heterocyclic group I, halogen atom I; the C1-C8 straight-chain or branched alkyl group I, C5-C 10 Cycloalkyl group I, C2-C8 alkenyl group I, C2-C8 alkynyl group I, C6-C 14 Aryl I, C7-C 15 Hydrocarbon aryl I, C7-C 15 Aromatic group I, C6-C 15 heteroaryl I, C4-C 15 The hydrogen atom on heterocyclic group I may optionally be replaced by one or more substituents X1;

[0027] Preferably, R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen, C1-C4 straight-chain or branched alkyl groups, C5-C8 cyclic hydrocarbon groups, C6-C9 aryl groups, and C7-C4 alkyl groups. 10 Hydrocarbon aryl I, C7-C 10 Aromatic group I, halogen atom; the C1-C4 straight-chain or branched alkyl group I, C5-C8 cyclic hydrocarbon group I, C6-C9 aryl group I, C7-C 10 Hydrocarbon aryl I, C7-C 10 The hydrogen atom on the aromatic group I may optionally be replaced by one or more substituents X1.

[0028] In a preferred embodiment, R5, R6, and R7 may be the same or different, and each may be independently selected from hydrogen, C1-C8 straight-chain or branched alkyl groups, C4-C6... 10 Cyclic hydrocarbon group I, C2-C8 alkenyl group II, C2-C8 alkynyl group II, C6-C 14 Aryl II, C7-C 15 Hydrocarbon aryl II, C7-C 15 Aromatic group II; the C1-C8 straight-chain or branched alkyl group II, C4-C 10 Cycloalkyl II, C2-C8 alkenyl II, C2-C8 alkynyl II, C6-C 14 Aryl II, C7-C 15 Hydrocarbon aryl II, C7-C 15The hydrogen atom on the aryl group II may optionally be replaced by one or more substituents X2; preferably, R5, R6, and R7 may be the same or different, and each is independently selected from hydrogen, C1-C4 straight-chain or branched alkyl II, C5-C8 cycloalkyl II, C6-C 10 Aryl III, C7-C 12 Hydrocarbon aryl I, C7-C 12 Aromatic group I; C1-C4 straight-chain or branched alkyl group II, C5-C8 cyclic alkyl group II, C6-C 10 Aryl III, C7-C 12 Hydrocarbon aryl I, C7-C 12 The hydrogen atom on the aromatic group I can optionally be replaced by one or more substituents X2.

[0029] In a preferred embodiment, R8 and R9 may be the same or different, and each is independently selected from hydrogen, C1-C8 alkyl groups or halogens; preferably, R8 and R9 are each selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, chlorine atom or bromine atom.

[0030] As a preferred embodiment, R 10 and R 11 Whether they are the same or different, they are each independently selected from C1 to C2. 10 The alkyl group, wherein the hydrogen atom on the alkyl group is optionally substituted with a halogen; more preferably, R 10 and R 11 They may be the same or different, and each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0031] As a preferred embodiment, R 12 and R 13 Whether they are the same or different, each is independently selected from C6-C. 20 Aryl IV, C7-C 20 Aromatic group IV or C7-C 20 Hydrocarbon aryl IV; the C6-C 20 Aryl IV, C7-C 20 Aromatic group IV or C7-C 20 The hydrogen atom on the aryl group IV is optionally replaced by an alkyl group or a halogen; preferably, R 12 and R 13 Each is independently selected from C6-C 15 Aryl or C7-C 20 Aryl group.

