CN109553709B - Catalyst component for olefin polymerization and catalyst thereof - Google Patents

Catalyst component for olefin polymerization and catalyst thereof Download PDF

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CN109553709B
CN109553709B CN201710887556.0A CN201710887556A CN109553709B CN 109553709 B CN109553709 B CN 109553709B CN 201710887556 A CN201710887556 A CN 201710887556A CN 109553709 B CN109553709 B CN 109553709B
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dioxane
dione
compound
bis
catalyst component
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CN109553709A (en
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王军
高明智
陈建华
马晶
刘海涛
马吉星
蔡晓霞
胡建军
李昌秀
何世雄
张志会
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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

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Abstract

The invention discloses a catalyst component for olefin polymerization, which is prepared by a method comprising the following steps: 1) mixing a magnesium compound with an organic alcohol compound and an inert solvent, and adding a compound shown in a structural general formula I for treatment to obtain an alcohol compound; 2) contacting the alcohol compound with a titanium compound at a low temperature, adding an internal electron donor compound for reaction, and separating out first solid particles; 3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating second solid particles; 4) washing the second solid particles obtained in step 3) with an inert solvent to obtain the catalyst component;

Description

Catalyst component for olefin polymerization and catalyst 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.
In general, the most used auxiliary agents in the reports are 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 precipitation assistant in each patent 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. Chinese patent CN101864009B discloses a preparation method of a titanium-containing catalyst component, wherein glycol ester compounds are adopted to replace phthalic anhydride compounds as a precipitation aid, and 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 present invention, there is provided a catalyst component for olefin polymerization, which is prepared by a process comprising the steps of:
1) mixing a magnesium compound with an organic alcohol compound and an inert solvent, and adding a compound shown in a structural general formula I for treatment to obtain an alcohol compound;
2) contacting the alcohol compound with a titanium compound at low temperature, adding an internal electron donor compound for reaction, and separating out first solid particles;
3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating second solid particles;
4) washing the second solid particles obtained in step 3) with an inert solvent to obtain the catalyst component;
Figure BDA0001420360440000031
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 groupChlorine, bromine, iodine, hydroxyl 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 hetero atom includes a halogen 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, di-n-butyl-3, 6-dimethyl-1, 4-dioxane-2, 5-dione, di-n-butyl-,
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-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-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-diphospho-3, 6-dione, 2, 5-diethyl-1, 4-dioxane-2, 5-diphospho-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-diphosphine-3, 6-dione, 2, 5-dimethoxyethyl-1, 4-dioxane-2, 5-diphosphine-3, 6-dione, 2, 5-dimethoxypropyl-1, 4-dioxane-2, 5-diphosphine-3, 6-dione, 2, 5-diethoxymethyl-1, 4-dioxane-2, 5-diphosphine-3, 6-dione, 2, 5-diethoxyethyl-1, 4-dioxane-2, 5-diphosphine-3, 6-dione and 2, 5-diethoxypropyl-1, 4-dioxane-2, 5-diphosphine-3, 6-dione, one or more 6-diketones.
Among the above compounds, the fact that a normal or abnormal compound is not indicated means that the normal or abnormal group is included.
In some embodiments, the compound of general structural formula I described in step 1) is added during or after mixing.
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 compound of formula I is used in an amount of 0.01 to 6 moles, preferably 0.01 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 0.001 to 15 moles, preferably 0.005 to 10 moles, more preferably 0.05 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 some embodiments of the present invention, the organic alcohol compound is not particularly limited, and those commonly used in the art are selectedOrganic alcohol compounds; according to a preferred embodiment of the present invention, the organic alcohol compound includes at least one of aliphatic alcohol, alicyclic alcohol and aromatic alcohol. Wherein the fatty alcohol is preferably C1-C10Of straight-chain fatty alcohols or C3-C10The branched fatty alcohol of (1). The alicyclic alcohol is preferably C3-C12The fatty alcohol of (1). The aromatic alcohol is preferably C6-C20Of aryl alcohol or C7-C20An alkyl aromatic alcohol of (1). In some specific embodiments, the alcohol compound suitable for the present invention preferably includes at least one of ethanol, propanol, butanol, 2-ethylhexanol, isooctanol, benzyl alcohol, and phenethyl alcohol.
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 a preferred embodiment of the present invention, the magnesium compound is preferably mixed with the organic alcohol compound and the inert solvent at 30 to 150 ℃ for 0.5 to 10 hours in the step 1) until the magnesium compound is completely dissolved; then adding the compound shown in the structural general formula I, and continuously reacting for 0.5-3h at the temperature of 30-150 ℃ to obtain the alcohol compound.
In some specific examples, the organic alcohol compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 5 moles, per mole of magnesium.
According to a preferred embodiment of the present invention, in the step 2), the alcohol hydrate is preferably cooled to room temperature, added to a titanium compound at a temperature of-40 to 0 ℃ for contacting for 0.5 to 5 hours, then heated to 50 to 150 ℃, added with an internal electron donor compound for reacting for 0.5 to 6 hours at a temperature of 20 to 120 ℃, and filtered to separate out the first solid particles.
According to a preferred embodiment of the present invention, the first solid particles obtained in step 2) are preferably added to a solution of titanium compound in step 3), reacted at a temperature of 50 to 150 ℃ for 1 to 6 hours, and then filtered to separate the second solid particles.
According to a preferred embodiment of the present invention, the second solid particles obtained in step 3) are preferably washed in step 4) with an inert solvent and dried to obtain the catalyst component.
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, expressed as the aluminium/titanium ratio, is (5-1000): 1; and/or the molar ratio of component c to component a, in terms of silicon/titanium ratio, 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.
The external electron donor compounds suitable for use in the present invention are preferably of the general 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 or C1-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%).
And performing nuclear magnetic assay on the product, wherein the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.32～7.29(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 anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent were added to a 500ml reactor equipped with a stirrer under nitrogen protection, heated to 130 ℃ and reacted for 1.5 hours until the magnesium chloride was completely dissolved. Adding the compound 3, 6-diphenyl-1, 4-dioxane-2, 5-diketone (8mmol) of the structural general formula I, and continuously maintaining the temperature at 130 ℃ for reacting for 1 hour to obtain the alcohol compound. The alcohol hydrate was cooled to room temperature. Under the protection of nitrogen, the alcohol compound is added dropwise into 120ml titanium tetrachloride solution which is precooled to minus 22 ℃, slowly heated to 100 ℃, 6mmol of 2, 4-dibenzyl carboxyl pentane compound is added, and the temperature is raised to 110 ℃ and maintained for 2 hours. Filtering while the solution is hot, adding 120ml of titanium tetrachloride, heating to 110 ℃, reacting for 2 hours, and filtering. The solid particles were washed 4 times with anhydrous hexane and dried to obtain a solid catalyst.
(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) in an amount of 0.1mol, 8 to 10mg of the solid component prepared in the above example and 1.2NL of hydrogen were added thereto, and 2.3L of liquid propylene was introduced, and the temperature was raised to 70 ℃ and maintained 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 16, only the compound 2, 4-dibenzylcarboxypentane therein was replaced by 2, 4-di (n-butylbenzocarboxypentane).
Example 19
In example 16, only the compound 2, 4-diphenylmethylcarboxypentane was replaced with 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 BDA0001420360440000151
As can be seen from the comparison of the data of examples 11-16 with the data of comparative example 1, the catalyst components and catalysts prepared by using the precipitation aid of the present application have catalytic activity, isotacticity and melt index which all reach or even exceed the level of the prior art, and under the same conditions, the polymers obtained by using the catalyst components and catalysts prepared by using the precipitation aid of the present application have wider molecular weight distribution than those obtained by using phthalic anhydride as the precipitation aid. Under the condition of high hydrogen, the catalyst component and the catalyst prepared by the auxiliary precipitator have higher melt index of the obtained polymer, 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 (18)

