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

Abstract

The invention relates to a catalytic component, an olefin prepolymerization reaction or polymerization reaction catalyst and an olefin prepolymerization reaction or polymerization reaction method. The catalyst component for olefin polymerization comprises a magnesium element, a titanium element and an internal electron donor, the internal electron donor comprises a compound as shown in a general formula (I), and an R4 structure in the general formula (I) is one of three structures as shown in a general formula (II), a general formula (III) and a general formula (IV). When the catalyst component is used for propylene polymerization reaction, the polymerization activity is high, and the obtained polymerization product is wide in molecular weight distribution, relatively high in melt index and large in adjustable range of isotactic index.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of olefin polymerization catalysts, and relates to a catalytic component, an olefin prepolymerization or polymerization catalyst, an olefin prepolymerization or polymerization method, in particular to an olefin polymerization catalytic component containing a polyethylene oxide / polyethylene glycol derivative compound, a catalyst and application. BACKGROUND

[0002] Polypropylene is one of the largest synthetic resin materials in the world, and has been widely used in packaging, building materials, medical and health fields, and more than 90% of polypropylene materials are prepared by Ziegler-Natta catalyst. The Ziegler-Natta catalyst takes magnesium, titanium, halogen and internal donor as basic components, and the type and content of the internal donor have important influence on the activity, stereoregularity, hydrogen regulation sensitivity, molecular weight distribution and other properties of the catalyst. So far, the development of Ziegler-Natta catalyst has experienced five generations, and the research and development of new internal donor compounds have been an important research direction to promote the innovation of polypropylene catalyst. A large number of internal donor compounds have been reported and successfully applied to polypropylene catalysts. For example, patent CN85100997A uses phthalate compounds as internal donor; patent CN1015062B uses diether compounds as internal donor; patent CN1169845C uses diol ester compounds as internal donor; patent CN1313869A uses succinate compounds as internal donor, etc.

[0003] However, the catalyst prepared by using the reported internal donor compounds has some shortcomings. For example, the hydrogen regulation sensitivity of the catalyst is poor, which will make the melt index of the obtained polymerization product low, and there is a deficiency in developing high melt index products. For another example, the molecular weight distribution of the obtained resin product is narrow, which limits the mechanical properties of the product, and is weak in developing high value-added products. Therefore, the existing problem is to research and develop new compounds as internal donor of Ziegler-Natta catalyst to overcome the defects of the prior art. SUMMARY

[0004] In view of the problems existing in the prior art, the present inventors have found through a large number of experiments that a kind of polyethylene oxide / polyethylene glycol derivative compound with specific structure as shown in general formula (I) is used as internal donor to prepare Ziegler-Natta catalyst component, and the obtained catalyst component is used together with a cocatalyst and an external donor in the olefin polymerization reaction. When used for propylene polymerization, the polymerization activity is high, the molecular weight distribution of the obtained polymerization product is wide, the melt index is high, and the isotacticity can be adjusted in a large range.

[0005] In a first aspect, the present application provides a catalytic component comprising a magnesium element, a titanium element and an internal electron donor compound selected from at least one of the compounds represented by the general formula (I);

[0006]

[0007] In formula (I), 3 ≤ n ≤ 1000;

[0008] R1, R2, R3may optionally be linked to form a ring;

[0009] R1, R2, R3are the same or different, each independently selected from hydrogen, C 1- C 12 linear or branched alkyl group I, C3-C 12 cycloalkyl group I, C2-C 12 alkenyl group I, C2-C 12 alkynyl group I, C6-C 20 aryl group I, C7-C 20 hydrocarbyl group I, C7-C 20 aromatic hydrocarbyl group I, C6-C 20 heteroaryl group I, C4-C 20 heterocyclic group I, halogen atom;

