CN107840905B - Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst - Google Patents

Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst Download PDF

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CN107840905B
CN107840905B CN201610839236.3A CN201610839236A CN107840905B CN 107840905 B CN107840905 B CN 107840905B CN 201610839236 A CN201610839236 A CN 201610839236A CN 107840905 B CN107840905 B CN 107840905B
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electron donor
internal electron
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titanium
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CN107840905A (en
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李昌秀
马晶
陈建华
蔡晓霞
马吉星
高明智
刘海涛
王军
胡建军
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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
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Abstract

The invention provides a solid catalyst component for olefin polymerization, a catalyst system and a prepolymerization catalyst, wherein the solid catalyst component comprises magnesium, titanium, halogen and an internal electron donor compound, and the internal electron donor compound comprises a first internal electron donor compound shown in a formula (I) and a second internal electron donor compound shown in a formula (II); r1And R2Are each selected from C1～C10Alkyl of (C)6～C20Aryl groups of (1), etc.; r3And R4Each selected from the following groups: c1～C10Straight chain alkyl group of (1), C3～C15Cycloalkyl of, C6～C20Aryl of (C)7～C20And alkylaryl groups of (a). When the catalyst containing the solid catalyst component is used in olefin polymerization reaction, the polymerization activity can be improved, and the polymer has good comprehensive performance.

Description

Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a solid catalyst component for olefin polymerization, a catalyst system and a prepolymerization catalyst.
Background
It is known that a solid titanium catalyst component having magnesium, titanium, halogen and an electron donor as basic components can be used for the polymerization of ethylene and/or α -olefin, and particularly, α -olefin having 3 or more carbon atoms can obtain a polymer with higher yield and higher stereoregularity.
Although the phthalate ester compound is the most commonly used polypropylene catalyst internal electron donor in the industry at present, researches show that the compound can cause serious damage to the growth and development of animals and reproductive systems and has similar influence on human beings. In addition, when a phthalate compound is used as an internal electron donor, the obtained polymer has a narrow molecular weight distribution and unsatisfactory toughness and processability, thereby limiting the application range thereof. Therefore, finding an alternative internal electron donor compound is a problem that needs to be solved at present.
At present, most of the electron donors reported are oxygen, nitrogen, phosphorus and sulfur-containing compounds. In these catalytic polymerization systems, the electron donor has varying degrees of influence on the activity, stereospecificity, molecular weight distribution and polymer properties.
In addition, the existing olefin polymerization catalyst needs to be improved in all aspects, and because a compound with extremely strong corrosivity and instability is used in the synthesis process, the catalyst is not beneficial to environmental protection and safety. Therefore, it is also necessary to develop an olefin polymerization catalyst having high activity and good stereoregularity and excellent overall performance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention uses a 1, 4-cyclohexane dicarboxylic ester compound and a diether compound with special positions to compound as an internal electron donor to obtain the catalyst with excellent comprehensive performance. The catalyst has high activity and good stereospecificity when used in olefin polymerization reaction. In view of this, the present invention provides a solid catalyst component, a catalyst system and a prepolymerized catalyst for olefin polymerization.
According to a first aspect of the present invention, the present invention provides a solid catalyst component for olefin polymerization, the solid catalyst component comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor compound comprising a first internal electron donor compound represented by formula (i) and a second internal electron donor compound represented by formula (ii), wherein a molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100): 100-1;
Figure BDA0001118083270000021
in the formula (I), R1And R2Are the same or different and are each selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1);
in the formula (II), R3And R4Are the same or different and are each selected fromSubstituted or unsubstituted of the following groups: c1～C10Straight chain alkyl group of (1), C3～C15Branched alkyl of C3～C15Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20Aralkyl of (2), R3And R4Optionally bonded to form a ring or not.
