CN109553704B - Catalyst component for olefin polymerization, catalyst and application - Google Patents

Catalyst component for olefin polymerization, catalyst and application Download PDF

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CN109553704B
CN109553704B CN201710886613.3A CN201710886613A CN109553704B CN 109553704 B CN109553704 B CN 109553704B CN 201710886613 A CN201710886613 A CN 201710886613A CN 109553704 B CN109553704 B CN 109553704B
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methyl
acid
methyl ester
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CN109553704A (en
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王军
高明智
陈建华
刘海涛
马吉星
蔡晓霞
马晶
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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    • 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
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Abstract

The invention discloses a catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor comprises a compound shown as a general formula I,
Figure DDA0001420276810000011
wherein A is selected from carbon atom or silicon atom; r1～R2May be the same or different and is selected from hydrogen, substituted or unsubstituted C1～C30A substituted or unsubstituted C2～C30Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Alkoxy of R1And R2Can be linked to form a ring; r and R' may be the same or different and are selected from substituted or unsubstituted C1～C30And substituted or unsubstituted C2～C30The heterocyclic group of (1). 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, catalyst and application
Technical Field
The invention relates to a catalyst component for olefin polymerization, a preparation method thereof and a catalyst system for olefin polymerization, and application of the catalyst component and the catalyst system in olefin polymerization reaction and an olefin polymerization method, belonging to the field of olefin polymerization.
Background
For the conventional Ziegler-Natta catalysts, polyolefin catalysts are continuously updated with the development of electron donor compounds in the catalysts. Development of the catalyst from the first TiCl3AlCl3/AlEt2Cl system and second generation of TiCl3/AlEt2Cl system, magnesium chloride of the third generation as a carrier, monoester or aromatic dibasic acid ester as an internal electron donor, and TiCl with silane as an external electron donor4·ED·MgCl2/AlR3The catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved by an ED system. In the prior art, a titanium catalyst system for propylene polymerization mostly uses magnesium, titanium, halogen and an electron donor as basic components, wherein the electron donor compound is one of the essential components in the catalyst component. Currently, various electron donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyethers, alcohols, amines, etc. and derivatives thereof, among which aromatic dicarboxylic acid esters (such as di-n-butyl phthalate or diisobutyl phthalate, etc., see US4784983) are more commonly used. In the components disclosed in U.S. Pat. No. 4,497,1937 and EP0728769 for olefin polymerization catalysts, specific 1, 3-diether compounds containing two ether groups are used as electron donors, such as 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-diethanolIsobutyl-1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene, and the like. Thereafter, a special class of aliphatic dicarboxylic acid ester compounds such as succinate, malonate, glutarate and the like is disclosed (see WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), and the use of the electron donor compound can not only improve the activity of the catalyst, but also obviously widen the molecular weight distribution of the obtained propylene polymer.
In recent years, many electron donor compounds with novel structures for olefin polymerization catalysts have emerged, such as ether alcohol ester internal electron donor compounds with both ether group and ester group in the molecular structure (WO2012175425, US20100974322, US20100974667), phenylacetate (WO2013/174759) and phenylpropionate ester electron donor compounds (WO 2013057026). Chinese patent reports that tricarboxylic acid ester compounds (CN102399329) and disubstituted succinic anhydride compounds (CN102286117) are used as catalysts for olefin polymerization synthesized by internal electron donors, but the overall effect of the obtained catalysts is not outstanding.
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, wherein a compound functional group compound is introduced into the catalyst component as an internal electron donor, so that the catalyst for olefin polymerization is further provided.
According to one aspect of the present invention, there is provided a catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor comprising a compound represented by formula I,
Figure BDA0001420276800000021
wherein A is selected from carbon atom or silicon atom; r1～R2Can be the same as orDifferent, 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); r1And R2Can be linked to form a ring;
r and R' may be the same or different and are independently selected from substituted or unsubstituted C1～C30And substituted or unsubstituted C2～C30Preferably selected from 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～C30And substituted or unsubstituted C4～C30The aromatic heterocyclic group of (1).