[0032] Specifically, the first internal electron donor compound represented by formula (I) may be selected from, but is not limited to, the following compounds: poly(benzoyl glycidyl ester), poly(2-methylbenzoyl glycidyl ester), poly(3-methylbenzoyl glycidyl ester), poly(4-methylbenzoyl glycidyl ester), poly(2-ethylbenzoyl glycidyl ester), poly(3-ethylbenzoyl glycidyl ester), poly(4-ethylbenzoyl glycidyl ester), poly(2-n-propylbenzoyl glycidyl ester), poly(3-n-propylbenzoyl glycidyl ester), poly(4-n-propylbenzoyl glycidyl ester), poly(2-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(4-iso ...3-isopropylbenzoyl glycidyl ester), poly(4-isopropylbenzoyl glycidyl ester), poly(2-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl glycidyl ester), poly(3-isopropylbenzoyl g Benzoyl glycidyl ester), poly(2-n-butylbenzoyl glycidyl ester), poly(3-n-butylbenzoyl glycidyl ester), poly(4-n-butylbenzoyl glycidyl ester), poly(2-tert-butylbenzoyl glycidyl ester), poly(3-tert-butylbenzoyl glycidyl ester), poly(4-tert-butylbenzoyl glycidyl ester), poly(2-fluorobenzoyl glycidyl ester), poly(3-fluorobenzoyl glycidyl ester), poly(4-fluorobenzoyl glycidyl ester), poly(2-chlorobenzoyl glycidyl ester), poly(3-chlorobenzoyl glycidyl ester), poly(4-chlorobenzoyl glycidyl ester), poly(2-bromobenzoyl glycidyl ester), poly(3-bromobenzoyl glycidyl ester), poly(4- 1-Bromobenzoyl glycidyl ester, poly(2-iodobenzoyl glycidyl ester), poly(3-iodobenzoyl glycidyl ester), poly(4-iodobenzoyl glycidyl ester), poly(2-oxymethylbenzoyl glycidyl ester), poly(3-oxymethylbenzoyl glycidyl ester), poly(4-oxymethylbenzoyl glycidyl ester), poly(methyl benzoate), poly(2-methylbenzoate), poly(3-methylbenzoate), poly(4-methylbenzoate), poly(2-ethylbenzoate), poly(3-ethylbenzoate), poly(4-ethylbenzoate), poly(2-propylbenzoate) Glycol oxide ester), poly(3-n-propylbenzoic acid methyl glycol oxide ester), poly(4-n-propylbenzoic acid methyl glycol oxide ester), poly(2-isopropylbenzoic acid methyl glycol oxide ester), poly(3-isopropylbenzoic acid methyl glycol oxide ester), poly(4-isopropylbenzoic acid methyl glycol oxide ester), poly(2-n-butylbenzoic acid methyl glycol oxide ester), poly(3-n-butylbenzoic acid methyl glycol oxide ester), poly(4-n-butylbenzoic acid methyl glycol oxide ester), poly(2-tert-butylbenzoic acid methyl glycol oxide ester), poly(3-tert-butylbenzoic acid methyl glycol oxide ester), poly(4-tert-butylbenzoic acid methyl glycol oxide ester), poly(2-fluorobenzoic acid methyl glycol oxide ester), poly(3-fluorobenzoic acid methyl glycol oxide ester).Poly(4-fluorobenzoic acid methyl glycidol), poly(2-chlorobenzoic acid methyl glycidol), poly(3-chlorobenzoic acid methyl glycidol), poly(4-chlorobenzoic acid methyl glycidol), poly(2-bromobenzoic acid methyl glycidol), poly(3-bromobenzoic acid methyl glycidol), poly(4-bromobenzoic acid methyl glycidol), poly(2-iodobenzoic acid methyl glycidol), poly(3-iodobenzoic acid methyl glycidol), poly(4-iodobenzoic acid methyl glycidol), poly(2-oxomethylbenzoic acid methyl glycidol), poly(3-oxomethylbenzoic acid methyl glycidol), poly(4-oxomethylbenzoic acid methyl glycidol), poly(formyl glycidol), poly(acetyl glycidol). Poly(n-propionyl glycidyl ester), poly(isopropionyl glycidyl ester), poly(n-butyryl glycidyl ester), poly(isobutyryl glycidyl ester), poly(tert-butyryl glycidyl ester), poly(glycidyl methacrylate), poly(phenyl glycidyl ether), poly(2-methylphenyl glycidyl ether), poly(3-methylphenyl glycidyl ether), poly(4-methylphenyl glycidyl ether), poly(2-ethylphenyl glycidyl ether), poly(3-ethylphenyl glycidyl ether), poly(4-ethylphenyl glycidyl ether), poly(2-n-propylphenyl glycidyl ether), poly(3-n-propylphenyl glycidyl ether), poly(4-n-propylphenyl glycidyl ether), poly(2-isopropylphenyl glycidyl ether), poly(3- Isopropylphenyl glycidyl ether), poly(4-isopropylphenyl glycidyl ether), poly(2-n-butylphenyl glycidyl ether), poly(3-n-butylphenyl glycidyl ether), poly(4-n-butylphenyl glycidyl ether), poly(2-tert-butylphenyl glycidyl ether), poly(3-tert-butylphenyl glycidyl ether), poly(4-tert-butylphenyl glycidyl ether), poly(2-fluorophenyl glycidyl ether), poly(3-fluorophenyl glycidyl ether), poly(4-fluorophenyl glycidyl ether), poly(2-chlorophenyl glycidyl ether), poly(3-chlorophenyl glycidyl ether), poly(4-chlorophenyl glycidyl ether), poly(2-bromophenyl glycidyl ether), poly(3-bromophenyl glycidyl ether), poly(4-bromophenyl glycidyl ether) Poly(2-iodophenyl glycidyl ether), poly(3-iodophenyl glycidyl ether), poly(4-iodophenyl glycidyl ether), poly(2-oxymethylphenyl glycidyl ether), poly(3-oxymethylphenyl glycidyl ether), poly(4-oxymethylphenyl glycidyl ether), poly(benzyl glycidyl ether), poly(methylbenzyl glycidyl ether), poly(ethylbenzyl glycidyl ether), poly(propylbenzyl glycidyl ether), poly(butylbenzyl glycidyl ether), poly(fluorobenzyl glycidyl ether), poly(chlorobenzyl glycidyl ether), poly(bromobenzyl glycidyl ether), poly(iodobenzyl glycidyl ether), poly(naphthyl glycidyl ether), poly(anthrayl glycidyl ether), poly(phenanthrene glycidyl ether), poly(pyrene glycidyl ether).Poly(peryl glycidyl ether), poly(fluorenyl glycidyl ether), poly(2-pyridine glycidyl ether), poly(2-furan glycidyl ether), poly(2-thiophene glycidyl ether), poly(2-tetrahydrofuran glycidyl ether), poly(2-tetrahydropyran glycidyl ether), poly(3-pyridine glycidyl ether), poly(3-furan glycidyl ether), poly(3-thiophene glycidyl ether), poly(3-tetrahydrofuran glycidyl ether), poly(3-tetrahydropyran glycidyl ether), poly(4-tetrahydropyran The following are some of the following: glycidyl ether, poly(3-(2,2,3,3-tetrafluoropropoxy)-1,2-propene oxide), poly(2-phenylethylene oxide-1-carboxylic acid methyl ester), poly(2-phenylethylene oxide-1-carboxylic acid ethyl ester), poly(2-phenylethylene oxide-1-carboxylic acid propyl ester), poly(2-phenylethylene oxide-1-carboxylic acid butyl ester), poly(2-phenylethylene oxide-1-carboxylic acid phenol ester), poly(2-phenylethylene oxide-1-carboxylic acid benzyl alcohol ester), and poly(myricetin).

[0033] Specifically, the second internal electron-donating compound shown in formula (II) is selected from, but not limited to, the following compounds: 2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-methylbenzoate, 2,4-pentanediol di-m-methylbenzoate, 2,4-pentanediol di-o-methylbenzoate, 2,4-pentanediol di-p-ethylbenzoate, 2,4-pentanediol di-p-propylbenzoate, 2,4-pentanediol di-p-n-butylbenzoate, 2,4-pentanediol di-p-tert-butylbenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3- Ethyl-2,4-pentanediol dibenzoate, 3-propyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol di-p-methylbenzoate, 3-ethyl-2,4-pentanediol di-p-ethylbenzoate, 3-ethyl-2,4-pentanediol di-p-propylbenzoate, 3-ethyl-2,4-pentanediol di-p-butylbenzoate, 3-ethyl-2,4-pentanediol di-p-tert-butylbenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 3-chloro -2,4-Pentanediol dibenzoate, 3-bromo-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-p-ethylbenzoate, 3,5-heptanediol di-p-propylbenzoate, 3,5-heptanediol di-p-butylbenzoate, 3,5-heptanediol di-p-tert-butylbenzoate, 4-methyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4 One or more of the following: 4-ethyl-3,5-heptanediol di-p-methylbenzoate, 4-ethyl-3,5-heptanediol di-p-ethylbenzoate, 4-ethyl-3,5-heptanediol di-p-propylbenzoate, 4-ethyl-3,5-heptanediol di-p-butylbenzoate, 4-ethyl-3,5-heptanediol di-p-tert-butylbenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 4-chloro-3,5-heptanediol dibenzoate, and 4-bromo-3,5-heptanediol dibenzoate.