According to a second aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
a component a: the above solid catalyst component;
and (b) component b: an alkyl aluminum compound;
optionally, component c: an external electron donor compound, preferably of the formula R1 kSi(OR2)4-kWherein k is not less than 0 and not more than 3; r1Selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen; r2Selected from alkyl, cycloalkyl, aryl, haloalkyl or amino.
According to a third aspect of the present invention, there is provided a prepolymerized catalyst for olefin polymerization, comprising a prepolymer obtained by prepolymerizing the catalyst system with a prepolymerized olefin, wherein the prepolymerization ratio of the prepolymer is 0.1 to 1000g of the olefin polymer per g of the solid catalyst component.
The catalyst comprising the solid catalyst component of the invention has excellent combination properties when used in olefin polymerization: not only can improve the polymerization activity, but also the polymer prepared has high stereoregularity.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, the present invention provides a solid catalyst component for olefin polymerization, the solid catalyst component comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor compound comprising a first internal electron donor compound represented by formula (i) and a second internal electron donor compound represented by formula (ii), wherein a molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100): 100-1;
Figure BDA0001118083270000031
Figure BDA0001118083270000041
in the formula (I), R1And R2Are the same or different and are each selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1); preferably, R1And R2Are the same or different and are each selected from C2～C8Alkyl of (C)3～C8Cycloalkyl of, C6～C15Aryl or C of7～C15An aralkyl group of (2).
In the formula (II), R3And R4The same or different, each selected from the group consisting of substituted or unsubstituted: c1～C10Straight chain alkyl group of (1), C3～C15Branched alkyl of C3～C15Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20Aralkyl of (2), R3And R4Optionally bonded to form a ring or not; preferably, R3And R4The same or different, each selected from the group consisting of substituted or unsubstituted: c1～C8Straight chain alkyl group of (1), C3～C10Branched alkyl of C3～C10Cycloalkyl of, C6～C15Aryl of (C)7～C15Alkylaryl or C of7～C15Aralkyl of (2), R3And R4Optionally bonded to form a ring or not.
In the present invention, C1～C10Specific examples of the alkyl group of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl.
C3～C10Examples of cycloalkyl groups of (a) may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl.
C6～C20Examples of aryl groups of (a) may include, but are not limited to: phenyl, naphthyl.
C7～C20Examples of the alkylaryl group of (a) may include, but are not limited to: 4-methylphenyl and 4-ethylphenyl.
C7～C20Examples of the aralkyl group of (a) may include, but are not limited to: benzyl, phenylethyl, phenyl n-propyl, phenyl n-butyl, phenyl t-butyl, phenyl isopropyl, phenyl n-pentyl and phenyl n-butyl.
More specifically, the first internal electron donor compound of formula (I) may be selected from, but not limited to, the following compounds: methyl 1, 4-cyclohexanedicarboxylate, ethyl 1, 4-cyclohexanedicarboxylate, n-propyl 1, 4-cyclohexanedicarboxylate, isopropyl 1, 4-cyclohexanedicarboxylate, n-butyl 1, 4-cyclohexanedicarboxylate, isobutyl 1, 4-cyclohexanedicarboxylate, tert-butyl 1, 4-cyclohexanedicarboxylate, n-pentyl 1, 4-cyclohexanedicarboxylate, isoamyl 1, 4-cyclohexanedicarboxylate, n-hexyl 1, 4-cyclohexanedicarboxylate, cyclohexyl 1, 4-cyclohexanedicarboxylate, cyclohexylmethyl 1, 4-cyclohexanedicarboxylate, benzyl 1, 4-cyclohexanedicarboxylate, 2-ethyl-hexyl 1, 4-cyclohexanedicarboxylate, and the like.