According to some embodiments of the invention, the R is1～R2Independently selected from hydrogen, substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20A branched alkyl or cycloalkyl group of,Substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl, substituted or unsubstituted C7～C20Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C20A substituted or unsubstituted C4～C20Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C20Preferably selected from the group consisting of 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; r1And R2Optionally linked to form a ring, preferably R on each X1And R2Optionally linked to substituted or unsubstituted C3～C10Cycloalkyl, substituted or unsubstituted C3～C10Or is substituted or unsubstituted C2～C10And heterocyclic groups such as cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl and cyclopentadienyl.
According to a preferred embodiment of the invention, said R and R', which may be identical or different, are independently selected from substituted or unsubstituted C1～C10And substituted or unsubstituted C2～C10Preferably selected from 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～C10And substituted or unsubstituted C4～C10The aromatic heterocyclic group of (a) is preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group and hydroxyalkyl.
According to the invention, said substitution means R1～R2The hydrogen atom bonded to a carbon atom in the alkyl, cycloalkyl, aryl, alkaryl or aralkyl group in R and R' may be optionally substituted with a heteroatom, an alkyl group or an alkoxy group, and the carbon atom on 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 (ethoxycarbonyl) (phenyl) methyl benzoate, (propoxycarbonyl) (phenyl) methyl benzoate, (butoxycarbonyl) (phenyl) methyl benzoate, (pentyloxycarbonyl) (phenyl) methyl benzoate, (ethoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (propoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (butoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (ethoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, and mixtures thereof, (ethoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 2-propylbenzoate, (ethoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (propoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (butoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (ethoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, 2-Chlorobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 2-Chlorobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 2-Chlorobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 2-Chlorobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 3-Chlorobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 3-Chlorobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 3-Chlorobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 3-Chlorobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-Chlorobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 4-Chlorobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-Chlorobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-Chlorobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 2-Bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 2-Bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (propyloxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (propyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylmethylbenzoic acid (butyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, benzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-methylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, (cyclopentyloxycarbonyl) (phenyl) methyl benzoate, 4-methylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, (ethoxycarbonyl) (phenyl) methyl acetate, (propoxycarbonyl) (phenyl) methyl n-propionate, (butoxycarbonyl) (phenyl) methyl iso-propionate, (pentyloxycarbonyl) (phenyl) methyl n-butyrate, (ethoxycarbonyl) (phenyl) methyl 3-methylbutyrate, (ethoxycarbonyl) (phenyl) methyl n-pentanoate, (ethoxycarbonyl) (phenyl) methyl n-valerate, (propoxycarbonyl) (phenyl) methyl iso-valerate, (propoxycarbonyl) (phenyl) methyl n-hexanoate, (propoxycarbonyl) (phenyl) methyl hexanoate, (ethoxycarbonyl) (phenyl) methyl phenylacetate, (propoxycarbonyl) (phenyl) methyl phenylacetate, (butoxycarbonyl) (phenyl) methyl phenylacetate, (2-furylmethoxycarbonyl) (phenyl) methyl benzoate, (2-furylmethoxycarbonyl) (phenyl) methyl 4-methylbenzoate, 4-n-butylbenzoic acid (2-furanmethyloxycarbonyl) (phenyl) methyl ester, 4-iso-butylbenzoic acid (2-furanmethyloxycarbonyl) (phenyl) methyl ester, benzoic acid (2-pyranyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (2-pyranyloxycarbonyl) (phenyl) methyl ester and 4-isopropylbenzoic acid (2-pyranyloxycarbonyl) (phenyl) methyl ester.
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 some preferred embodiments of the present invention, the catalyst component further comprises a second internal electron donor compound, i.e. the compound represented by the general formula I is used in combination with the second internal electron donor compound.
Wherein the second 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 benzoates, phthalates, malonates, succinates and glutarates. 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 invention, the compound of formula I is present in the catalyst component in an amount of 0.05 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 2 to 10% by weight; and/or the second external electron donor compound is contained in the catalyst component in an amount of 0 to 20 wt%, preferably 0.01 to 15 wt%, and more preferably 1 to 10 wt%.