[0010] said C 1- C 12 linear or branched alkyl group II, C3-C 12 cycloalkyl group II, C2-C 12 alkenyl group II, C2-C 12 alkynyl group II, C6-C 20 aryl group II, C7-C 20 hydrocarbyl group II, C7-C 20 aromatic hydrocarbyl group II, C6-C 20 heteroaryl group II, C4-C 20 the hydrogen on the heterocyclic group II can be optionally substituted with one or more substituents X1;

[0011] R4is one of the structures represented by formula (III), formula (IV), formula (V):

[0012]

[0013] R5, R6, R7are the same or different, each independently selected from hydrogen, C 1- C 12 linear or branched alkyl group II, C3-C 12 cycloalkyl group II, C2-C 12 alkenyl group II, C2-C 12 alkynyl group II, C6-C 20aryl II, C7-C 20 hydrocarbon aryl II, C7-C 20 aromatic hydrocarbon group II, C6-C 20 heteroaryl II, C4-C 20 heterocyclyl II, halogen atom;

[0014] said C 1- C 12 straight-chain or branched alkyl II, C3-C 12 cycloalkyl II, C2-C 12 alkenyl II, C2-C 12 alkynyl II, C6-C 20 aryl II, C7-C 20 hydrocarbon aryl II, C7-C 20 aromatic hydrocarbon group II, C6-C 20 heteroaryl II, C4-C 20 the hydrogens on the heterocyclyl II can optionally be substituted by one or more substituents X2;

[0015] said substituents X1, X2are independently selected from the group consisting of C1-C6 straight-chain or branched alkyl, C3-C 10 cycloalkyl, hydroxyl, amino, C1-C6 alkoxy, C1-C6 alkyl-substituted amino, halogen atom and cyano.

[0016] As a preferred technical solution, in the catalytic component, the molar ratio of magnesium element, titanium element and the electron donor compound represented by general formula (I) is 1:(0.5-150):(0.02-0.4).

[0017] As a preferred technical solution, in general formula (I), 3≤n≤100; further preferably, 4≤n≤20.

[0018] According to some embodiments of the present application, said substituents X1, X2are independently selected from the group consisting of C1-C6 hydrocarbon group (such as methyl, ethyl n-propyl or isopropyl), hydroxyl, amino, C1-C6 alkoxy (such as methoxy, ethoxy, n-propoxy or isopropoxy), C1-C6 alkyl-substituted amino (such as -NHCH3or -N(CH3)2), halogen atom (such as fluorine atom, chlorine atom, bromine atom or iodine atom), cyano.

[0019] In the present application, the term "cycloalkyl" is cycloalkyl, cycloalkenyl or cycloalkynyl, and also includes cycloalkyl connected by alkyl, such as methylcyclohexyl.

[0020] In the present application, the term "hydrocarbon aryl" is alkylaryl, alkenylaryl or alkynylaryl.

[0021] In the present application, the term "aromatic hydrocarbon group" is arylalkyl, arylalkenyl or arylalkynyl.

[0022] 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.

[0023] 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.

[0024] Preferably, 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.

[0025] 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.

[0026] Preferably, 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... 10Cyclic 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.

[0027] 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.

[0028] According to some embodiments of the present invention, the compound with the general formula (I) structure may be selected from, but is not limited to, the following compounds:

[0029] 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-isopropylbenzoyl glycidyl ester), poly(2-n-butylbenzoyl glycidyl ester), poly(3-n-butylbenzoyl glycidyl ester) Benzoyl 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-bromobenzoyl glycidyl ester), poly(2-iodobenzoyl glycidyl ester), poly(3-iodobenzoyl glycidyl ester) Formic acid 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-methyl benzoate), poly(3-methyl benzoate), poly(4-methyl benzoate), poly(2-ethyl benzoate), poly(3-ethyl benzoate), poly(4-ethyl benzoate), poly(2-n-propyl benzoate), poly(3-n-propyl benzoate), poly(4-n-propyl benzoate), poly(2-n-propyl benzoate), poly(3-n-propyl benzoate), poly(4-n-propyl benzoate) Methyl glycidol ester), poly(2-isopropylbenzoate methyl glycidol ester), poly(3-isopropylbenzoate methyl glycidol ester), poly(4-isopropylbenzoate methyl glycidol ester), poly(2-n-butylbenzoate methyl glycidol ester), poly(3-n-butylbenzoate methyl glycidol ester), poly(4-n-butylbenzoate methyl glycidol ester), poly(2-tert-butylbenzoate methyl glycidol ester), poly(3-tert-butylbenzoate methyl glycidol ester), poly(4-tert-butylbenzoate methyl glycidol ester), poly(2-fluorobenzoate methyl glycidol ester), poly(3-fluorobenzoate methyl glycidol ester), poly(4-fluorobenzoate methyl glycidol ester), poly(2-chlorobenzoate methyl glycidol ester)Poly(3-chlorobenzoic acid methyl glycidol ester), poly(4-chlorobenzoic acid methyl glycidol ester), poly(2-bromobenzoic acid methyl glycidol ester), poly(3-bromobenzoic acid methyl glycidol ester), poly(4-bromobenzoic acid methyl glycidol ester), poly(2-iodobenzoic acid methyl glycidol ester), poly(3-iodobenzoic acid methyl glycidol ester), poly(4-iodobenzoic acid methyl glycidol ester), poly(2-oxymethylbenzoic acid methyl glycidol ester), poly(3-oxymethylbenzoic acid methyl glycidol ester), poly(4-oxymethylbenzoic acid methyl glycidol ester), poly(formyl glycidol ester), poly(acetyl glycidol ester), poly(n-propionic acid glycidol ester), poly(isopropionic acid glycidol ester), poly(n-butyryl glycidol ester) Glyceryl ester), poly(isobutyryl glyceryl ester), poly(tert-butyryl glyceryl ester), poly(glyceryl methacrylate), poly(phenyl glyceryl ether), poly(2-methylphenyl glyceryl ether), poly(3-methylphenyl glyceryl ether), poly(4-methylphenyl glyceryl ether), poly(2-ethylphenyl glyceryl ether), poly(3-ethylphenyl glyceryl ether), poly(4-ethylphenyl glyceryl ether), poly(2-n-propylphenyl glyceryl ether), poly(3-n-propylphenyl glyceryl ether), poly(4-n-propylphenyl glyceryl ether), poly(2-isopropylphenyl glyceryl ether), poly(3-isopropylphenyl glyceryl ether), poly(4-isopropylphenyl glyceryl ether), poly(2-n-butyl... 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 ether), poly(2-iodophenyl glycidyl ether), poly(3-iodophenyl glycidyl ether), poly(4-iodophenyl ether) Poly(2-oxymethylphenylglycidyl ether), poly(3-oxymethylphenylglycidyl ether), poly(4-oxymethylphenylglycidyl 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 glycidyl ether), poly(3-(2, (2,3,3-Tetrafluoropropoxy)-1,2-propylene 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), poly(myricetin).

[0030] 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.

[0031] 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).

[0032] The magnesium compound represented by formula (VI):

[0033] MgR a R b Formula (VI)

[0034] 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.

[0035] The hydrate of the magnesium compound represented by formula (VII):

[0036] MgR c R d ·eH2O formula (VII)

[0037] Among them, R c and R dWhether 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.

[0038] The alcohol adduct of the magnesium compound represented by formula (VIII):

[0039] MgR f R g ·hR j OH formula (VIII)

[0040] 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.

[0041] 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.

[0042] According to some embodiments of the present invention, the magnesium compound is selected from one or more of magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, magnesium dihalides hydrates or alcoholic compounds thereof, and derivatives in which the halogen atom in magnesium dihalides is replaced by an alkoxy or haloalkoxy group; preferably magnesium dihalides and their alcoholic compounds, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and their alcoholic compounds.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] According to some embodiments of the present invention, the titanium compound comprises the general formula TiX. m (OR 1 ) 4-m At least one of the compounds, wherein R 1 For C1~C 20 The hydrocarbon group, where X is a halogen, and 1 ≤ m ≤ 4.