[0034] In a preferred embodiment, the magnesium element is derived from at least one of magnesium compounds such as magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide alcohol, and derivatives in which the halogen atom in magnesium dihalide is replaced by an alkoxy or haloalkoxy group; preferably magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium dichloride alcohol, magnesium dibromide alcohol, or magnesium diiodide alcohol.

[0035] In a specific embodiment of the present invention, the magnesium element is in the form of a magnesium compound. In particular, the magnesium compound is at least one of the magnesium compound of formula (VI), the hydrate of the magnesium compound of formula (VII), and the alcohol adduct of the magnesium compound of formula (VIII).

[0036] The magnesium compound represented by formula (VI):

[0037] MgR a R b Formula (VI)

[0038] Among them, R a and R b Whether the substances are the same or different, each independently is at least one of halogen, straight-chain alkoxy with 1 to 5 carbon atoms, branched-chain alkoxy with 3 to 5 carbon atoms, straight-chain alkyl with 1 to 5 carbon atoms, and branched-chain alkyl with 3 to 5 carbon atoms.

[0039] The hydrate of the magnesium compound represented by formula (VII):

[0040] MgR c R d ·eH2O formula (VII)

[0041] Among them, R c and R d Whether the substances are the same or different, each is independently at least one of halogen, straight-chain alkoxy with 1 to 5 carbon atoms, branched-chain alkoxy with 3 to 5 carbon atoms, straight-chain alkyl with 1 to 5 carbon atoms, and branched-chain alkyl with 3 to 5 carbon atoms; e is 0.1 to 6.

[0042] The alcohol adduct of the magnesium compound represented by formula (VIII):

[0043] MgR f R g ·hR j OH formula (VIII)

[0044] Among them, R f and R g Whether identical or different, each independently comprises at least one of halogen, a straight-chain alkoxy group having 1 to 5 carbon atoms, a branched-chain alkoxy group having 3 to 5 carbon atoms, a straight-chain alkyl group having 1 to 5 carbon atoms, and a branched-chain alkyl group having 3 to 5 carbon atoms; R j It is a hydrocarbon group with 1 to 18 carbon atoms; h is 0.1 to 6, preferably 2 to 3.5.

[0045] According to some embodiments of the present invention, the magnesium compound can be dissolved in a solvent system containing an organic epoxy compound and an organophosphorus compound, or in a 1,3-diol ester compound.

[0046] According to some embodiments of the present invention, the organic epoxy compound includes one or more of the following: aliphatic olefins, dienes, or oxides of halogenated aliphatic olefins or dienes, glycidyl ethers, and internal ethers, having 2 to 8 carbon atoms. Specific examples include, but are not limited to, one or more of the following: ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

[0047] According to some embodiments of the present invention, the organophosphorus compound is a hydrocarbon ester or halohydrocarbon ester of phosphoric acid or phosphorous acid, and the specific compound is selected from trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl phosphite, etc.

[0048] In a preferred embodiment, the titanium element is derived from the general formula compound TiX. m (OR 1 ) 4-m At least one of them, R 1 For C1-C 20 The hydrocarbon group, where X is a halogen, 1 ≤ m ≤ 4; according to some embodiments of the present invention, R 1 For C1-C 20 Alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C6 alkyl; preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy, and most preferably titanium tetrachloride.

[0049] In a preferred embodiment, the molar ratio of magnesium, titanium and the internal electron donor in the composition is 1:(0.5-150):(0.02-0.4); the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100):(100-1); more preferably (1-50):(50-1), and even more preferably (1-20):(20-1).

[0050] In a preferred embodiment, the catalyst component of the olefin polymerization reaction further contains halogen; the molar ratio of magnesium, titanium, halogen and the internal electron donor in the component is 1:(0.5-150):(0.1-800):(0.02-0.4).

[0051] According to a second aspect of the invention, the invention also provides an olefin prepolymerization or polymerization catalyst, said catalyst containing a product prepared from component materials; said component materials include component a and component b;

[0052] Component a is the catalyst component described in the first aspect of this invention;

[0053] Component b is an organoaluminum compound, preferably an alkylaluminum compound.

[0054] According to some embodiments of the present invention, the organoaluminum compound is an alkylaluminum compound, and the alkylaluminum compound has the general formula AlR 2 j X 3-j Compounds, where R 2 The group consists of hydrogen atoms and a hydrocarbon group with 1 to 20 carbon atoms, where X is a halogen and j is a number between 1 and 3. Specifically, it can be selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and dichloroethylaluminum, with triethylaluminum and triisobutylaluminum being preferred.

[0055] According to the catalyst of the present invention, the amount of the organoaluminum compound can be a conventional amount in the art. Preferably, the alkylaluminum compound is based on aluminum, the catalyst component is based on titanium, and the molar ratio of the alkylaluminum compound to the catalyst component is (5-5000):1, preferably (20-1000):1, more preferably (25-100):1.

[0056] As a preferred technical solution, the component material further includes component c, which is an external electron donor compound, and the external electron donor compound includes compounds with the general formula R. 3 k Si(OR 4 ) 4-k One or more organosilicon compounds; wherein 0 ≤ k ≤ 3; R 3 Selected from C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 Cycloalkyl, aryl, haloalkyl, amino, halogen, or hydrogen atom; R 4 Selected from C1-C 10 Straight-chain or branched alkyl groups, C3-C 10Cycloalkyl, aryl, haloalkyl, or amino groups; specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, benzene The silane is selected from one or more of the following: dipropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyl tert-butyldimethoxysilane. Preferably, it is selected from one or more of the following: dipropyltrimethoxysilane, n-butyltrimethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, and dicyclopentyldimethoxysilane. More preferably, it is selected from cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, or dicyclopentyldimethoxysilane.

[0057] As a preferred technical solution, in the catalyst, the molar ratio of titanium to silicon in the external electron donor compound is 1:(0.1-500), preferably 1:(25-100).

[0058] As a preferred technical solution, the type and content of the external electron donor compound are not particularly limited. Preferably, the molar ratio of the alkylaluminum compound (calculated as aluminum) to the external electron donor compound is (0.1–500):1, more preferably (1–300):1, and even more preferably (3–100):1.

[0059] From the perspective of improving the stereoregularity of olefin polymers, preferably, the molar ratio of the catalyst component, alkylaluminum compound and external electron donor compound described in the first aspect is 1:(25-100):(1-100) based on titanium:aluminum:silicon.