According to some embodiments of the invention, the catalyst component comprises a reaction product of a magnesium compound, a titanium compound, and an internal electron donor compound; the internal electron donor comprises a compound shown in a general formula I.
According to a preferred embodiment of the invention, the catalyst component is prepared by a process comprising the steps of:
s1, mixing a magnesium compound with an organic solvent to form a solution, and optionally adding a titanium compound for treatment;
s2, treating the mixture obtained in the step S1 by adopting an internal electron donor compound, and optionally treating the mixture by using a titanium compound and/or an inert diluent to obtain the catalyst component; the internal electron donor comprises a compound shown in a general formula I.
According to some embodiments of the present invention, the treatment in step S1 can be performed with or without the addition of a titanium compound.
According to a preferred embodiment of the present invention, the internal electron donor further comprises a second internal electron donor compound, i.e., the compound represented by the general formula I is used in combination with the second internal electron donor compound.
According to a preferred embodiment of the present invention, the second 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. . 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 10 moles, preferably 0.01 to 5 moles, more preferably 0.2 to 5 moles per mole of magnesium; and/or the second internal electron donor compound is used in an amount of 0 to 10 moles, preferably 0 to 5 moles, more preferably 0.01 to 5 moles.
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 titanium compound comprises a compound of formula Ti (OR)4)aM4-aAnd/or derivatives thereof, wherein R4Is C1-C20Is preferably C1-C10Alkyl groups of (a); m is halogen, preferably chlorine, bromine or iodine; a is 1 to 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 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 some embodiments of the invention, the "optionally treated with a titanium compound and/or an inert diluent" means that the solid may be treated with or without a titanium compound and/or an inert diluent, as desired.
According to a preferred embodiment of the present invention, the preparation method of the above catalyst set may comprise the following specific steps:
1) dissolving magnesium halide in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a uniform solution, then mixing the uniform solution with a titanium compound, and precipitating a solid in the presence of a precipitation aid;
2) the solid is treated by adopting an internal electron donor compound to be loaded on the solid, then is optionally treated by a titanium compound and/or an inert diluent, and finally is filtered, washed and dried to obtain the catalyst component containing components such as titanium, magnesium, halogen, an internal electron donor and the like.
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 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 amount of the titanium compound is 0.5 to 50 mol, preferably 1 to 40 mol;
according to a preferred embodiment of the present invention, the preparation method of the above catalyst set may comprise the following specific steps:
1) suspending alkoxy magnesium or alkoxy magnesium chloride in an inert solvent to form a suspension, and then mixing and contacting with a titanium compound to obtain a solid;
2) the solid is treated by adopting an internal electron donor compound to be loaded on the solid, then is optionally treated by a titanium compound and/or an inert diluent, and finally is filtered, washed and dried to obtain the catalyst component containing components such as titanium, magnesium, halogen, an internal electron donor and the like.
According to some embodiments of the invention, the inert solvent comprises at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
According to a preferred embodiment of the invention, the titanium compound is used in an amount of 0.5 to 50 moles, preferably 1 to 40 moles, per mole of magnesium;
according to a preferred embodiment of the present invention, the preparation method of the above catalyst set may comprise the following specific steps:
1) mixing a magnesium compound, an organic alcohol compound and a titanium compound in an inert solvent to form a uniform solution, heating the uniform solution, and cooling to obtain a spherical carrier;
2) mixing the spherical carrier and a titanium compound, maintaining the mixture at a low temperature for a period of time, heating the mixture, then using an internal electron donor compound, optionally using a titanium compound and/or an inert diluent for treatment, and finally filtering, washing and drying the mixture to obtain the catalyst component containing titanium, magnesium, halogen, an internal electron donor and other components.
According to some embodiments of the present invention, the organic alcohol compound is not particularly limited, and an organic alcohol compound commonly used in the art may be selected; 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 toolsIn the embodiment, 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 present invention, the preparation method of the above catalyst set may comprise the following specific steps:
1) mixing a magnesium compound, an organic alcohol compound and a titanium compound in an inert solvent to form an alcohol compound solution;
2) mixing the alcohol compound solution with a titanium compound, maintaining the mixture at a low temperature for a period of time, heating the mixture, adding an internal electron donor compound for treatment, optionally treating the mixture with a titanium compound and/or an inert diluent, and finally filtering, washing and drying the mixture to obtain the catalyst component containing titanium, magnesium, halogen, an internal electron donor and other components.