[0047] According to some embodiments of the present invention, R 1 For C1~C 20 Alkyl groups, preferably C1 to C2. 10 The alkyl group, more preferably a C1 to C6 alkyl group.

[0048] According to some embodiments of the present invention, X is selected from fluorine, chlorine, bromine and iodine.

[0049] According to some embodiments of the present invention, the titanium compound includes one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy. Preferably, the titanium compound is titanium tetrachloride.

[0050] The catalytic component also contains halogens; in the component, the molar ratio of magnesium, titanium, halogens and electron-donating compound shown in general formula (I) is 1:(0.5-150):(0.1-800):(0.02-0.4).

[0051] The internal electron donor compound can also be added in any step of the above catalyst preparation method.

[0052] According to some embodiments of the present invention, the catalytic components and / or catalysts of the present invention can be directly added to the reactor for the polymerization process. Alternatively, the catalytic components and / or catalysts 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.

[0053] In a second aspect, the present invention also provides a catalyst system for olefin polymerization, comprising:

[0054] Component a, the catalyst component described in the first aspect of the present invention;

[0055] Component b, an organoaluminum compound, preferably an alkylaluminum compound;

[0056] Component c, optionally, is an external electron donor compound, preferably an organosilicon compound.

[0057] According to some embodiments of the present invention, the alkylaluminum compound is of 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.

[0058] According to some embodiments of the present invention, the external electron donor includes a general formula R 3 k Si(OR 4 ) 4-k One or more organosilicon compounds. Where 0 ≤ k ≤ 3, R 3 and R 4 R can be the same or different alkyl, cyclic, aryl, haloalkyl, or amino groups. 3It can also be a halogen or a hydrogen atom. Specifically, it can be selected from trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane. The silane is selected from one or more of the following: n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyl tert-butyldimethoxysilane. Preferably, it is selected from one or more of the following: n-propyltrimethoxysilane, n-butyltrimethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, and dicyclopentyldimethoxysilane. More preferably, it is selected from one or more of the following: cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, or dicyclopentyldimethoxysilane.

[0059] According to some embodiments of the present invention, in the above-described catalytic components, the molar ratio of titanium in the catalytic components to aluminum in the alkylaluminum compound is 1:(5-1000), preferably 1:(25-100). The molar ratio of titanium in the catalytic components to silicon in the external electron donor compound is 1:(0-500), preferably 1:(25-100).

[0060] In a third aspect, the present invention provides the use of the catalytic 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 catalytic 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 conversion level. According to the invention, the prepolymerization catalyst comprises the above-described solid catalyst component and a prepolymer obtained by prepolymerization with an olefin, wherein the prepolymerization ratio is 0.1–1000 g olefin polymer / g solid catalyst component.

[0062] 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.

[0063] The prepolymerization ratio is 0.1–1000 g olefin polymer / g solid catalyst component. The olefin has the general formula CH2=CHR, where R is hydrogen or a C1–C6 alkyl group.

[0064] 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.

[0065] 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 catalytic 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 prepolymerized product obtained from the prepolymerization reaction as described in the third aspect of the present invention.

[0066] 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.

[0067] The olefin polymerization method provided by this invention can be used for homopolymerization of olefins, or for copolymerization of multiple olefins.

[0068] 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.

[0069] 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.

[0070] The olefin has the general formula CH2=CHR, where R is hydrogen or C1~C1. 12 Alkyl or C6-C 12Aryl; 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.

[0071] The olefin polymerization method provided by this invention can be used for homopolymerization of olefins, or for copolymerization of multiple olefins.

[0072] This invention has the following characteristics:

[0073] (1) The internal electron donor compound with a specific structure shown in general formula (I) used in this invention and its use in the preparation of olefin polymerization catalysts and olefin polymerization reactions have not been reported in the literature.