The second internal electron donor compound represented by formula (II) may be selected from, but not limited to, the following compounds: 2, 2-dimethyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-di-n-propyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-di-n-butyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-di-n-pentyl-1, 3-dimethoxypropane, 2-diisopentyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-n-propyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-n-butyl-1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2-n-pentyl-1, 3-dimethoxypropane, 2-methyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-n-propyl-1, 3-dimethoxypropane, 2-ethyl-2-isopropyl-1, 3-dimethoxypropane, 2-ethyl-2-n-butyl-1, 3-dimethoxypropane, 2-dimethyl-2-isopropyl-1, 3-dimethoxypropane, 2-dimethyl-2-n-butyl-1, 3-dimethoxypropane, methyl-2-isopropyl-1, 3-dimethoxypropane, 2-, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-ethyl-2-n-pentyl-1, 3-dimethoxypropane, 2-ethyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopropyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-butyl-1, 3-dimethoxypropane, 2-n-propyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopent, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-butyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isopentyl-1, 3-dimethoxypropane, 2-isobutyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, and mixtures thereof, 2-isobutyl-2-phenyl-1, 3-dimethoxypropane, 2-isopentyl-2-phenyl-1, 3-dimethoxypropane, 2- (2-methyl-n-butyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-phenyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-ethyl-2-phenyl-1, 3-dimethoxypropane, 2-isobutyl-2-benzyl-1, 3-dimethoxypropane, 2-isopentyl-2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-benzyl-1, 3-dimethoxypropane, 2-n-propyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, a salt thereof, a base thereof, 2- (2-methylbutyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-methyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-ethyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-bis (2-methylbutyl) -1, 3-dimethoxypropane, 2-bis (2-ethylhexyl) -1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene, etc.
According to the present invention, the molar ratio of the first internal electron donor compound to the second internal electron donor compound is preferably (1-50): 50-1, and more preferably (1-20): 20-1.
According to an embodiment, the solid catalyst component includes a reaction product of a magnesium compound, a titanium compound, and the internal electron donor compound, wherein a molar ratio of the magnesium compound, the titanium compound, and the internal electron donor compound may be 1: 0.5-150: 0.02-0.5.
Wherein the magnesium compound may be at least one selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one halogen atom in the molecular formula is replaced by an alkoxy group or haloalkoxy group.
Preferably, the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide.
Further preferably, the magnesium compound is an alcoholate of magnesium dihalide.
The titanium compound may be at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
Preferably, the titanium compound is titanium tetrachloride.
According to a preferred embodiment of the present invention, the solid catalyst component is prepared by a process comprising the steps of:
1) reacting magnesium dihalide with an alcohol compound in the presence of a hydrocarbon compound and a precipitation assistant to obtain a uniform solution of the alcohol compound of the magnesium dihalide;
2) adding the uniform solution of the alcohol compound into the titanium compound at the temperature of between 40 ℃ below zero and 40 ℃ to obtain a mixed solution;
3) adding the internal electron donor compound into the mixed solution at a temperature of-40 ℃ to 150 ℃ to obtain a solid precipitate;
4) the solid precipitate is treated with a titanium compound and then washed with an inert diluent.
In step 1), the hydrocarbon compound may be selected from C6～C12And C is a linear or branched alkane6～C15At least one aromatic hydrocarbon.
In particular, the hydrocarbon compound may be selected from, but not limited to, the following compounds: hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, and the like.
The precipitation aid can be selected from at least one of organic acid anhydride, organic acid, ether and ketone. Preferably, the precipitation aid is at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether.
The alcohol compound may be selected from C1～C10Straight-chain or branched fatty alcohols of (C)3～C10Alicyclic alcohol of (C)7～C20At least one of the aromatic alcohols of (a).
Specifically, the alcohol compound may be ethanol, propanol, butanol, pentanol, hexanol, octanol, isooctanol, etc., or a mixture thereof.