According to a preferred embodiment of the present invention, the preparation method of the above catalyst set may comprise the following specific steps:
dissolving magnesium halide in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a uniform solution, adding a compound shown as a general formula I, mixing with a titanium compound, maintaining at a low temperature for a period of time, heating, treating with the titanium compound and/or the inert diluent, treating with an internal electron donor compound, and finally filtering, washing and drying to obtain the catalyst component containing titanium, magnesium, halogen, the internal electron donor and other components.
The catalyst component for olefin polymerization obtained by the preparation method 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 (0.01-100): 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.
Suitable alkylaluminum compounds 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 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, the compound shown in the general formula I is used as an internal electron donor compound for olefin polymerization, the catalytic activity is high, the activity decay is slow, 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 (ethoxycarbonyl) (phenyl) methyl benzoate, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.02 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.40 g of benzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.04 g of a product (yield 72%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):8.06～8.04(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.22～4.20(2H,q,CH2),1.30～1.27(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 284.
EXAMPLE 2 Synthesis of 4-n-butylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of tetrahydrofuran and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.96 g of 4-n-butylbenzoyl chloride dissolved in 40 ml of tetrahydrofuran solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 12 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.27 g of a product (yield: 67%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.94～7.92(2H,m,ArH),7.35～7.33(5H,m,ArH),7.23～7.21(2H,m,ArH),6.10～6.08(1H,m,CH),4.22～4.20(2H,q,CH2),2.55～2.53(2H,m,CH2),1.66～1.64((2H,m,CH2),1.38～1.36(2H,m,CH2),1.30～1.28(3H,m,CH3),1.25～1.22(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 3 Synthesis of 4-isobutylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. 1.96 g of 4-isobutylbenzoyl chloride dissolved in 40 ml of toluene solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then heated under reflux for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.15 g of a product (yield 63%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.95～7.93(2H,m,ArH),7.39～7.36((5H,m,ArH),7.24～7.21(2H,m,ArH),6.10～6.08(1H,m,CH),4.20～4.18(2H,q,CH2),2.53～2.51(2H,m,CH2),2.25～2.22(1H,m,CH3),1.30～1.27(3H,t,CH3),1.25～1.22(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 4 Synthesis of 4-tert-Butylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.96 g of 4-tert-butylbenzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.97～7.95(2H,m,ArH),7.43～7.40(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.20～4.18(2H,q,CH2),1.36～1.32(9H,m,CH3),1.28～1.25(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 5 Synthesis of (Cyclohexyloxycarbonyl) (phenyl) methyl benzoate, a Compound
In a 250 ml three-necked flask, after nitrogen purging, 2.34 g of cyclohexyl mandelate, 100ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.40 g of benzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to 85 ℃ for reflux reaction for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.20 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):8.07～8.05(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.36(5H,m,ArH),6.08～6.06(1H,s,CH),3.93～3.91(1H,m,CH),1.80～1.78(2H,m,CH2),1.56～1.53(4H,m,CH2),1.49～1.47(2H,m,CH2),1.43～1.41(2H,m,CH2) (ii) a Mass Spectrometry, FD-mass spectrometry: 338.
EXAMPLE 6 Synthesis of 3-methylbutanoic acid (ethoxycarbonyl) (phenyl) methyl ester, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of tetrahydrofuran and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropping 1.20 g of 3-methylbutyryl chloride dissolved in 40 ml of tetrahydrofuran solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 14 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 1.58 g of a product (yield 60%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.38～7.35(5H,m,ArH),6.07～6.05(1H,s,CH),4.21～4.19(2H,q,CH),2.40～2.38(1H,m,CH),2.16～2.14(2H,m,CH2),1.30～1.28(3H,t,CH3),0.94～0.92(6H,d,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 264.