1. A catalyst component for the polymerization of olefins prepared by a process comprising the steps of:
1) mixing a magnesium compound with an organic alcohol compound and an inert solvent, and adding a compound shown in a structural general formula I for treatment to obtain an alcohol compound;
2) contacting the alcohol compound with a titanium compound at a temperature of between 40 ℃ below zero and 0 ℃, adding an internal electron donor compound, and separating out a first solid particle;
3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating to obtain second solid particles;
4) washing the second solid particles obtained in step 3) with an inert solvent to obtain the catalyst component;
Figure FDA0002745250710000011
wherein A is- (XR)1R2)n-, Q is- (XR)3R4)a-, where X is a carbon atom, 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 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 one of claims 1 to 5, 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.
7. The catalyst component according to claim 6, characterized in that the halogen is chlorine and/or bromine.
8. 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.
9. The catalyst component according to claim 8, 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.
10. The catalyst component according to any of claims 1 to 5 in which the compound of formula I is used in an amount of 0.01 to 6 moles per mole of magnesium.
11. The catalyst component according to any of claims 1 to 5 in which the compound of formula I is used in an amount of 0.01 to 2 moles per mole of magnesium.
12. The catalyst component according to any of claims 1 to 5 in which the compound of formula I is used in an amount of 0.02 to 1 mole per mole of magnesium.
13. The catalyst component according to any of claims 1 to 5, wherein the internal electron donor compound is used in an amount of 0.001 to 15 moles per mole of magnesium.
14. The catalyst component according to any of claims 1 to 5 wherein the internal electron donor compound is used in an amount of 0.005 to 10 moles per mole of magnesium.
15. The catalyst component according to any of claims 1 to 5, characterized in that the internal electron donor compound is used in an amount of 0.05 to 5 moles per mole of magnesium.
16. A catalyst system for olefin polymerization comprising the reaction product of:
a. the catalyst component of any one of claims 1 to 15;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
17. The catalyst system of claim 16 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.
18. 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 15 or a catalyst system as claimed in claim 16 or 17.
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