CN109553708B - Catalyst component for olefin polymerization and preparation method thereof - Google Patents

Catalyst component for olefin polymerization and preparation method thereof Download PDF

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CN109553708B
CN109553708B CN201710887536.3A CN201710887536A CN109553708B CN 109553708 B CN109553708 B CN 109553708B CN 201710887536 A CN201710887536 A CN 201710887536A CN 109553708 B CN109553708 B CN 109553708B
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dioxane
dione
bis
compound
catalyst component
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CN109553708A (en
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王军
高明智
刘海涛
马晶
蔡晓霞
陈建华
马吉星
胡建军
李昌秀
何世雄
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Abstract

The invention discloses a catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown as a general formula I is added in the preparation process of the catalyst component as a precipitation aid;
Figure DDA0001420353630000011
wherein A is selected from- (XR)1R2)n-and- (YR)5)m-, Q is selected from- (XR)3R4)a-or- (YR)6)b-, wherein X is a carbon atom or a silicon atom, Y is a nitrogen atom or a phosphorus atom, and m, n, a, b are 1 to 6; r1～R6May be the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C30A substituted or unsubstituted C2～C30Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Alkoxy group of (2). The catalyst component and the catalyst prepared by the catalyst component are used for olefin polymerization, and have high activity and adjustable orientation capability, good hydrogen regulation sensitivity of the catalyst, and wide molecular weight distribution of the prepared polymer.

Description

Catalyst component for olefin polymerization and preparation method thereof
Technical Field
The invention relates to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst system for olefin polymerization, application of the catalyst component and the catalyst system in olefin polymerization reaction and an olefin polymerization method, and belongs to the field of olefin polymerization.
Background
As is well known, a polyolefin catalyst containing magnesium, titanium, halogen and an electron donor as essential components is obtained by supporting a transition metal compound on an inorganic substance such as magnesium chloride or silica as a carrier. The early magnesium chloride carrier prepared by grinding method has the disadvantages of poor particle shape of catalyst, poor particle shape of polymer obtained by catalysis, more fine powder and low apparent density. Currently, more chemical methods are used, i.e. the magnesium compound is dissolved in a solvent to prepare a homogeneous solution, and then precipitated by crystallization. In the process of dissolution, solid substances with uniform particle size can be obtained only in the presence of the precipitation aid. The auxiliary precipitation agent is usually a compound such as an organic acid anhydride, an organic ketone, an ether, or the like. The precipitation aids reported in the prior art can be of various types of compounds. Such as those reported using alkanes (CN200810223088.8 and CN03123950.1) or organosilicon compounds without active hydrogen as a precipitation aid (CN 201110269970.8). In CN101643519A, a diol ester compound with a special structure is taken as a precipitation aid, and a diol ester compound or a dicarboxylic acid ester compound with a special structure is simultaneously matched and applied as an electron donor to load at least one surface modifier, the catalyst shows high stereospecificity when used for olefin polymerization, and the obtained polymer has wide molecular weight distribution and less fine powder. CN1955195A discloses a catalyst system for olefin polymerization or copolymerization, which is prepared by compounding aromatic monocarboxylic ester and polycarboxylic ester, wherein the aromatic monocarboxylic ester is both a precipitation aid and an electron donor, the catalyst has good particle morphology and impurity resistance, and the obtained polymer has wider molecular weight distribution and less fine powder.
The most reported auxiliary agents in the patent literature include organic acid anhydrides, organic acids, ketones, ethers and other compounds, such as (CN200910091115.5, CN201010204493.2, CN201010294618.5, CN85100997, CN200910083987.7, CN200910209546.7, CN201110335576.x, CN201010283061.5, CN98101108.x, CN98126383.6, CN200810117895.6, CN98126385.2, CN98126383.6, CN98111780.5, CN98101108.x, CN201110335576.x, CN201010294618.5, CN201010283061.5, CN201010204493.2, CN200910209546.7, cn2009177286. x, CN200910091115.5, CN200910086590.3, CN200910084912.1, CN200810117895.1, CN200510114544.1, CN200410062290.9, CN99102813.9, CN98126385.2, CN98126383.6, CN98111780.5, cn98101108.x) and the like. The auxiliary precipitation agent mainly comprises one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and amyl ether, or a mixture of the acetic anhydride, the phthalic anhydride, the succinic anhydride, the maleic anhydride, the pyromellitic anhydride, the acetic acid, the propionic acid, the butyric acid, the acrylic acid, the methacrylic acid, the acetone, the methyl ethyl. Chinese patent CN101864009B discloses a preparation method of a titanium-containing catalyst component, wherein glycol ester compounds are used as a precipitation aid instead of phthalic anhydride compounds, so that the catalyst component with high activity and high directionality is obtained.