EXAMPLE 7 Synthesis of the Compound 4-n-propylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. 1.82 g of 4-n-propylbenzoyl chloride dissolved in 40 ml of toluene solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.99～7.97(2H,m,ArH),7.38～7.35(5H,m,ArH),6.95～7.93(2H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),2.65～2.63(2H,q,CH2),1.65～1.62(2H,m,CH2),1.28～1.25(3H,t,CH3),0.94～0.92(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 326.
EXAMPLE 8 Synthesis of 4-isopropylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester as Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.82 g of 4-isopropylbenzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.96～7.95(2H,m,ArH),7.42～7.40(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),2.88～2.86(1H,m,CH),1.29～1.26(3H,t,CH3),1.23～1.21(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 326.
EXAMPLE 9 Synthesis of 4-chlorobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.74 g of 4-chlorobenzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.13 g of a product (yield: 67%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.89～7.87(2H,m,ArH),7.62～7.60(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),1.27～1.25(3H,t,CH3) (ii) a Mass Spectrometry, FD-massspectrometry: 318.
EXAMPLE 10 Synthesis of 3-chlorobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.74 g of 3-chlorobenzoyl chloride dissolved in 40 ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.10 g of a product (yield 66%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.98～7.97(1H,m,ArH),7.93～7.91(1H,m,ArH),7.70～7.68(1H,m,ArH),7.50～7.48(1H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.22～4.20(2H,q,CH2),1.29～1.27(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 318.
Preparation of component in catalyst and propylene polymerization
Example 11
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, the solution is cooled to the temperature below minus 25 ℃, and TiCl is dropwise added within 1 hour460mL of the reaction solution was slowly heated to 80 ℃ to gradually precipitate a solid, and the compound, benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (6mmol), was added thereto and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. 100mL of toluene was added, the temperature was raised to 110 ℃ and three washes were carried out for 10 minutes each. Then 60mL of hexane is added for washing three times, and the solid component of the catalyst is obtained after vacuum drying.
(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)5mL of Al/Si (mol) () 25, 10mg of the solid fraction prepared above and 1.2NL of hydrogen gas were added thereto, 2.5L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, and the temperature was lowered, and the pressure was released to obtain a PP resin, and the results are shown in Table 1.
Example 12
In the same manner as in example 11, only the compound of benzoic acid (ethoxycarbonyl) (phenyl) methyl ester was replaced with 4-n-butylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester.
Example 13
In the same manner as in example 11, only the compound of (ethoxycarbonyl) (phenyl) methyl benzoate was replaced with (ethoxycarbonyl) (phenyl) methyl 4-isobutylbenzoate.
Example 14
In the same manner as in example 11, only the compound benzoic acid (ethoxycarbonyl) (phenyl) methyl ester was replaced with 4-n-propylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester.
Example 15
In the same manner as in example 11, only the compound benzoic acid (ethoxycarbonyl) (phenyl) methyl ester was replaced with 4-isopropylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester.
Example 16
In the same manner as in example 11, only the compound benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (6mmol) was replaced with benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (3mmol) and 2, 4-dibenzylcarboxypentane (3 mmol).
Example 17
In example 16, only the compound 2, 4-dibenzylcarboxypentane therein was changed to DNBP (di-n-butyl phthalate).
Example 18
In example 16, only the compound 2, 4-diphenylmethylcarboxypentane was replaced with DIBP (diisobutylphthalate).
Example 19
In example 16, only the compound 2, 4-dibenzylcarboxypentane was changed to 2, 4-bis (n-propylbenzoyloxy) pentane.
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 example 16, only the compound 2, 4-dibenzylcarboxypentane was changed to 1, 8-dibenzylcarboxynaphthol.
Example 23
In the same manner as in example 16, only the compound 2, 4-dibenzylcarboxypentane was changed to 3-tert-butyl-1, 2-dibenzylcarboxyphenol.
Example 24
In the same manner as in example 16, only the compound 2, 4-diphenylmethylcarboxypentane in the example was replaced with diethyl 2, 3-diisopropylsuccinate.