[0060] In a third aspect, the present invention provides the use of the catalyst component according to the first aspect and / or the catalyst according to the second aspect in an olefin polymerization reaction, wherein an olefin-containing feedstock is contacted with the catalyst to undergo a prepolymerization reaction, said catalyst comprising the catalyst component as described in the first aspect of the present invention and / or the catalyst as described in the second aspect of the present invention.

[0061] In this invention, the term "prepolymerization" refers to polymerization at a lower degree of conversion.

[0062] The prepolymerization ratio of the prepolymer is 0.1 to 1000 g olefin polymer / g solid catalyst component.

[0063] According to some embodiments of the present invention, the catalyst components and / or catalyst of the present invention can be directly added to the reactor for the polymerization process. Alternatively, the catalyst components and / or catalyst of the present invention may participate in prepolymerization before being added to the reactor, i.e., prepolymerize with olefins to obtain a prepolymerized catalyst before adding it to the reactor.

[0064] According to the present invention, the prepolymerization catalyst comprises the above-mentioned solid catalyst component and the prepolymer obtained by prepolymerization with olefin, wherein the prepolymerization ratio is 0.1 to 1000 g olefin polymer / g solid catalyst component.

[0065] The same α-olefin as the aforementioned olefin can be used for prepolymerization, wherein the olefin used for prepolymerization is preferably ethylene or propylene. Specifically, it is particularly preferred to use a mixture of ethylene or propylene and one or more α-olefins in an amount of up to 20 mol% for prepolymerization. Preferably, the conversion degree of the catalyst component in the prepolymerization is about 0.2 to 800 g polymer / g solid catalyst component.

[0066] The prepolymerization process can be carried out in a liquid or gas phase at a temperature of -40 to 80°C, preferably -20 to 50°C. The prepolymerization step can be performed online as part of a continuous polymerization process or independently in a batch operation. For preparing polymers with a solid catalyst component in an amount of 0.5 to 20 g / g, batch prepolymerization of the catalyst of the present invention with propylene is particularly preferred. The polymerization pressure is 0.01 to 10 MPa.

[0067] In a fourth aspect, the present invention provides an olefin polymerization method in which an olefin-containing feedstock is contacted with a catalyst to undergo a polymerization reaction, wherein the catalyst comprises the catalyst component as described in the first aspect of the present invention and / or the catalyst as described in the second aspect of the present invention and / or the prepolymer product obtained from the prepolymerization reaction as described in the third aspect of the present invention.

[0068] The olefin has the general formula CH2=CHR, where R is hydrogen or C1~C1. 12 Alkyl or C6-C 12 Aryl; the olefin is preferably at least one selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, and more preferably, the olefin can be ethylene and propylene.

[0069] According to some embodiments of the present invention, the prepolymerization reaction conditions include: a temperature of -40 to 80°C, preferably -20 to 50°C; and a pressure of 0.01 to 10 MPa.

[0070] According to some embodiments of the present invention, the polymerization reaction conditions include: a polymerization temperature of 0 to 150°C, preferably 60 to 90°C; and a pressure of 0.01 to 10 MPa.

[0071] The olefin polymerization reaction of the present invention is carried out according to known polymerization methods, which can be carried out in the liquid phase or gas phase, or in a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry polymerization and gas-phase fluidized bed polymerization are employed. Preferably, the following reaction conditions are used: polymerization temperature 0–150°C, preferably 60–90°C.

[0072] The olefin polymerization method provided by this invention can be used for homopolymerization of olefins, or for copolymerization of multiple olefins.

[0073] Catalysts containing the solid catalyst components provided in this invention are used for olefin polymerization reactions, exhibiting excellent polymerization activity and high hydrogen sensitivity, resulting in polymers with high melt index (6.5–9.5 g / 10 min) and wide molecular weight distribution (7.4–8.4). Detailed Implementation

[0074] The embodiments given below are for explanation and illustration only and do not constitute any limitation on the present invention.

[0075] In this invention, the method for preparing the catalytic composition of this invention can be carried out by conventional methods for preparing olefin catalyst components in the art. For example, the catalytic composition of this invention can be prepared by the following methods.

[0076] Method 1: The catalytic composition was prepared according to the method disclosed in patent CN1506384. First, a magnesium compound and an organic alcohol compound were mixed with an inert solvent at a molar ratio of 2–5, and the mixture was heated to 120–150°C and reacted for 1–5 hours at a magnesium / anhydride molar ratio of 5–10 and a magnesium / silicon molar ratio of 20–50. Then, the alcohol compound cooled to room temperature was added to a titanium compound solution pre-cooled to -15 to -40°C at a titanium / magnesium molar ratio of 20–50, and the mixture was heated to 90–110°C. An electron donor compound was added at a magnesium / ester molar ratio of 2–10, and the mixture was reacted at 100–130°C for 1–3 hours. The solid particles were then separated by filtration. Next, the solid particles were added to the titanium compound solution at a titanium / magnesium molar ratio of 20–50, stirred, and reacted at 100–130°C for 1.5–3 hours. The solid particles were then separated by filtration. Finally, the solid particles were washed with an inert solvent at 50–80°C and dried to obtain the catalyst component.

[0077] Method 2: The catalytic composition is prepared according to the method disclosed in patent CN85100997. First, a magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. The solid is then treated with the internal electron-donating compound of this invention to allow it to adhere to the solid. If necessary, the solid is further treated with titanium tetrahalide and an inert diluent. The precipitation aid used is one or more of organic anhydrides, organic acids, ethers, ketones, and esters. Examples include: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonic acid ester, glutaric acid ester, 2,4-pentanediol ester, and 3,5-heptanediol ester. The amounts of each component, per mole of magnesium halide, are as follows: organic epoxy compound 0.2–10 moles, organic phosphorus compound 0.1–3 moles, precipitation aid 0–1.0 moles, titanium compound 0.5–150 moles, and electron donor compound 0.02–0.5 moles.

[0078] Method 3: The catalytic composition was prepared according to the method disclosed in CN1091748. The magnesium chloride alcohol melt was dispersed in a dispersant system of white oil and silicone oil by high-speed stirring to form an emulsion. This emulsion was then discharged into a cooling liquid for rapid cooling and shaping, forming magnesium chloride alcohol microspheres. The cooling liquid was an inert hydrocarbon solvent with a low boiling point, such as petroleum ether, pentane, hexane, or heptane. The obtained magnesium chloride alcohol microspheres were washed and dried to form a spherical carrier. The molar ratio of alcohol to magnesium chloride was 2–3, preferably 2–2.5. The carrier particle size was 10–300 micrometers, with 30–150 micrometers being optimal.