In the step 4), the inert diluent is selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
In addition, the solid catalyst component may be prepared with reference to the method of CN1040379A, specifically, the method comprises:
firstly, mixing magnesium dihalide and an alcohol compound with a hydrocarbon compound according to a molar ratio of 2-5, heating to 120-150 ℃, adding an anhydride compound (a precipitation aid) according to a magnesium/anhydride molar ratio of 5-10, and reacting for 1-5 hours to obtain the alcohol compound of magnesium dihalide;
then, adding the alcohol compound cooled to room temperature into a titanium compound solution pre-cooled to minus 15 ℃ to minus 40 ℃ according to the molar ratio of titanium to magnesium of 20-50, heating to 90-110 ℃, adding the internal electron donor compounds shown in the formula (I) and the formula (II) according to the molar ratio of magnesium to electron donor of 2-10, reacting for 1-3 hours at 100-130 ℃, and filtering to separate solid particles;
then, adding the solid particles into the titanium compound solution according to the molar ratio of titanium to magnesium of 20-50, stirring, reacting at 100-130 ℃ for 1.5-3 hours, and filtering to separate out the solid particles;
and finally, washing the solid particles by using an inert diluent at the temperature of 50-80 ℃, and drying to obtain the solid catalyst component.
According to a second aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
a component a: the above solid catalyst component;
and (b) component b: an alkyl aluminum compound;
optionally, component c: an external electron donor compound, preferably of the formula R1 kSi(OR2)4-kWherein k is not less than 0 and not more than 3; r1Is alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen; r2Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
In the catalyst system, the molar ratio of the component a, the component b and the component c is 1: 5-1000: 0-500 in terms of titanium: aluminum: silicon.
From the viewpoint of improving the stereoregularity of the olefin polymer, the molar ratio of the component a, the component b and the component c is preferably 1: 25 to 100: 1 to 100 in terms of titanium: aluminum: silicon.
In the invention, the alkyl aluminum compound has a general formula of AlR3 nX3-nA compound of (1), wherein R3Is hydrogen or alkyl with 1-20 carbon atoms, X is halogen, and n is a number which is more than 1 and less than or equal to 3; specifically, the alkyl aluminum compound may be selected from at least one of Triethylaluminum (TEA), tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
Non-limiting examples of the external electron donor compound may include at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and methyl-t-butyldimethoxysilane; preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and/or diphenyldimethoxysilane.
According to different requirements on polymer performance, the catalyst system can be directly used for olefin polymerization; or the catalyst can be prepolymerized with olefin to produce prepolymerized catalyst, and then the prepolymerized catalyst is polymerized with olefin.
The olefin has the general formula CH2Where R may be hydrogen or C1～C12The catalyst system of the present invention is suitable for the production of homopolymers of polyethylene, polypropylene, etc., and copolymers of ethylene with other α -olefins such as propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene.
According to a third aspect of the present invention, the present invention provides a prepolymerized catalyst for olefin polymerization, the prepolymerized catalyst comprising a prepolymer obtained by prepolymerizing the above catalyst system with a prepolymerized olefin, wherein the prepolymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of solid catalyst component.
The term "prepolymerized olefin" means ethylene and/or α -olefin used in the prepolymerization with the catalyst system described in the present invention to obtain a prepolymerized catalyst, wherein the olefin is preferably one or more of ethylene, propylene and 1-butene.
According to a preferred embodiment, the prepolymerization is carried out with ethylene and the remainder up to 20 mol% of at least one α -olefin.
Preferably, in the prepolymerization, the degree of conversion of the solid catalyst component is 0.2 to 500g of the olefin polymer per g of the solid catalyst component.
The prepolymerization step of the present invention can be carried out at a temperature of-20 ℃ to 80 ℃, preferably 0 ℃ to 50 ℃, in a liquid or gas phase. The prepolymerization step can be carried out in-line as part of a continuous polymerization process or independently in a batch operation. For the preparation of a prepolymerized catalyst having a degree of conversion of 0.5 to 200g polymer/g solid catalyst component, the catalyst system of the invention is preferably prepolymerized with an olefin in a batch operation. The prepolymerization pressure can be 0.01-10 MPa.