In summary, the precipitation assistant with good effect for preparing the olefin polymerization catalyst reported in the patent literature is phthalic anhydride, and the presence of the compound is likely to form phthalate compounds, which is not good for the current environmental protection requirement, so that innovative work needs to be carried out on the basis of the prior art to obtain a polyolefin catalyst with good comprehensive performance and industrial practicability.
Disclosure of Invention
The invention aims to provide a catalyst component for olefin polymerization and a preparation method thereof aiming at the defects of the prior art, a compound with a special structure is introduced as a precipitation aid in the preparation process of the catalyst component, the use of a phthalic anhydride compound is omitted or reduced, and further the catalyst for olefin polymerization is provided.
According to one aspect of the invention, a catalyst component for olefin polymerization is provided, which comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown in a general formula I is added in the preparation process of the catalyst component;
Figure BDA0001420353620000021
wherein A is selected from- (XR)1R2)n-and- (YR)5)m-, Q is selected from- (XR)3R4)a-or- (YR)6)b-, wherein X is a carbon atom or a silicon atom, Y is a nitrogen atom or a phosphorus atom, and m, n, a, b are each an integer of 1 to 6; r1～R6May be the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C30A substituted or unsubstituted C2～C30Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Preferably selected from hydrogen, substituted or unsubstituted C1～C30Linear alkyl, substituted or unsubstituted C of3～C30Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C30Linear alkenyl of (A), substituted or unsubstituted C3～C30Substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C7～C30Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C30A substituted or unsubstituted C4～C30Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Alkoxy group of (a); and R is1～R6Not hydrogen at the same time.
According to a preferred embodiment of the invention, m is an integer from 1 to 6, preferably from 1 to 4; n is an integer of 1-6, preferably 1-4; a is an integer of 1-6, preferably 1-4; b is an integer of 1-6, preferably 1-4; the R is1～R6May be the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C10A substituted or unsubstituted C4～C10Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C10Preferably from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, propoxy, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group, chloro, bromo, iodo, hydroxy and hydroxyalkyl.
According to the invention, said substitution means R1～R6The hydrogen atom bonded to the carbon atom in the alkyl, cycloalkyl, aryl, alkaryl or aralkyl group in (1) may be optionally substituted with a heteroatom, an alkyl group or an alkoxy group, and the carbon atom in the main chain may be optionally substituted with a heteroatom. The heteroatom comprisesHalogen atom, and the like.
According to some embodiments of the invention, the compound of formula I is selected from the group consisting of 3, 6-diphenyl-1, 4-dioxane-2, 5-dione, 3, 6-bis (4-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, -bis (2, 4-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2,4, 6-trimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2, 4-dimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2,4, 6-trimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2-methylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diphenyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-1, 4-dioxane-2, 5-dione, 3, 6-diethyl-1, 4-dioxane-2, 5-dione, 3, 6-di-n-propyl-1, 4-dioxane-2, 5-dione, 3, 6-diisopropyl-1, 4-dioxane-2, 5-dione, 3, 6-di-n-butyl-1, 4-dioxane-2, 5-dione, 3, 6-diisobutyl-1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylpropyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylbutyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylpentyl) -1, 4-dioxane-2, 5-dione, 3, 6-di-n-pentyl-1, 4-dioxane-2, 5-dione, 3, 6-diisoamyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-propyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diisopropyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-butyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diisobutyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-pentyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diisoamyl-1, 4-dioxane-2, 5-dione, 2,5, 5-tetramethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2,5, 5-tetraethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2,5, 5-tetrapropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2,5, 5-tetrabutyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2,5, 5-disilicon-2, 5-disilicon-3, 6-dione, 2, 2-dimethyl-5, 5-diethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dimethyl-5, 5-dipropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dimethyl-5, 5-dibutyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-diethyl-5, 5-diethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-diethyl-5, 5-dipropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-diethyl-5, 5-dibutyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dipropyl-5, 5-diethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dipropyl-5, 5-dipropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dipropyl-5, 5-dibutyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dibutyl-5, 