Example 25
(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. 1.4g of phthalic anhydride was added, and the reaction was continued at 130 ℃ for 1 hour to obtain an alcohol complex, which 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 ℃,2, 4-dibenzyl carboxyl pentane (3mmol) and a compound benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (3mmol) are added, and the temperature is raised to 110 ℃ 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 under vacuum to obtain a catalyst solid 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 the resin was prepared by adding 10mg of the solid component prepared in the above example and 1.2NL of hydrogen to CHMMS5mL (mol) so that Al/Si (25) was obtained, introducing 2.5L of liquid propylene, heating to 70 ℃ and maintaining the temperature for 1 hour, cooling, depressurizing, and discharging to obtain a PP resin, the results of which are shown in Table 1.
Example 26
(1) Preparation of solid catalyst component
300ml of LTiCl is added into a reactor which is fully replaced by high-purity nitrogen4Cooling to-20 deg.C, adding 7.0g of magnesium chloride alcoholate carrier (see patent CN1330086A), stirring, heating to 40 deg.C, adding 2, 4-dibenzylcarboxypentane (3mmol) and benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (3mmol), maintaining the temperature for 2 hr, and filtering. Then adding TiCl4100mL of the solution was heated to 110 ℃ and treated three times. 60mL of hexane was added thereto for washingAnd thirdly, vacuum drying to obtain the catalyst solid 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 the resin was prepared by adding 10mg of the solid component prepared in the above example and 1.2NL of hydrogen to CHMMS5mL (mol) so that Al/Si (25) was obtained, introducing 2.5L of liquid propylene, heating to 70 ℃ and maintaining the temperature for 1 hour, cooling, depressurizing, and discharging to obtain a PP resin, the results of which are shown in Table 1.
Example 27
(1) Preparation of solid catalyst component
300ml of LTiCl is added into a reactor which is fully replaced by high-purity nitrogen4Cooling to-20 deg.C, adding 7.0g of magnesium ethoxide, stirring, heating to 40 deg.C, adding 2, 4-dibenzylcarboxypentane (3mmol) and benzoic acid (ethoxycarbonyl) (phenyl) methyl ester (3mmol), maintaining the temperature for 3 hr, and filtering. Adding TiCl4100mL of the solution was heated to 110 ℃ and treated three times. Then 60mL of hexane was added for washing three times, and the solid catalyst component was obtained after drying.
(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 the resin was prepared by adding 10mg of the solid component prepared in the above example and 1.2NL of hydrogen to CHMMS5mL (mol) so that Al/Si (25) was obtained, introducing 2.5L of liquid propylene, heating to 70 ℃ and maintaining the temperature for 1 hour, cooling, depressurizing, and discharging to obtain a PP resin, the results of which are shown in Table 1.
Example 28
The same as example 17 except that the amount of hydrogenation in example was changed to 7.2NL, the results are shown in Table 1.
Comparative example 1
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with stirring and maintained for 2.5 hours. After the solid was completely dissolved, 1.4g of phthalic anhydride was added and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl within 1 hour4Slowly raising the temperature to 80 ℃, gradually removingA solid was gradually precipitated, DNBP (6mmol) was added, and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. 100mL of toluene was added, the temperature was raised to 110 ℃ and three washes were carried out for 10 minutes each. Then 60mL of hexane was added for washing three times, and the solid catalyst component was obtained after drying.
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of the resin was prepared by adding 10mg of the solid component prepared above and 1.2NL of hydrogen gas to CHMMS5mL (Al/Si (mol)) 25, introducing 2.5L of liquid propylene, heating to 70 ℃ for 1 hour, cooling, depressurizing, and discharging to obtain PP resin, the results are shown in Table 1.
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 BDA0001420276800000201
As can be seen from Table 1, under the same conditions, the catalyst component prepared by using the compound of the structural formula I of the present application as an internal electron donor alone or in combination with other internal electron donors, the catalytic activity of the catalyst and the isotacticity of the prepared polymer reach or even exceed the level of the prior art, and the obtained polymer has higher melt index and wider molecular weight distribution. Under the condition of high hydrogen, the catalyst component and the catalyst prepared by the electron donor compound 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 (22)

1. A catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a compound shown as a general formula I,
Figure FDA0002878768940000011
wherein A is a carbon atom; r1～R2Independently selected from hydrogen, substituted or unsubstituted C1～C30And substituted or unsubstituted C1～C30Alkoxy of R1And R2Can be linked to form a ring; r and R' are the same or different and are independently selected from substituted or unsubstituted C1～C30A hydrocarbon group of (1).