The solid catalyst component or catalyst system, the prepolymerized catalyst of the present invention are suitable for use in olefin polymerization under various conditions, for example, the olefin polymerization may be carried out in liquid phase or gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. The olefin polymerization may be carried out according to known polymerization techniques, for example, using conventional techniques such as slurry processes, gas phase fluidized beds, and the like. The polymerization temperature may be 0 to 150 ℃, preferably 60 to 90 ℃.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
(1) the polymer isotactic index is measured by adopting a heptane extraction method, and the specific operation is as follows: a 2g sample of the dried polymer was placed in an extractor and after 6 hours of extraction with boiling heptane, the residue was dried to constant weight; the ratio of the weight (g) of the resulting polymer to 2 is the isotactic index.
(2) Molecular weight distribution MWD (MWD ═ M) of polymerw/Mn): measured at 150 ℃ by the gel permeation chromatography method (GPC) using PL-GPC220 with trichlorobenzene as a solvent (standard: polystyrene; flow rate: 1.0 mL/min; column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
Examples 1 to 5 and comparative example 1
(1) Preparation of solid catalyst component a
Under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent into a 500mL reactor provided with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 1.1g of phthalic anhydride, and continuously maintaining the temperature of 130 ℃ to react for 1 hour to obtain an alcohol compound; cooling the alcoholic mixture to room temperature;
under the protection of nitrogen, the alcohol compound is dropwise added into 120mL of titanium tetrachloride solution precooled to minus 22 ℃, the temperature is slowly increased to 100 ℃, 6mmol of the compound internal electron donor compound shown in the table 1 are respectively added, the temperature is increased to 110 ℃, the mixture is maintained for 2 hours, and the mixture is filtered while the mixture is hot. Then adding 120mL of titanium tetrachloride, heating to 110 ℃ for reaction 2 to obtain solid particles, filtering, washing the solid particles with anhydrous hexane for 4 times, and drying to obtain the solid catalyst component a of examples 1-5 and comparative example 1.
(2) Experiment on propylene polymerization
The solid catalyst component a obtained above was subjected to propylene polymerization reaction, respectively. The propylene polymerization process comprises the following steps: after a stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, 2.5mmol of AlEt is added3And 0.lmmol of cyclohexyl methyl dimethoxy silane, adding 8-10 mg of solid catalyst component a and 1.2NL of hydrogen, and introducing 2.3L of hydrogenHeating the liquid propylene to 70 ℃, and maintaining the temperature for 1 hour; and (5) cooling and decompressing to obtain the PP powder. The performance data for each catalyst are shown in table 1.
TABLE 1
Figure BDA0001118083270000111
Wherein:
a is 1, 4-cyclohexanedicarboxylic acid phenylmethyl ester: 9, 9-bis (methoxymethyl) fluorene: 6: 1;
b is 1, 4-cyclohexanedicarboxylic acid isobutyl ester: 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane: 1: 8;
c is 1, 4-cyclohexylmethyl cyclohexanedicarboxylate: 9, 9-bis (methoxymethyl) fluorene: 1;
d is 1, 4-cyclohexane dicarboxylic acid n-propyl ester: 9, 9-bis (methoxymethyl) fluorene: 1: 10;
e is 1, 4-cyclohexanedicarboxylic acid n-butyl ester: 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane: 8: 1.
As can be seen from Table 1, the catalyst system provided by the invention can obtain a polymer with a high isotactic index while maintaining the ultrahigh polymerization activity of the catalyst, and the polymer has excellent comprehensive performance, which is very beneficial to the development of resins with different grades.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims (14)

1. A solid catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor compound, and is characterized in that the internal electron donor compound comprises a first internal electron donor compound shown in a formula (I) and a second internal electron donor compound shown in a formula (II), and the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100): 100-1;
Figure FDA0002309342390000011
in the formula (I), R1And R2Are the same or different and are each selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1);
in the formula (II), R3And R4The same or different, each selected from the group consisting of substituted or unsubstituted: c1～C10Straight chain alkyl group of (1), C3～C15Branched alkyl of C3～C15Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20Aralkyl of (2), R3And R4Optionally bonded to form a ring or not.