[0074] (2) The internal electron-donating compound of general formula (I) in this invention is a polymer, which can be prepared by a certain chemical reaction using the corresponding epoxy compound and / or ethylene glycol derivative as monomers. Alternatively, the corresponding epoxy compound and / or ethylene glycol derivative can be used as monomers, and the compound of general formula (I) can be generated in situ by adding an initiator during the catalyst preparation process.

[0075] (3) Using the internal electron donor compound of general formula (I) of the present invention, a catalyst component and catalyst with excellent comprehensive performance can be obtained. When used in propylene polymerization reaction, the polymerization activity is high, the resulting polymer product has a high melt index (4.7-18.8 g / 10 min), a wide molecular weight distribution (7.2-8.5), and a large adjustable range of isotactic index (90.2-96.4). Detailed Implementation

[0076] The embodiments given below are for explanation and illustration only and do not constitute any limitation on the present invention.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] The embodiments given below are for explanation and illustration only and do not constitute any limitation on the present invention.

[0088] As one embodiment of the present invention, the method for preparing solid catalyst components includes the following steps:

[0089] Preparation method of the catalytic component: 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 precipitation aid. The solid is then treated with an internal electron donor compound to attach it 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, 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.

[0090] In the above preparation method, the required electron-donating 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 electron-donating compound. For example, using the internal electron-donating compound represented by general 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 catalyst preparation process to allow the epoxy compound and / or ethylene glycol derivative precursor to react in situ to generate the internal electron-donating compound represented by general formula (I).

[0091] The internal electron donor compound can also be added in any step of the above catalyst preparation method.

[0092] ID-1, ID-2, ID-3, ID-4, ID-5, ID-6, ID-7, ID-8, ID-9, ID-10, ID-11, ID-12, ID-13, and ID-14 prepared in Preparation Examples 1 to 14 were used as internal electron donor compounds for the catalysts in Examples 1 to 16.

[0093] Product yield = product mass / reactant (monomer) mass × 100%.

[0094] Preparation Example 1: Preparation of poly(benzoyl glycidyl ester) (ID-1)

[0095]

[0096] 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%.

[0097] Preparation Example 2: Preparation of poly(4-n-butylbenzoyl glycidyl ester) (ID-2)

[0098]

[0099] 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%.

[0100] Preparation Example 3: Preparation of poly(4-chlorobenzoyl glycidyl ester) (ID-3)

[0101]

[0102] 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.

[0103] Preparation Example 4: Preparation of poly(4-ethoxybenzoyl glycidyl ester) (ID-4)

[0104]

[0105] 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%.

[0106] Preparation Example 5: Preparation of poly(methyl glycidol benzoate) (ID-5)

[0107]

[0108] Under nitrogen protection, 4 mL of methyl glycidol benzoate and 0.14 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 obtain product ID-5 in 80% yield.

[0109] Preparation Example 6: Preparation of poly(n-butyryl glycidyl ester) (ID-6)

[0110]

[0111] 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.

[0112] Preparation Example 7: Preparation of poly(glycidyl methacrylate) (ID-7)

[0113]

[0114] Under nitrogen protection, glycidyl methacrylate (10 g) and potassium tert-butoxide (0.40 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, poly(glycidyl methacrylate), in 51% yield.

[0115] Preparation Example 8: Preparation of poly(phenyl glycidyl ether) (ID-8)

[0116]

[0117] 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-8, with a yield of 55%.

[0118] Preparation Example 9: Preparation of poly(2-toluene glycidyl ether) (ID-9)

[0119]

[0120] Under nitrogen protection, 6 g of 2-tolueneglycidyl ether and 0.14 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-9 in 55% yield.