[0079] The spherical support was treated with an excess of titanium tetrachloride at low temperature, with the temperature gradually increased. An electron donor was added during the treatment process. After treatment, the catalyst was repeatedly thawed with an inert solvent and dried to obtain a solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride was 20–200, preferably 30–60; the initial treatment temperature was -30–0°C, preferably -25–-20°C; and the final treatment temperature was 80–136°C, preferably 100–130°C.

[0080] The obtained spherical catalyst has the following characteristics: titanium content 1.5–3.0 wt%; ester content 6.0–20.0 wt%; chlorine content 52–60 wt%; magnesium content 10–20 wt%; inert solvent content 1–6 wt%; and a catalyst specific surface area greater than 250 m². 2 / g.

[0081] Method 4: Dialkoxymagnesium is added to an aromatic hydrocarbon compound and stirred to form a suspension. The suspension is treated with tetravalent titanium chloride at -20 to 100°C and reacted at 0 to 130°C. During this process, an electron donor is added at -20 to 130°C to initiate the reaction. The resulting solid is washed with the aromatic hydrocarbon compound. Then, at 0 to 130°C, it is treated again with tetravalent titanium chloride in an aromatic hydrocarbon solvent. Finally, it is washed with an inert solvent and dried to obtain a solid catalyst. The amount of tetravalent titanium chloride used per mole of dialkylmagnesium is 0.5 to 100 mol, and the amount of electron donor is 0.01 to 10 mol.

[0082] Method 5: Halogenate dialkoxymagnesium compounds such as magnesium dialkoxy or magnesium diaryloxy with TiCl4 or its aromatic solution at 80–130 °C. The treatment with TiCl4 or its aromatic solution can be repeated once or multiple times, and an electron donor compound is added during one or more such treatments.

[0083] Method Six: Prepare the catalytic composition according to the method disclosed in patent US4540679. A transition metal compound (preferably a tetravalent titanium compound) and an alkoxy magnesium compound react with an electron donor in a certain ratio in an inert solvent, wherein the molar ratio of the transition metal element to magnesium element is at least 0.5:1, and the amount of the electron donor compound is at most 1.0 mol / g titanium atom. The inert solvent needs to be easily removable and needs to be dehydrated, deoxygenated, and free of gases that can poison the catalyst. The reaction is carried out at -10 to 170°C for a period of several minutes to several hours.

[0084] Another method for preparing catalysts is to form an emulsion of magnesium compounds and electron donors in a diluent, add titanium compounds to fix it to obtain spherical solids, and then process it to obtain solid catalysts.

[0085] The embodiments given below are for explanation and illustration only and do not constitute any limitation on the present invention.

[0086] As one embodiment of the present invention, the method for preparing solid catalyst components includes the following steps:

[0087] Catalyst component preparation method: First, a magnesium compound is dissolved in a solvent system composed of epichlorohydrin, tributyl phosphate, and toluene to form a homogeneous solution. This solution is then mixed with titanium tetrachloride, and a solid is precipitated in the presence of a co-precipitant. The solid is then treated with an internal electron-donating compound to allow it to attach to the solid. If necessary, the solid is further treated with titanium tetrahalide and an inert diluent. The co-precipitant used is one or more of organic anhydrides, organic acids, ethers, ketones, and esters. Examples include: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonic acid, glutaric acid, 2,4-pentanediol ester, and 3,5-heptanediol ester. The amounts of each component, calculated per mole of magnesium halide, are as follows: organic epoxy compound 0.2–10 moles, organophosphorus compound 0.1–3 moles, precipitation aid 0–1.0 moles, titanium compound 0.5–150 moles, and internal electron donor compound 0.02–0.5 moles. Regarding the reaction temperature, the reaction temperature for dissolving the magnesium compound in a solvent system composed of epichlorohydrin, tributyl phosphate, and toluene can be selected from 0–110°C, preferably 20–90°C; the mixing temperature of the resulting homogeneous solution with titanium tetrachloride can be selected from -60–110°C, preferably -40–0°C; and the temperature for treating the internal electron donor compound can be selected from -40–110°C, preferably 40–90°C.

[0088] In the preparation of the above catalyst components, the required internal electron donor compound can be added either in the form of a compound or in other ways, such as by obtaining it in situ using a suitable precursor of the internal electron donor compound. For example, using the first internal electron donor compound shown in formula (I) as the precursor of the corresponding epoxy compound and / or ethylene glycol derivative monomer of the polymer, an initiator is added during the preparation of the catalyst to allow the epoxy compound and / or ethylene glycol derivative precursor to react in situ to generate the first internal electron donor compound shown in formula (I).

[0089] The internal electron donor compound can also be added in any step of the above catalyst preparation method.

[0090] ID-1, ID-2, ID-3, ID-4, ID-5, ID-6, ID-7, and ID-8, prepared in Preparation Examples 1 to 8, were used as the first internal electron donor compounds of the catalysts in Examples 1 to 10.

[0091] Product yield = product mass / reactant (monomer) mass × 100%.

[0092] Preparation Example 1: Preparation of poly(benzoyl glycidyl ester) (ID-1)

[0093]

[0094] Under nitrogen protection, benzoyl glycidyl ester (4 mL) and potassium tert-butoxide (0.14 g) were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was completed, the reactants were cooled to room temperature, ethyl acetate (100 mL) was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-1, with a yield of 52%.

[0095] Preparation Example 2: Preparation of poly(4-n-butylbenzoyl glycidyl ester) (ID-2)

[0096]

[0097] Under nitrogen protection, 6 mL of 4-n-butylbenzoyl glycidyl ester and 0.17 g of potassium tert-butoxide were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was completed, the reactants were cooled to room temperature, 100 mL of ethyl acetate was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-2, with a yield of 63%.

[0098] Preparation Example 3: Preparation of poly(4-chlorobenzoyl glycidyl ester) (ID-3)

[0099]

[0100] Under nitrogen protection, 5 g of 4-chlorobenzoyl glycidyl ester and 0.13 g of potassium tert-butoxide were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was complete, the reactants were cooled to room temperature, 100 mL of ethyl acetate was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-3 in 88% yield.