5-diethyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dibutyl-5, 5-dipropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dibutyl-5, 5-dipropyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2-dibutyl-5, 5-dibutyl-1, 4-dioxane-2, 5-disilicon-3, 6-dione, 2, 5-dimethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-diethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dipropyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dibutyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-diamyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dihexyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dimethoxymethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dimethoxyethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dimethoxypropyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-diethoxymethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-diethoxyethyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-diethoxypropyl-1, 4-dioxane-2, 5-diaza-3, 6-dione, 2, 5-dimethyl-1, 4-dioxane-2, 5-diphospha-3, 6-dione, 2, 5-diethyl-1, 4-dioxane-2, 5-diphospha-3, 6-dione, 2, 5-dipropyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-dibutyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-diamyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-dihexyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-dimethoxymethyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-dimethoxyethyl-1, 4-dioxane-2, 5-diphospho-3, 6-dione, 2, 5-dimethoxypropyl-1, 5-dimethoxypropyl-2, 5-dioxane-3, 6-dione, 4-dioxane-2, 5-diphosphine-3, 6-diketone, 2, 5-diethoxymethyl-1, 4-dioxane-2, 5-diphosphine-3, 6-diketone, 2, 5-diethoxyethyl-1, 4-dioxane-2, 5-diphosphine-3, 6-diketone and one or more of 2, 5-diethoxypropyl-1, 4-dioxane-2, 5-diphosphine-3, 6-diketone.
Among the above compounds, the fact that a normal or abnormal compound is not indicated means that the normal or abnormal group is included.
According to a preferred embodiment of the present invention, the compound of formula I is added as a precipitation aid during the preparation of the catalyst component.
According to some embodiments of the invention, the catalyst component is prepared by a process comprising the steps of:
1) dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a homogeneous solution;
2) mixing the uniform solution with a titanium compound to obtain a mixture;
3) adding an internal electron donor compound into the mixture obtained in the step 2), and then treating the mixture with a titanium compound or an inert diluent to obtain the catalyst component;
wherein, the compound shown in the structural general formula I is added in the step 1) and/or the step 2).
According to a preferred embodiment of the present invention, the compound of formula I is used in an amount of 0.01 to 6 moles, preferably 0.05 to 2 moles, more preferably 0.02 to 1 mole per mole of magnesium.
According to a preferred embodiment of the present invention, the internal electron donor compound is used in an amount of 0.01 to 15 moles, preferably 0.05 to 10 moles, more preferably 0.1 to 5 moles, per mole of magnesium.
According to some embodiments of the present invention, the magnesium compound comprises at least one of magnesium dihalide, a hydrate of magnesium dihalide, a water or alcohol complex of magnesium dihalide, alkyl magnesium halide, alkoxy magnesium and alkoxy magnesium halide, the halogen being selected from at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine. In some specific embodiments, the magnesium compound preferably includes at least one of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, ethoxymagnesium, and ethoxymagnesium chloride.
According to a preferred embodiment of the invention, the organic epoxide comprises C2-C10At least one of an oxide of an aliphatic olefin, a diene, a halogenated aliphatic olefin, a glycidyl ether and an internal ether. In some specific embodiments, the organic epoxide comprises at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, and diglycidyl ether, preferably epichlorohydrin.
According to one embodiment of the invention, the organophosphorus compound comprises a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid. In some specific embodiments, the organophosphorus compound comprises at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, tributyl phosphite, and triphenyl phosphite, preferably trimethyl orthophosphate.
According to some preferred embodiments of the present invention, the inert diluent is not particularly limited, as long as it does not react with the other components; inert diluents suitable for use in the present invention include at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
According to a preferred embodiment of the invention, the titanium compound comprises a compound of formula Ti (OR)7)xM4-xAnd/or derivatives thereof, wherein R7Is C1-C20Is preferably C1-C10Alkyl groups of (a); m is halogen, preferably chlorine, bromine or iodine; x is 1-4. In some specific embodiments, the titanium compound preferably comprises at least one of a titanium tetrahalide, an alkoxy titanium trihalide, a dialkoxy titanium trihalide, and a trialkoxy titanium halide; more preferably, it comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxyide, titanium tetrabutoxide, titanium monochlorotriethoxyide, titanium dichlorodiethoxylate and titanium trichloroethoxylate. According to one embodiment of the invention, the titanium compound is preferably titanium tetrachloride.