2. The catalyst component according to claim 1 in which R is1～R2Same or different, independently selected fromHydrogen, substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl, substituted or unsubstituted C7～C20And substituted or unsubstituted C1～C20Alkoxy group of (a); r1And R2Optionally linked to substituted or unsubstituted C3～C10Cycloalkyl, substituted or unsubstituted C3～C10Or is substituted or unsubstituted C2～C10The heterocyclic group of (1).
3. The catalyst component according to claim 2 in which R is1～R2Selected 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; r1And R2Optionally linked to one or more of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl, and cyclopentadienyl.
4. The catalyst component according to claim 1 in which R and R', which are identical or different, are each independently selected from substituted or unsubstituted C1～C20A hydrocarbon group of (1).
5. The catalyst component according to claim 4 in which R and R' are chosen from substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl and substituted or unsubstituted C7～C20Or an alkylaryl or arylalkyl group.
6. The catalyst component according to claim 5 wherein R and R' are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, and biphenyl.
7. The catalyst component according to claim 1 in which the compound of formula I is selected from the group consisting of (ethoxycarbonyl) (phenyl) methyl benzoate, (propoxycarbonyl) (phenyl) methyl benzoate, (butoxycarbonyl) (phenyl) methyl benzoate, (pentyloxycarbonyl) (phenyl) methyl benzoate, (ethoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (propoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (butoxycarbonyl) (phenyl) methyl 4-methylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (ethoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-methylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (ethoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 4-ethylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 2-ethylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (propoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (butoxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (pentyloxycarbonyl) (phenyl) 4-propylbenzoic acid methyl ester, (ethoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-propylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 2-propylbenzoate, (ethoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (ethoxycarbonyl) (phenyl) methyl ] ester, (propoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (butoxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (pentyloxycarbonyl) (phenyl) methyl 4-n-butylbenzoate, (ethoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, (propoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, (butoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, or (butoxycarbonyl) (phenyl) methyl 2-n-butylbenzoate, 2-n-Butyloxycarbonyl (phenyl) methyl benzoate, 2-ethoxycarbonyl (phenyl) methyl chlorobenzoate, 2-propoxycarbonyl (phenyl) methyl chlorobenzoate, 2-butoxycarbonyl (phenyl) methyl chlorobenzoate, 2-pentoxycarbonyl (phenyl) methyl chlorobenzoate, 3-ethoxycarbonyl (phenyl) methyl chlorobenzoate, 3-propoxycarbonyl (phenyl) methyl chlorobenzoate, 3-butoxycarbonyl (phenyl) methyl chlorobenzoate, 3-pentoxycarbonyl (phenyl) methyl chlorobenzoate, 4-ethoxycarbonyl (phenyl) methyl chlorobenzoate, 4-propoxycarbonyl (phenyl) methyl chlorobenzoate, 4-butoxycarbonyl (phenyl) methyl benzoate, 4-pentoxycarbonyl (phenyl) methyl chlorobenzoate, 2-Bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-bromochlorobenzoic acid [ (pentyloxycarbonyl) (phenyl) methyl ] ester, 4-isobutylbenzoic acid [ (ethoxycarbonyl) (phenyl) methyl ] ester, 4-isobutylbenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (ethoxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 2-isobutylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid [ (ethoxycarbonyl) (phenyl) methyl ] ester, 4-tert-butylbenzoic acid (propoxycarbonyl) (phenyl) methyl ester, 4-tert-butylmethylbenzoic acid (butoxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (pentyloxycarbonyl) (phenyl) methyl ester, n-butyl benzoic acid (n-butyl) methyl ester, n-butyl benzoic acid (pentyloxycarbonyl) (phenyl, (cyclohexyloxycarbonyl) (phenyl) methyl benzoate, 4-methylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclohexyloxycarbonyl) (phenyl) methyl ester, (cyclopentyloxycarbonyl) (phenyl) methyl benzoate, 4-methylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclopentyloxycarbonyl) (phenyl) methyl ester, (ethoxycarbonyl) (phenyl) methyl acetate, (propoxycarbonyl) (phenyl) methyl n-propionate, (butoxycarbonyl) (phenyl) methyl isopropionate, (pentyloxycarbonyl) (phenyl) methyl n-butyrate, one or more of (ethoxycarbonyl) (phenyl) methyl n-pentanoate, (propoxycarbonyl) (phenyl) methyl isovalerate, (propoxycarbonyl) (phenyl) methyl n-hexanoate, (propoxycarbonyl) (phenyl) methyl isocaproate, (ethoxycarbonyl) (phenyl) methyl phenylacetate, (propoxycarbonyl) (phenyl) methyl phenylacetate, and (butoxycarbonyl) (phenyl) methyl phenylacetate.