[0101] Preparation Example 4: Preparation of poly(4-ethoxybenzoyl glycidyl ester) (ID-4)

[0102]

[0103] Under nitrogen protection, 8 g of 4-ethoxybenzoyl glycidyl ester and 0.20 g of potassium tert-butoxide were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was completed, the reactants were cooled to room temperature, 100 mL of ethyl acetate was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-4, with a yield of 74%.

[0104] Preparation Example 5: Preparation of poly(n-butyryl glycidyl ester) (ID-5)

[0105]

[0106] Under nitrogen protection, phenyl glycidyl ether (5.5 g) and potassium tert-butoxide (0.14 g) were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was complete, the reactants were cooled to room temperature, ethyl acetate (100 mL) was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-5 in 55% yield.

[0107] Preparation Example 6: Preparation of poly(n-butyryl glycidyl ester) (ID-6)

[0108]

[0109] Under nitrogen protection, methyl glycidyl n-butyrate (12 mL) and potassium tert-butoxide (0.46 g) were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was completed, the reactants were cooled to room temperature, ethyl acetate (100 mL) was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to obtain product ID-6, poly(n-butyryl glycidyl ester), in 54% yield.

[0110] Preparation Example 7: Preparation of Poly(Myricetin) (ID-7)

[0111]

[0112] Under nitrogen protection, myricetin (12 g) and potassium tert-butoxide (0.33 g) were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was completed, the reactants were cooled to room temperature, ethyl acetate (100 mL) was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to obtain product ID-7, with a yield of 75%.

[0113] Preparation Example 8: Preparation of poly(3-(2,2,3,3-tetrafluoropropoxy)-1,2-propene oxide)(ID-8)

[0114]

[0115] Under nitrogen protection, 12 g of 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propene oxide and 0.36 g of potassium tert-butoxide were added to a reaction flask, and the mixture was heated to 80 °C with stirring for 3 hours. After the reaction was complete, the reactants were cooled to room temperature, 100 mL of ethyl acetate was added, and the mixture was stirred for 5 minutes. The organic phase was washed three times with water, and the solvent was removed under vacuum to give product ID-8, with a yield of 44%.

[0116] Preparation of catalyst components in Examples 1-12

[0117] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate (TBP) were added sequentially. The mixture was stirred and heated to 50 °C, and maintained for 2.5 h. After the solid was completely dissolved, 1.4 g of phthalic anhydride was added, and the mixture was maintained for another h. The solution was then cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, during which solids gradually precipitated. After reaching 80 °C for one hour, 6 mmol of the complex internal electron donor compound from Table 1 was added (for ease of calculation, the amount of the first internal electron donor compound shown in formula (I) is always calculated based on the relative molecular mass of the corresponding epoxy monomer, i.e., assuming the degree of polymerization n=1 of the first internal electron donor compound shown in formula (I) is used for calculation), and the temperature was maintained for 1 h. After hot filtration at 80 °C, 150 mL of toluene was added, and the mixture was washed twice to obtain a solid precipitate. Then add 60 mL of toluene and 40 mL of TiCl4, heat to 110 °C, and maintain for 2 h. After removing the filtrate, add another 60 mL of toluene and 40 mL of TiCl4, heat to 110 °C, and maintain for 2 h. Remove the filtrate. Add 70 mL of toluene and wash three times at 110 °C for 10 min each time. Add 60 mL of hexane and wash twice at room temperature. After vacuum drying, obtain the solid catalyst component.

[0118] Comparative Examples 1-7

[0119] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate (TBP) were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. After the solid was completely dissolved, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another 1 h. The solution was then cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly increased to 80 °C, during which time a solid gradually precipitated. After reaching 80 °C for one hour, 6 mmol of the internal electron-donating compound from Table 1 was added, and the temperature was maintained for 1 h. After hot filtration at 80 °C, 150 mL of toluene was added, and the mixture was washed twice to obtain a solid precipitate. Then, 60 mL of toluene and 40 mL of TiCl4 were added, and the temperature was increased to 110 °C and maintained for 2 h. After removing the filtrate, another 60 mL of toluene and 40 mL of TiCl4 were added, and the temperature was increased to 110 °C and maintained for 2 h. The filtrate was then removed. Add 70 mL of toluene and wash three times at 110 °C for 10 min each time. Add 60 mL of hexane and wash twice at room temperature. After vacuum drying, obtain the solid catalyst component.

[0120] Application example: propylene polymerization experiment

[0121] The solid catalyst components obtained in Examples 1-12 and Comparative Examples 1-7 were subjected to propylene polymerization.

[0122] The propylene polymerization procedure was as follows: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMDMS, as an external electron donor) were added to achieve an Al / Si (mol) ratio of 25. Then, 10 mg of a solid catalyst and 1.2L of hydrogen were added, followed by the introduction of 2.3L of liquid propylene. The temperature was raised to 70°C and maintained for 1 hour. The reactor was then cooled, depressurized, and discharged to obtain PP resin. Performance tests were performed on various PP resins, and the data are shown in Table 1.

[0123] Table 1 Catalyst composition and propylene polymerization results

[0124]

[0125]

[0126] Wherein: DB is 2,4-pentanediol dibenzoate (a diol ester compound), EB is ethyl benzoate, DB-Cl is 2,4-pentanediol di(m-chlorobenzoate), and PB is 3,5-heptanediol dibenzoate.

[0127] The isotactic index of polymers is determined by heptane extraction. 2g of dried polymer sample (PP resin prepared in the example) is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotactic index.

[0128] Test method for melt index (MI) of polymer: The melt index of the polymer used to prepare PP resin in the application example shall be determined according to GB / T 3682-2000.

[0129] Polymer molecular weight distribution (MWD, MWD = M) w / M n Test method: Gel permeation chromatography was used to determine the polymer molecular weight distribution of PP resin at 150℃ using PL-GPC220 with trichlorobenzene as solvent (standard: polystyrene, flow rate: 1.0 mL / min, column: 3xPlgel 10um M1xED-B 300x7.5nm). Application example: Preparation of PP resin polymer molecular weight distribution.

[0130] Polymer polymerization activity (kgPP / gcat): The polymer polymerization activity is the ratio of the weight of the PP resin prepared in the application example to the weight of the catalyst added in the propylene polymerization reaction.