According to some preferred embodiments of the present invention, the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines, preferably from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds, and more preferably comprises one or more of benzoate compounds, phthalate compounds, malonate compounds, succinate compounds and glutarate compounds. In some specific embodiments, the second internal electron donor compound comprises di-n-butyl phthalate, diisobutyl phthalate, 2, 4-diphenylmethylcarboxylpentane, 2, 4-di (methylbenzocarboxyl) pentane, 2, 4-di (ethylbenzylcarboxyl) pentane, 2, 4-di (n-propylbenzylcarboxyl) pentane, 2, 4-di (isopropylbenzylcarboxyl) pentane, 2, 4-di (n-butylbenzylcarboxyl) pentane, 2, 4-di (isobutylbenzylcarboxyl) pentane, 2, 4-di (tert-butylbenzylcarboxyl) pentane, 9-dimethoxymethylfluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxyfluorene, 1, 8-diphenylcarboxynaphthol, 3-tert-butyl-1, one or more of 2-dibenzyl carboxyl phenol and 2, 3-diisopropyl diethyl succinate.
According to a preferred embodiment of the present invention, the organic epoxy compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 5 moles, per mole of magnesium; the amount of the organic phosphorus compound is 0.1 to 3 mol, preferably 0.2 to 2 mol; the titanium compound is used in an amount of 0.5 to 50 mol, preferably 1 to 40 mol.
According to an embodiment of the present invention, the precipitation-aiding agent further comprises a second precipitation-aiding agent, i.e., the compound represented by the general formula I is used in combination with the second precipitation-aiding agent.
According to a preferred embodiment of the invention, the second precipitation aid comprises phthalic anhydride. In some specific embodiments, the second precipitation aid is used in an amount of 0 to 0.3 mol, preferably 0.01 to 0.2 mol, per mol of magnesium.
According to a preferred embodiment of the present invention, said step 1) is preferably carried out by dissolving the magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent, and maintaining at 30 to 150 ℃ for 0.5 to 10 hours until the magnesium compound is completely dissolved to form a homogeneous solution.
According to a preferred embodiment of the present invention, the homogeneous solution is preferably cooled to-40 to 0 ℃ in the step 2), and then a titanium compound is added to contact for 0.5 to 5 hours to obtain a mixture.
According to a preferred embodiment of the present invention, in the step 3), the temperature of the mixture in the step 2) is preferably raised to 50 to 150 ℃, then the internal electron donor compound is added to react at a temperature of 20 to 120 ℃ for 0.5 to 6 hours, and solid particles are separated by filtration; and treating the solid particles with a titanium compound and/or an inert diluent, and drying to obtain the catalyst component.
According to some embodiments of the Pentium bulgaricus, the compound of the general structural formula I can be added in step 1) and/or 2), preferably before the homogeneous solution of step 2) is mixed with the titanium compound.
The catalyst component for olefin polymerization obtained according to the present invention can be used for preparing an olefin polymerization catalyst system.
According to another aspect of the present invention, there is provided a catalyst system for the polymerization of olefins comprising the reaction product of:
a. the above catalyst component for olefin polymerization;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
According to a preferred embodiment of the invention, the molar ratio of component b to component a, calculated as aluminium/titanium, is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500):1, preferably (0.01-50): 1.
According to some embodiments of the present invention, the alkylaluminum compound is not particularly limited, and an alkylaluminum compound that can be used in a ziegler-natta type catalyst, which is commonly used in the art, may be selected.
The aluminum alkyl compounds suitable for use in the present invention are preferably of the formula AlR'n'X'3-n'The alkyl aluminum compound is shown in the specification, wherein R' is selected from hydrogen and C1-C20Alkyl and C6-C20Aryl of (a); x 'is halogen, and n' is an integer of 1 to 3.
In some specific embodiments, as a specific example of the alkylaluminum compound, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride can be selected.
According to a particular embodiment of the invention, said component c being optionally an organosilicon compound means that the catalyst system for the polymerization of olefins may or may not contain organosilicon compounds. According to a preferred embodiment of the present invention, the external electron donor compound is not particularly limited, and an external electron donor compound that can be used in a ziegler-natta type catalyst, which is generally used in the art, may be selected.
Is suitable for the bookThe external electron donor compounds of the invention are preferably of the formula R "m'Si(OR”')4-m'The organic silicon compound is shown in the specification, wherein R' is selected from hydrogen, halogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20A haloalkyl group of (a); m' is an integer of 1 to 3.
In some specific examples, as specific examples of the organosilicon compound, at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, etc., preferably at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane and diphenyldimethoxysilane.