[0121] Preparation Example 10: Preparation of poly(benzyl glycidyl ether) (ID-10)

[0122]

[0123] Under nitrogen protection, benzyl glycidyl ether (12 g) and potassium tert-butoxide (0.41 g) were added to a reaction flask, and the mixture was heated to 80 °C for 3 hours with stirring. 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-10, poly(benzyl glycidyl ether), with a yield of 72%. Preparation Example 11: Preparation of poly(3-(2,2,3,3-tetrafluoropropoxy)-1,2-propene oxide)(ID-11)

[0124]

[0125] 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 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 obtain product ID-11, with a yield of 44%. Preparation Example 12: Preparation of poly(2-phenylethylene oxide-1-carboxylic acid methyl ester) (ID-12)

[0126]

[0127] Under nitrogen protection, methyl 2-phenylethylene oxide-1-carboxylate (10.4 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-12, with a yield of 53%. Preparation Example 13: Preparation of 5-poly(Myricetin) (ID-13)

[0128]

[0129] 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 give product ID-13, with a yield of 75%.

[0130] Preparation Example 14: Preparation of Poly(3-phenylethylene oxide carboxylate) (ID-14)

[0131]

[0132] Under nitrogen protection, ethyl 3-phenylethylene oxide carboxylate (10 g) and potassium tert-butoxide (0.28 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-14, with a yield of 60%.

[0133] Example 1: Preparation of Catalytic Components

[0134] 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 at this temperature 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 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 solids gradually precipitated. After reaching 80 °C for one hour, 12 mmol of poly(benzoyl glycidyl ester) (ID-1) (for ease of calculation, the amount of the internal electron donor compound shown in general 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 internal electron donor compound in general formula (I)) was added as the internal electron donor, 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 again. 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, the catalytic component is obtained.

[0135] Example 2 Preparation of catalytic components

[0136] The method is the same as in Example 1, except that the amount of internal electron donor compound ID-1 added is 24 mmol, as shown in Table 1.

[0137] Example 3 Preparation of catalytic components

[0138] The method is the same as in Example 1, except that the internal electron donor is replaced with poly(4-n-butylbenzoyl glycidyl ester) (ID-2), as shown in Table 1.

[0139] Example 4 Preparation of Catalytic Components

[0140] The method is the same as in Example 1, except that the internal electron donor is replaced with poly(4-n-butylbenzoyl glycidyl ester) (ID-2), and the amount of ID-2 added is 24 mmol, as shown in Table 1.

[0141] Example 5 Preparation of Catalytic Components

[0142] The method is the same as in Example 1, except that the internal electron donor is replaced with poly(4-chlorobenzoyl glycidyl ester) (ID-3), as shown in Table 1.

[0143] Example 6 Preparation of Catalytic Components

[0144] The method is the same as in Example 1, except that the internal electron donor is replaced with poly(4-ethoxybenzoyl glycidyl ester) (ID-4), as shown in Table 1.

[0145] Example 7 Preparation of Catalytic Components

[0146] The method is the same as in Example 1, except that the internal electron donor is replaced with poly(methyl methacrylate) (ID-5), as shown in Table 1.

[0147] Example 8 Preparation of Catalytic Components

[0148] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(n-butyryl glycidyl ester) (ID-6), as shown in Table 1.

[0149] Example 9 Preparation of Catalytic Components

[0150] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(glycidyl methacrylate) (ID-7), as shown in Table 1.

[0151] Example 10 Preparation of Catalytic Components

[0152] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(phenyl glycidyl ether) (ID-8), as shown in Table 1.

[0153] Example 11 Preparation of catalytic components

[0154] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(2-tolueneglycidyl ether) (ID-9), as shown in Table 1.

[0155] Example 12 Preparation of Catalytic Components

[0156] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(benzyl glycidyl ether) (ID-10), as shown in Table 1.

[0157] Example 13 Preparation of Catalytic Components

[0158] The method is the same as in Example 1, except that the added internal electron donor is replaced with poly(3-(2,2,3,3-tetrafluoropropoxy)-1,2-propene oxide)(ID-11), as shown in Table 1.

[0159] Example 14 Preparation of Catalytic Components

[0160] The method is the same as in Example 1, except that the added internal electron donor compound is replaced with poly(2-phenylethylene oxide-1-carboxylic acid methyl ester) (ID-12), as shown in Table 1.

[0161] Example 15 Preparation of Catalytic Components

[0162] The method is the same as in Example 1, except that the added internal electron donor is poly(myricetin) (ID-13), as shown in Table 1.