8. The catalyst component according to any of claims 1 to 7, further comprising a second internal electron donor compound selected from one or more of esters, ethers, carboxylic acids, ketones, and amines.
9. The catalyst component according to claim 8, wherein the second 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 claim 8, wherein the compound of formula I is present in the catalyst component in an amount of 0.05 to 20% by weight; and/or the weight percentage of the second internal electron donor compound in the catalyst component is 0-20%.
11. The catalyst component according to claim 10, wherein the compound of formula I is present in the catalyst component in an amount of 0.5 to 15% by weight; and/or the weight percentage of the second internal electron donor compound in the catalyst component is 0.01-15%.
12. The catalyst component according to claim 11, wherein the compound of formula I is present in the catalyst component in an amount of 2 to 10% by weight; and/or the weight percentage of the second internal electron donor compound in the catalyst component is 1-10%.
13. The catalyst component according to any one of claims 1 to 7, characterized in that it comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound; the internal electron donor comprises a compound shown in a general formula I.
14. The catalyst component according to claim 13, characterized by being prepared by a process comprising the steps of:
s1, mixing a magnesium compound with an organic solvent to form a solution, and then optionally adding a titanium compound for treatment;
s2, treating the mixture obtained in the step S1 by adopting an internal electron donor compound, and optionally treating the mixture by using a titanium compound and/or an inert diluent to obtain the catalyst component; the internal electron donor comprises a compound shown in a general formula I.
15. The catalyst component according to claim 14, wherein the internal electron donor further comprises a second internal electron donor compound selected from one or more of esters, ethers, carboxylic acids, ketones, and amines.
16. The catalyst component according to claim 15 in which the second 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.
17. The catalyst component according to claim 14 or 15, characterized in that the compound of formula I is used in an amount of 0.01 to 10 moles per mole of magnesium; and/or the second internal electron donor compound is used in an amount of 0 to 10 mol.
18. The catalyst component according to claim 14 or 15, characterized in that the compound of formula I is used in an amount of 0.01 to 5 moles per mole of magnesium; and/or the second internal electron donor compound is used in an amount of 0 to 5 mol.
19. The catalyst component according to claim 14 or 15, characterized in that the compound of formula I is used in an amount of 0.2 to 5 moles per mole of magnesium; and/or the second internal electron donor compound is used in an amount of 0.01 to 5 mol.
20. A catalyst system for olefin polymerization comprising the reaction product of:
a. the catalyst component of any one of claims 1 to 19;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
21. The catalyst system of claim 20 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.
22. 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 19 or a catalyst system as claimed in claim 20 or 21.
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CN1436796A (en) * 2002-02-07 2003-08-20 中国石油化工股份有限公司 Solid catalyst component for olefine polymerization, catalyst with the component and its application
CN102372797A (en) * 2010-08-12 2012-03-14 中国石油化工股份有限公司 Catalyst components for olefin polymerization and catalyst thereof
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CN102712704B (en) * 2009-12-02 2015-01-07 陶氏环球技术有限责任公司 Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture
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