According to another aspect of the present invention there is provided the use of a catalyst system as described above in the polymerisation of olefins.
According to another aspect of the present invention, there is provided an olefin polymerization process comprising carrying out an olefin polymerization reaction using one or more olefins in the presence of the above catalyst component or the above catalyst system.
According to a preferred embodiment of the invention, at least one of said olefins is of formula CH2Olefins represented by ═ CHR, where R is hydrogen or C1-C7Alkyl group of (1).
The olefin polymerization process of the invention can be used for the polymerization of olefins of the general formula CH2Homopolymerization of olefins represented by ═ CHR, can also be used for the preparation of the compound of formula CH2Olefins represented by ═ CHR are copolymerized with various olefins. R is hydrogen orC1-C7Alkyl group of (1). Said general formula is CH2Specific examples of olefins represented by ═ CHR include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
According to the olefin polymerization process of the present invention, the olefin polymerization conditions are not particularly limited, and the conditions conventional in the art may be selected; the amount of the catalyst to be used is not particularly limited, and the amount of each catalyst to be used in the olefin polymerization of the prior art can be selected.
According to the invention, a compound with a special structure is introduced in the preparation process of the catalyst component as a precipitation aid, so that the use of a phthalic anhydride compound is omitted or reduced, the obtained catalyst component has high catalytic activity and slow activity decay, and the obtained polymer has high melt index, wide molecular weight distribution and high isotacticity. The catalyst provided by the invention has the advantages of excellent comprehensive catalytic activity performance, higher activity, adjustable orientation capability, good hydrogen regulation sensitivity, adjustable isotactic index of the prepared polymer and wider molecular weight distribution.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the following examples, the evaluation and testing methods involved are as follows:
1. polymer isotacticity (%): determination by heptane extraction: a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours and the residue was dried to constant weight, the ratio of the weight of the polymer (g) to 2g being the isotacticity.
2. Polymer melt index (g/10 min): measured according to ASTM D1238-99.
3. Polymer molecular weight distribution (Mw/Mn): measuring with gel permeation chromatograph manufactured by Waters company, and using 1,2, 4-trichlorobenzene and styrene as standard sample as solvent; nuclear magnetic analysis of the Compounds the 1H-NMR of the polymer was determined with a Bruke dmx 300MHz NMR spectrometer, solvent: deuterated chloroform with TMS as internal standard and temperature 275K.
Synthesis of Compound (I)
EXAMPLE 1 Synthesis of 3, 6-diphenyl-1, 4-dioxane-2, 5-dione, Compound
In a 250 ml three-necked flask, after nitrogen purging, 3.04 g of mandelic acid, 80 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 4 hours, the reaction was refluxed for 6 hours at elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 1.07 g of a product (yield 40%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3) 7.40 to 7.38(6H, m, ArH),7.36 to 7.34(4H, m, ArH),6.10 to 6.08(2H, m, CH); mass Spectrometry, FD-mass spectrometry: 268.
EXAMPLE 2 Synthesis of the Compound 3, 6-bis (4-ethylphenyl) -1, 4-dioxane-2, 5-dione
In a 250 ml three-necked flask, after nitrogen gas was purged, 3.60 g of 4-ethylmandelic acid, 80 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 1 hour, the reaction was refluxed for 8 hours at elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 1.23 g of a product (yield 38%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.32～7.30(4H,m,ArH),7.05～7.03(4H,m,ArH),6.10～6.08(2H,m,CH),2.58～2.56(4H,m,CH2),1.25～1.22(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 324.
EXAMPLE 3 Synthesis of 3, 6-bis (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione, Compound
In a 250 ml three-necked flask, after nitrogen purging, 3.88 g of 4-n-propylmandelic acid, 80 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 1 hour, the reaction was refluxed at elevated temperature for 12 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 1.33 g of a product (yield 38%).
Subjecting the product to nucleationMagnetic assay, test methods and results were:1H-NMR(δ,ppm,TMS,CDCl3):7.32～7.29(4H,m,ArH),7.05～7.03(4H,m,ArH),6.10～6.08(2H,m,CH),2.63～2.61(4H,m,CH2),1.64～1.62(4H,m,CH2),0.95～0.92(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 352.