[0163] Example 16 Preparation of Catalytic Components

[0164] The method is the same as in Example 1, except that the added internal electron donor is poly(3-phenylethylene oxide carboxylate) (ID-14), as shown in Table 1.

[0165] Example 17 Preparation of Catalytic Components

[0166] The method is the same as in Example 1, except that the added internal electron donor is benzoyl glycidyl ester (i.e., the epoxy monomer corresponding to ID-1), and the amount of the internal electron donor compound added is 6 mmol. Using TiCl4 present during the catalyst component preparation process as an initiator, benzoyl glycidyl ester undergoes in-situ ring-opening polymerization during the catalyst component preparation process to generate ID-1, ultimately obtaining the catalyst component. The results are shown in Table 1.

[0167] Comparative Example 1

[0168] The method is the same as in Example 1, except that the internal electron donor is replaced with DNBP (di-n-butyl phthalate), as shown in Table 1.

[0169] Application example: propylene polymerization experiment

[0170] The catalytic components obtained in Examples 1-16 and Comparative Example 1 were subjected to propylene polymerization.

[0171] The propylene polymerization procedure was as follows: A 5L stainless steel reactor was filled with propylene gas, followed by the addition of 2.5 mmol of AlEt and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMDMS, as an external electron donor), resulting in an Al / Si (mol) ratio of 25. Then, 10 mg of the prepared catalyst and 1.2L of hydrogen gas were added, and 2.3L of liquid propylene was introduced. 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.

[0172] Table 1 Catalyst composition and propylene polymerization results

[0173]

[0174] DNBP is di-n-butyl phthalate.

[0175] The isotactic index of polymers is determined by the heptane extraction method. A 2g dry polymer sample 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.

[0176] Test method for melt index (MI) of polymer: determined according to GB / T 3682-2000.

[0177] Polymer molecular weight distribution (MWD, MWD = M) w / M n Test method: Gel permeation chromatography was used, with PL-GPC220 and trichlorobenzene as solvent at 150℃ (standard: polystyrene, flow rate: 1.0 mL / min, column: 3xPlgel 10um M1xED-B 300x7.5nm).

[0178] 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.

[0179] As can be seen from the olefin polymerization experimental data in Table 1, using polyethylene oxide / polyethylene glycol derivative compounds with specific structures as shown in general formula (I) as internal electron donor compounds for preparing olefin polymerization catalyst components, the resulting catalyst components exhibit good polymerization activity in the polymerization reaction, and the resulting polymer products have a wide molecular weight distribution, high melt index, and a large adjustable range of isotactic index.

[0180] 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.

[0181] 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 catalytic component, characterized in that, The catalytic component comprises magnesium, titanium, and an internal electron donor compound, wherein the internal electron donor is selected from at least one of the electron donor compounds shown in general formula (I): 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.

2. The catalytic component according to claim 1, characterized in that, In the catalytic component, the molar ratio of magnesium, titanium and the electron-donating compound shown in general formula (I) is 1:(0.5-150):(0.02-0.4).

3. The catalytic component according to claim 1 or 2, 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.

4. The catalytic component according to any one of claims 1-3, 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.

5. The catalytic component according to any one of claims 1-4, 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.

6. The catalytic 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 catalytic 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 catalytic component according to claim 7, characterized in that, The catalytic component also contains halogens; in the component, the molar ratio of magnesium, titanium, halogens and electron-donating compound shown in general formula (I) is 1:(0.5-150):(0.1-800):(0.02-0.4).

9. 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 catalytic component according to any one of claims 1 to 8; Component b is an organoaluminum compound.

10. The catalyst according to claim 9, 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).

11. The catalyst according to claim 9 or 10, 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.

12. The catalyst according to claim 11, characterized in that, 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); the molar ratio of titanium to aluminum in the alkylaluminum compound is 1:(5-1000).

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 1-8 or is selected from the catalysts described in any one of claims 9-12.

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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