2. The solid catalyst component according to claim 1 in which,
in the formula (I), R1And R2Are the same or different and are each selected from C2～C8Alkyl of (C)3～C8Cycloalkyl of, C6～C15Aryl or C of7～C15Aralkyl group of (1);
in the formula (II), R3And R4The same or different, each selected from the group consisting of substituted or unsubstituted: c1～C8Straight chain alkyl group of (1), C3～C10Branched alkyl of C3～C10Cycloalkyl of, C6～C15Aryl of (C)7～C15Alkylaryl or C of7～C15Aralkyl of (2), R3And R4Optionally bonded to form a ring or not.
3. The solid catalyst component of claim 1, wherein the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-50): 50-1.
4. The solid catalyst component of claim 3, wherein the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-20): 20-1.
5. The solid catalyst component according to any one of claims 1 to 4, wherein the solid catalyst component comprises a reaction product of a magnesium compound, a titanium compound and the internal electron donor compound, and the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1: 0.5 to 150: 0.02 to 0.5.
6. The solid catalyst component according to claim 5 in which the magnesium compound is selected from at least one of magnesium dihalide, alkoxymagnesium, alkylmagnesium, hydrates or alcoholates of magnesium dihalide, and derivatives of magnesium dihalide in which one halogen atom in the molecular formula is replaced by alkoxy or haloalkoxy;
the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
7. The solid catalyst component according to claim 6 in which the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide; the titanium compound is titanium tetrachloride.
8. The solid catalyst component according to claim 6 in which the solid catalyst component is prepared by a process comprising the steps of:
1) reacting magnesium dihalide with an alcohol compound in the presence of a hydrocarbon compound and a precipitation assistant to obtain a uniform solution of the alcohol compound of the magnesium dihalide;
2) adding the uniform solution of the alcohol compound into the titanium compound at the temperature of between 40 ℃ below zero and 40 ℃ to obtain a mixed solution;
3) adding the internal electron donor compound into the mixed solution at a temperature of-40 ℃ to 150 ℃ to obtain a solid precipitate;
4) the solid precipitate is treated with a titanium compound and washed with an inert diluent.
9. The solid catalyst component according to claim 8 in which,
in step 1), the hydrocarbon compound is selected from C6～C12And C is a linear or branched alkane6～C15At least one aromatic hydrocarbon;
the alcohol compound is selected from C1～C10Straight-chain or branched fatty alcohols of (C)3～C10Alicyclic alcohol of (C)7～C20At least one of the aromatic alcohols of (a);
in the step 4), the inert diluent is selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
10. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
a component a: a solid catalyst component according to any one of claims 1 to 9;
and (b) component b: an alkyl aluminum compound;
optionally, component c: an external electron donor compound.
11. The catalyst system of claim 10 wherein component c is of the formula R1 kSi(OR2)4-kWherein k is not less than 0 and not more than 3; r1Selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen; r2Selected from alkyl, cycloalkyl, aryl, haloalkyl or amino.
12. The catalyst system of claim 11, wherein the molar ratio of component a, component b, and component c is 1: 5-1000: 0-500 based on titanium: aluminum: silicon.
13. The catalyst system of claim 12, wherein the molar ratio of component a, component b, and component c is 1: 25-100: 1-100 in terms of titanium: aluminum: silicon.
14. A prepolymerized catalyst for olefin polymerization comprising a prepolymer prepared by prepolymerizing the catalyst system of any one of claims 10 to 13 with a prepolymerized olefin, wherein the prepolymerization ratio of the prepolymer is 0.1 to 1000g of the olefin polymer per g of the solid catalyst component.
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