EXAMPLE 4 Synthesis of the Compound 3, 6-bis (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione
The same as in example 3, except that 4-n-propylmandelic acid was replaced with 4-isopropylmandelic acid, 1.40 g of a product was obtained (yield 40%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.28～7.26(4H,m,ArH),7.23～7.21(4H,m,ArH),6.08～6.06(2H,m,CH),2.88～2.86(2H,m,CH2),1.23～1.20(6H,m,CH3)，1.18～1.15(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 352.
EXAMPLE 5 Synthesis of the Compound 3-phenyl-6- (4-ethylphenyl) -1, 4-dioxane-2, 5-dione
In a 250 ml three-necked flask, after nitrogen gas was purged, 3.10 g of mandelic acid, 100 ml of toluene, 3.60 g of 4-ethylmandelic acid and 0.3 ml of concentrated sulfuric acid were added, and the mixture was stirred at room temperature for 8 hours and then heated under reflux for 10 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 0.97 g of a product (yield 33%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.38～7.36(5H,m,ArH),7.33～7.31(2H,m,ArH),7.03～7.01(2H,m,ArH),6.10～6.08(2H,m,CH),2.59～2.57(2H,m,CH2),1.26～1.24(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 296.
EXAMPLE 6 Synthesis of the Compound 3-phenyl-6- (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione
In a 250 ml three-necked flask, after nitrogen gas was purged, 3.10 g of mandelic acid, 3.88 g of 4-isopropylmandelic acid, 100 ml of toluene and 0.4 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 8 hours, the reaction was refluxed at elevated temperature for 10 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 0.96 g of a product (yield 31%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.38～7.36(5H,m,ArH),7.28～7.26(2H,m,ArH),7.23～7.21(2H,m,ArH),6.10～6.08(2H,m,CH),2.87～2.85(1H,m,CH),1.25～1.22(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 310.
EXAMPLE 7 Synthesis of the Compound 3, 6-bis (4-chlorophenyl) -1, 4-dioxane-2, 5-dione
In a 250 ml three-necked flask, after nitrogen purging, 3.72 g of 4-chloromandelic acid, 80 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 6 hours, the reaction was refluxed for 12 hours at an elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 1.41 g of a product (yield 42%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3) 7.42 to 7.40(4H, m, ArH),7.31 to 7.28(4H, m, ArH),6.08 to 6.06(2H, m, CH); mass Spectrometry, FD-mass spectrometry: 336.
EXAMPLE 8 Synthesis of 3, 6-diisobutyl-1, 4-dioxane-2, 5-dione, a Compound
In a 250 ml three-necked flask, after nitrogen gas was purged, 5.28 g of 2-hydroxy-4-methylpentanoic acid, 80 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring and reacting for 8 hours, the mixture was refluxed and reacted for 8 hours, and after concentration under reduced pressure, the mixture was subjected to column chromatography to obtain 1.45 g of a colorless liquid (yield: 32%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):4.80～4.78(2H,m,CH),1.89～1.86(4H,m,CH2),1.63～1.61(2H,m,CH),0.95～0.92(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 228.
EXAMPLE 9 Synthesis of 3, 6-di-n-propyl-1, 4-dioxane-2, 5-dione, Compound
In a 250 ml three-necked flask, after nitrogen purging, 4.73 g of 2-hydroxyvaleric acid, 100 ml of toluene and 0.3 ml of concentrated sulfuric acid were added and stirred at room temperature. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 10 hours. Concentration under reduced pressure and column chromatography gave 1.20 g of a colorless liquid (yield 30%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):4.80～4.78(2H,m,CH),1.95～1.92(4H,m,CH2)，1.33～1.30(4H,m,CH2),0.93～0.90(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 200.
EXAMPLE 10 Synthesis of the Compound 3, 6-bis (1-methylpropyl) -1, 4-dioxane-2, 5-dione
In a 250 ml three-necked flask, 5.28 g of 2-hydroxy-3-methylpentanoic acid, 100 ml of toluene and 0.3 ml of concentrated sulfuric acid were added after purging with nitrogen, and stirred at room temperature. After 4 hours of reaction with stirring, the mixture was refluxed for 10 hours, concentrated under reduced pressure and subjected to column chromatography to obtain 1.36 g of a colorless liquid (yield: 30%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):4.80～4.78(2H,m,CH),2.89～2.87(2H,m,CH),1.56～1.53(4H,m,CH2),0.99～0.97(6H,m,CH3),0.93～0.90(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 228.