[0131] As can be seen from Examples 1-12 and Comparative Examples 1-7 of the olefin polymerization experimental data in Table 1, using the catalyst provided by the present invention, and employing a combination of polyethylene oxide / polyethylene glycol derivatives (first internal electron donor) and glycol esters (second internal electron donor) with specific structures as internal electron donors, it is possible to maintain good polymerization activity of the catalyst while obtaining a polymer with a high melt index, a wide molecular weight distribution, and a high polymer isotactic index. These properties are beneficial to the processing and development of polypropylene resin products.

[0132] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50–90, in this specification it means specifically listing values ​​such as 51–89, 52–88… and 69–71 and 70–71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0133] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst component for olefin polymerization, characterized in that, The components include magnesium, titanium and an internal electron donor, the internal electron donor including a first internal electron donor compound shown in formula (I) and a second internal electron donor compound shown in formula (II); In equation (I), 3 ≤ n ≤ 1000; R1, R2, and R3 can be optionally keyed together to form a ring; R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen and C. 1- C 12 Straight-chain or branched alkyl groups I, C3-C 12 Cyclic hydrocarbon group I, C2-C 12 Alkenyl I, C2-C 12 alkynyl group I, C6-C 20 Aryl I, C7-C 20 Hydrocarbon aryl I, C7-C 20 Aromatic group I, C6-C 20 heteroaryl I, C4-C 20 Heterocyclic group I, halogen atom; The C 1- C 12 Straight-chain or branched alkyl groups I, C3-C 12 Cyclic hydrocarbon group I, C2-C 12 Alkenyl I, C2-C 12 alkynyl group I, C6-C 20 Aryl I, C7-C 20 Hydrocarbon aryl I, C7-C 20 Aromatic group I, C6-C 20 heteroaryl I, C4-C 20 The hydrogen atom on heterocyclic group I may optionally be replaced by one or more substituents X1; R4 is one of the structures shown in equations (III), (IV), and (V): R5, R6, and R7 may be the same or different, and each is independently selected from hydrogen and C. 1- C 12 Straight-chain or branched alkyl II, C3-C 12 Cyclic hydrocarbon group II, C2-C 12 Alkenyl II, C2-C 12 Alkyne II, C6-C 20 Aryl II, C7-C 20 Hydrocarbon aryl II, C7-C 20 Aromatic group II, C6-C 20 heteroaryl II, C4-C 20 Heterocyclic group II, halogen atom; The C 1- C 12 Straight-chain or branched alkyl II, C3-C 12 Cyclic hydrocarbon group II, C2-C 12 Alkenyl II, C2-C 12 Alkyne II, C6-C 20 Aryl II, C7-C 20 Hydrocarbon aryl II, C7-C 20 Aromatic group II, C6-C 20 heteroaryl II, C4-C 20 The hydrogen atom on heterocyclic group II may optionally be replaced by one or more substituents X2; The substituents X1 and X2 are independently selected from C1-C6 straight-chain or branched alkyl groups, C3-C6... 10 Cycloalkyl, hydroxyl, amino, C1-C6 alkoxy, C1-C6 alkyl-substituted amino, halogen atom and cyano; In formula (II), R8 and R9 can be optionally bonded into a ring. R8 and R9 may be the same or different, and each can be independently selected from hydrogen, halogen, or C1-C. 10 Alkyl I, C3-C 10 Cycloalkyl I, C6-C 10 Aryl I, C7-C 10 aryl hydrocarbons (I or C7-C) 10 Aromatic group I; R 10 and R 11 Whether they are the same or different, they are each independently selected from halogens, C1-C. 10 Alkyl II, C3-C 10 Cycloalkyl II, C6-C 10 aryl II, C7-C 10 Hydrocarbon aryl II or C7-C 10 The aromatic group II; the C1-C 10 Alkyl II, C3-C 10 Cycloalkyl II, C6-C 10 Aryl II, C7-C 10 Hydrocarbon aryl II or C7-C 10 The hydrogen atom on the aryl group II may optionally be replaced by an alkyl group or a halogen; R 12 and R 13 Whether they are the same or different, they are each independently selected from C3-C. 20 cycloalkyl, C6-C 20 Aryl III, C7-C 20 aryl hydrocarbons (III or C7-C) 20 Aromatic group III; the C3-C 20 cycloalkyl, C6-C 20 Aryl III, C7-C 20 aryl hydrocarbons (III or C7-C) 20 The hydrogen atom on the aryl group III can optionally be replaced by an alkyl group or a halogen, and R 12 and R 13 Cannot be C3-C at the same time 20 Cycloalkyl.

2. The olefin polymerization catalyst component according to claim 1, characterized in that, 3≤n≤100; preferably, 4≤n≤20; The cyclic hydrocarbon group is a cycloalkyl, cycloalkenyl, or cycloynyl group; The hydrocarbon aryl group is an alkylaryl, alkenylaryl, or alkynylaryl; The aromatic group is an aralkyl, arene, or arynyl group; The heteroaryl group is an aryl group containing heteroatoms; preferably, the heteroaryl group contains 1 to 3 heteroatoms; preferably, the heteroatoms are selected from at least one of N, O, and S; preferably, the heteroaryl group has a five-membered, six-membered, or seven-membered skeleton; the heteroaryl group is preferably pyridyl, pyrimidinyl, pyrazinyl, furanyl, or thiopheneyl. The heterocyclic group is a cycloalkyl group containing heteroatoms; preferably, the heterocyclic group contains 1 to 3 heteroatoms; preferably, the heteroatoms are selected from at least one of N, O, and S; preferably, the heteroaryl group has a ternary, tetra-membered, pentaneous, hexa-membered, or heptaneous skeleton; the heterocyclic group is preferably ethylene oxide, tetrahydrofuranyl, tetrahydropyranyl, or piperidinyl.