Preparation of component in catalyst and propylene polymerization
Example 11
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 97ml of toluene, 4ml of epichlorohydrin and 12.5ml of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, and the temperature is raised to 50 ℃ under stirring and maintained for 2.5 hours. After the solid is completely dissolved, adding the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione (8mmol), maintaining for 1 hr, cooling the solution to below-25 deg.C, and adding TiCl dropwise within 1 hr4Slowly heating to 80 ℃, adding 6mmol of electron donor compound 2, 4-dibenzyl carboxyl pentane, and keeping the temperature at 80 ℃ for 1 hourThen (c) is performed. After filtration, 70ml of toluene was added, and the mixture was washed twice. 60ml of toluene and TiCl were added440ml, heated to 110 ℃ and maintained for 2 hours. After filtration, 60ml of toluene was added and the mixture was washed at boiling temperature for 5 minutes. 60ml of hexane were added and the mixture was washed twice at boiling temperature for 5 minutes each time. Then 60ml of hexane was added, and the mixture was washed twice at normal temperature for 5 minutes each time and dried to obtain a solid catalyst component.
(2) Polymerization of propylene
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of methylcyclohexyldimethoxysilane (CHMMS) was added in an amount of 0.1mol, 10mg of the solid component prepared in the above example and 1.2NL of hydrogen gas were added, 2.3L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, and then the temperature was lowered and the pressure was released to obtain PP powder, and the results are shown in Table 1.
Example 12
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione was replaced by 3, 6-bis (4-ethylphenyl) -1, 4-dioxane-2, 5-dione.
Example 13
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione was replaced with 3, 6-bis (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione.
Example 14
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione was replaced by 3, 6-bis (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione.
Example 15
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione was replaced by 3, 6-diisobutyl-1, 4-dioxane-2, 5-dione.
Example 16
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione (6mmol) was replaced with 3-phenyl-6- (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione.
Example 17
In example 16, only the compound 2, 4-diphenylmethylcarboxypentane was replaced by DNBP (di-n-butyl phthalate).
Example 18
In the same manner as in example 11, only the compound 2, 4-dibenzylcarboxypentane therein was replaced by 2, 4-di (n-butylbenzocarboxypentane).
Example 19
In example 11, only the compound 2, 4-diphenylmethylcarboxypentane was replaced by DIBP (diisobutylphthalate).
Example 20
In the same manner as in example 16, only the compound 2, 4-diphenylcarboxypentane therein was replaced by 9, 9-dimethoxymethylfluorene.
Example 21
In the same manner as in example 16, only the compound 2, 4-dibenzylcarboxypentane therein was replaced by 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
Example 22
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione (8mmol) was replaced with 3, 6-diphenyl-1, 4-dioxane-2, 5-dione (4mmol) and phthalic anhydride (0.7 g).
Example 23
The same as example 11 except that the amount of hydrogenation in example was changed to 7.2NL, the results are shown in Table 1.
Comparative example 1
In the same manner as in example 11, only the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-dione (6mmol) was replaced with phthalic anhydride (1.4 g).
Comparative example 2
The same as in comparative example 1, except that the amount of hydrogen added at the time of polymerization was changed to 7.2 NL. The polymerization data are shown in Table 1.
TABLE 1
Figure BDA0001420353620000151
Figure BDA0001420353620000161
As can be seen from Table 1, the catalytic activity of the catalyst component and catalyst prepared by using the precipitation aid of the present application, the isotacticity and the melt index of the prepared polymer all reach or even exceed the levels of the prior art, and as can be seen from comparison of the data of examples 11 to 16 with the data of comparative example 1, the catalyst component and catalyst prepared by using the precipitation aid of the present application have wider molecular weight distribution under the same reaction conditions than those of using phthalic anhydride as the precipitation aid. Under the condition of high hydrogen, the catalyst component and the catalyst prepared by the precipitation aid have better catalytic activity, and the obtained polymer has higher melt index, which shows that the catalyst has better hydrogen regulation sensitivity.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (16)

1. A catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown as a general formula I is added in the preparation process of the catalyst component;
Figure FDA0002744771620000011
wherein A is- (XR)1R2)n-, Q is- (XR)3R4)a-, wherein X is a carbon atom, and n and a are each an integer of 1 to 6; r1～R4Same or different, each independently selected from hydrogen, substituted or unsubstituted C1～C30And substituted or unsubstituted C1～C30Alkoxy group of (a); and R is1～R4Not hydrogen at the same time.