3. The olefin polymerization catalyst component according to claim 1 or 2, characterized in that, R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen, C1-C8 straight-chain or branched alkyl groups, and C5-C6 alkyl groups. 10 Cycloalkyl group I, C2-C8 alkenyl group I, C2-C8 alkynyl group I, C6-C 14 Aryl I, C7-C 15 Hydrocarbon aryl I, C7-C 15 Aromatic group I, C6-C 15 heteroaryl I, C4-C 15 Heterocyclic group I, halogen atom I; the C1-C8 straight-chain or branched alkyl group I, C5-C 10 Cycloalkyl group I, C2-C8 alkenyl group I, C2-C8 alkynyl group I, C6-C 14 Aryl I, C7-C 15 Hydrocarbon aryl I, C7-C 15 Aromatic group I, C6-C 15 heteroaryl I, C4-C 15 The hydrogen atom on heterocyclic group I may optionally be replaced by one or more substituents X1; Preferably, R1, R2, and R3 may be the same or different, and each is independently selected from hydrogen, C1-C4 straight-chain or branched alkyl groups, C5-C8 cyclic hydrocarbon groups, C6-C9 aryl groups, and C7-C4 alkyl groups. 10 Hydrocarbon aryl I, C7-C 10 Aromatic group I, halogen atom; the C1-C4 straight-chain or branched alkyl group I, C5-C8 cyclic hydrocarbon group I, C6-C9 aryl group I, C7-C 10 Hydrocarbon aryl I, C7-C 10 The hydrogen atom on the aromatic group I may optionally be replaced by one or more substituents X1.

4. The olefin polymerization catalyst component according to claim 1, 2, or 3, characterized in that, R5, R6, and R7 may be the same or different, and each is independently selected from hydrogen, C1-C8 straight-chain or branched alkyl groups, C4-C6... 10 Cyclic hydrocarbon group I, C2-C8 alkenyl group II, C2-C8 alkynyl group II, C6-C 14 Aryl II, C7-C 15 Hydrocarbon aryl II, C7-C 15 Aromatic group II; the C1-C8 straight-chain or branched alkyl group II, C4-C 10 Cycloalkyl II, C2-C8 alkenyl II, C2-C8 alkynyl II, C6-C 14 Aryl II, C7-C 15 Hydrocarbon aryl II, C7-C 15 The hydrogen atom on the aryl group II may optionally be replaced by one or more substituents X2; Preferably, R5, R6, and R7 may be the same or different, and each is independently selected from hydrogen, C1-C4 straight-chain or branched alkyl group II, C5-C8 cyclic alkyl group II, C6-C 10 Aryl III, C7-C 12 Hydrocarbon aryl I, C7-C 12 Aromatic group I; C1-C4 straight-chain or branched alkyl group II, C5-C8 cyclic alkyl group II, C6-C 10 Aryl III, C7-C 12 Hydrocarbon aryl I, C7-C 12 The hydrogen atom on the aromatic group I can optionally be replaced by one or more substituents X2.

5. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, R8 and R9 may be the same or different, and each is independently selected from hydrogen, C1-C8 alkyl or halogen; preferably, R8 and R9 are each selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, chlorine or bromine. And / or, R 10 and R 11 Whether they are the same or different, each is independently selected from C1 to C2. 10 The alkyl group, wherein the hydrogen atoms on the alkyl group are optionally substituted with halogens; preferably, R 10 and R 11 Each is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl; And / or, R 12 and R 13 Whether they are the same or different, each is independently selected from C6-C. 20 Aryl IV, C7-C 20 Aromatic group IV or C7-C 20 Hydrocarbon aryl IV; the C6-C 20 Aryl IV, C7-C 20 Aromatic group IV or C7-C 20 The hydrogen atom on the aryl group IV is optionally replaced by an alkyl group or a halogen; preferably, R 12 and R 13 Each is independently selected from C6-C 15 Aryl or C7-C 20 Aryl alkyl group.

6. The olefin polymerization catalyst component according to any one of claims 1-5, characterized in that, The magnesium element is derived from at least one of magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide alcohol, or a derivative of magnesium dihalide in which the halogen atom is replaced by an alkoxy or haloalkoxy group; preferably magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium dichloride alcohol, magnesium dibromide alcohol, or magnesium diiodide alcohol.

7. The olefin polymerization catalyst component according to any one of claims 1-6, characterized in that, The titanium element is derived from the general formula compound TiX. m (OR 1 ) 4-m At least one of them, R 1 For C1-C 20 Hydrocarbon group, X is halogen, 1≤m≤4; preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

8. The olefin polymerization catalyst component according to any one of claims 1-7, characterized in that, In the composition, the molar ratio of magnesium, titanium and the internal electron donor is 1:(0.5~150):(0.02~0.4); The molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100):(100-1); preferably (1-50):(50-1), and more preferably (1-20):(20-1).

9. The olefin polymerization catalyst component according to claim 8, characterized in that, The catalyst component for the olefin polymerization reaction also contains halogens; the molar ratio of magnesium, titanium, halogens and the internal electron donor in the component is 1:(0.5-150):(0.1-800):(0.02-0.4).

10. A catalyst for olefin prepolymerization or polymerization, characterized in that, Contains products prepared from component materials; The component material includes component a and component b; Component a is the olefin polymerization catalyst component according to any one of claims 1 to 9; Component b is an organoaluminum compound.

11. The catalyst according to claim 10, characterized in that, The organoaluminum compound is an alkylaluminum compound; And / or, in the catalyst, the molar ratio of titanium to aluminum in the organoaluminum compound is 1:(5-1000), preferably 1:(25-100).

12. The catalyst according to claim 10 or 11, characterized in that, The component material also includes component c, which is an external electron donor compound; The external electron donor compound includes compounds with the general formula R. 3 k Si(OR 4 ) 4-k One or more of the organosilicon compounds; Where 0≤k≤3; R 3 and R 4 Same or different; R 3 Selected from C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 Cycloalkyl, aryl, haloalkyl, amino, halogen, or hydrogen atom; R 4 Selected from C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 Cycloalkyl, aryl, haloalkyl, or amino; In the catalyst, the molar ratio of titanium to silicon in the external electron donor compound is 1:(0.1-500), preferably 1:(25-100).

13. A method for olefin prepolymerization or polymerization, characterized in that, An olefin-containing feedstock comes into contact with a catalyst to undergo a prepolymerization or polymerization reaction, wherein the catalyst contains the catalyst component as described in any one of claims 1-9 or is selected from the catalysts described in any one of claims 10-12.

14. The olefin prepolymerization or polymerization method according to claim 13, characterized in that, The prepolymerization reaction conditions include: a temperature of -40 to 80°C, preferably -20 to 50°C; and a pressure of 0.01 to 10 MPa. The polymerization reaction conditions include: a polymerization temperature of 0–150°C, preferably 60–90°C; and a pressure of 0.01–10 MPa.

15. The method according to claim 13 or 14, characterized in that, At least one of the olefins is an olefin represented by the general formula CH2=CHR, where R is hydrogen or C1~C1. 12 Alkyl or C6-C 12 Aryl.

16. The method according to claim 15, characterized in that, The olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.

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