2. The catalyst component according to claim 1, wherein R is1～R4Selected from hydrogen, substituted or unsubstituted C1～C30Linear alkyl, substituted or unsubstituted C of3～C30Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C30Linear alkenyl of (A), substituted or unsubstituted C3～C30Substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C7～C30And substituted or unsubstituted C1～C30Alkoxy group of (2).
3. The catalyst component according to claim 1 in which R is1～R4Same or different, each independently selected from hydrogen, substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl of (5)Or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10And substituted or unsubstituted C1～C10Alkoxy group of (2).
4. The catalyst component according to claim 3 in which R is1～R4Selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, and propoxy.
5. The catalyst component according to claim 1, wherein the compound of formula I is selected from the group consisting of 3, 6-diphenyl-1, 4-dioxane-2, 5-dione, 3, 6-bis (4-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-ethylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-n-butylphenyl) -1, 4-dioxane-2, 5-dione, 3, -bis (2, 4-methylphenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2,4, 6-trimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (4-n-propylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (4-isopropylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2, 4-dimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2,4, 6-trimethylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2-methylphenyl) -1, 4-dioxane-2, 5-dione, 3-phenyl-6- (2-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (4-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (2-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (3-chlorophenyl) -1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diphenyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-1, 4-dioxane-2, 5-dione, 3, 6-diethyl-1, 4-dioxane-2, 5-dione, 3, 6-di-n-propyl-1, 4-dioxane-2, 5-dione, 3, 6-diisopropyl-1, 4-dioxane-2, 5-dione, 3, 6-di-n-butyl-1, 4-dioxane-2, 5-dione, 3, 6-diisobutyl-1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylpropyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylbutyl) -1, 4-dioxane-2, 5-dione, 3, 6-bis (1-methylpentyl) -1, 4-dioxane-2, 5-dione, 3, 6-di-n-pentyl-1, 4-dioxane-2, 5-dione, 3, 6-diisoamyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-propyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diisopropyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-butyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-diisobutyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-1, 4-dioxane-2, 5-dione, 3, 6-dimethyl-3, 6-di-n-amyl-1, 4-dioxane-2, 5-diketone, 3, 6-dimethyl-3, 6-diisoamyl-1, 4-dioxane-2, 5-diketone and 3, 6-diethyl-3, 6-di-n-propyl-1, 4-dioxane-2, 5-diketone.
6. The catalyst component according to any of claims 1 to 5, characterized in that it is prepared by a process comprising the following steps:
1) dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a homogeneous solution;
2) mixing the uniform solution with a titanium compound to obtain a mixture;
3) adding an internal electron donor compound into the mixture obtained in the step 2), and then treating the mixture with a titanium compound or an inert diluent to obtain the catalyst component;
wherein, the compound shown in the structural general formula I is added in the step 1) and/or the step 2).
7. The catalyst component according to claim 6, wherein the magnesium compound comprises at least one of a magnesium dihalide, a hydrate of a magnesium dihalide, a water or alcohol complex of a magnesium dihalide, an alkyl magnesium halide, an alkoxy magnesium and an alkoxy magnesium halide, and the halogen is selected from at least one of fluorine, chlorine, bromine and iodine.
8. The catalyst component according to claim 7 in which the halogen is chlorine and/or bromine.
9. The catalyst component according to any of claims 1 to 5 wherein the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines.
10. The catalyst component according to claim 9, wherein the internal electron donor compound is selected from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds.
11. The catalyst component according to any of claims 1 to 5 characterized in that the compound of formula I is used in an amount of 0.01 to 6 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.01 to 15 mol.
12. The catalyst component according to any of claims 1 to 5 characterized in that the compound of formula I is used in an amount of 0.05 to 2 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.05-10 mol.
13. The catalyst component according to any of claims 1 to 5 characterized in that the compound of formula I is used in an amount of 0.02 to 1 mole per mole of magnesium; and/or the amount of the internal electron donor compound is 0.1 to 5 mol.
14. A catalyst system for olefin polymerization comprising the reaction product of:
a. the catalyst component of any one of claims 1 to 13;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
15. The catalyst system of claim 14 wherein the molar ratio of component b to component a is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500): 1.
16. A process for the polymerization of olefins comprising the polymerization of olefins using one or more olefins in the presence of a catalyst component as claimed in any of claims 1 to 13 or a catalyst system as claimed in claim 14 or 15.
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CN102146146A (en) * 2010-02-10 2011-08-10 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst

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