CN107840917B - 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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CN107840917B
CN107840917B CN201610839940.9A CN201610839940A CN107840917B CN 107840917 B CN107840917 B CN 107840917B CN 201610839940 A CN201610839940 A CN 201610839940A CN 107840917 B CN107840917 B CN 107840917B
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cyclohexanedicarboxylate
titanium
magnesium
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CN107840917A (en
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李昌秀
马晶
陈建华
马吉星
蔡晓霞
高明智
刘海涛
胡建军
王军
张志会
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides a solid catalyst component for olefin polymerization, a catalyst system and a pre-polymerized catalyst. The solid catalyst component comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound is at least one compound selected from compounds shown in a formula (I): wherein R is1Is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1); r2Selected from hydrogen, halogen, C1～C10Alkyl of (C)1～C10Alkoxy group of (C)6～C20Aryl of (C)7～C20Aralkyl of (2), C1～C10Acyl group of (1), C1～C10Ester groups of (a) and the like. 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 well known that solid titanium catalyst components based on magnesium, titanium, halogen and electron donors can be used in the polymerization of ethylene and/or alpha-olefins, and in particular in the polymerization of alpha-olefins having 3 or more carbon atoms, polymers with higher yields and higher stereoregularity can be obtained. Among them, the electron donor compound is one of the indispensable components in the catalyst components, and the polyolefin catalyst is continuously updated with the development of the internal electron donor compound. Numerous internal electron donor compounds have been disclosed, such as polycarboxylic acids, mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyethers, alcohols, amines, and derivatives thereof, among which dibasic aromatic carboxylic acid esters, such as di-n-butyl phthalate or diisobutyl phthalate, are more commonly used (see chinese patent document CN 85100997A).
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 also has similar influence on human beings; moreover, in the field of olefin polymerization, when a phthalate ester compound is used as an internal electron donor, the molecular weight distribution of the obtained polymer is narrow, and the toughness and processability of the polymer are not satisfactory, thereby limiting the application range thereof. Therefore, finding an alternative internal electron donor compound is a problem that needs to be solved urgently at present.
At present, most of the electron donors reported are compounds containing oxygen, nitrogen, phosphorus and sulfur. In these catalytic polymerization systems, the electron donor has varying degrees of influence on the activity, stereospecificity, molecular weight distribution and polymer properties.
Chinese patent document CN102212154A reports that a 1, 2-cyclohexane dicarboxylic acid ester compound is used for olefin polymerization, but the polymerization activity of the catalyst is still to be improved, and the comprehensive performance of the polymer is not satisfactory.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention uses the 1, 3-cyclohexane dicarboxylic ester compound with special positions as an internal electron donor to obtain the catalyst with excellent comprehensive performance; the reason for this is probably that the ester groups of the 1, 3-cyclohexanedicarboxylate compounds are far away and the performance thereof is less affected by cis-trans isomers. 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, there is provided a solid catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen and an internal electron donor compound selected from at least one of the compounds represented by formula (I):
Figure BDA0001118088050000021
wherein R is1Is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1); r2Selected from hydrogen, halogen, C1～C10Alkyl of (C)1～C10Alkoxy group of (C)6～C20Aryl of (C)7～C20An aralkyl group of,C1～C10Acyl group of (1), C1～C10Ester group of (1), C1～C10Amide group of (A) or (C)1～C10An amino group of (a).
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: the catalyst system and prepolymerized olefin are prepolymerized to obtain a prepolymer, wherein the prepolymerization multiple of the prepolymer is 0.1-1000 g of olefin polymer/g of solid catalyst component.
When the catalyst containing the solid catalyst component is used for olefin polymerization reaction, the polymerization activity can be improved, and the prepared polymer has higher isotactic index and wider molecular weight distribution, namely, the polymer has good comprehensive performance.
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, there is provided a solid catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen and an internal electron donor compound selected from at least one of the compounds represented by formula (I):
Figure BDA0001118088050000031
wherein R is1Is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1); preferably, R1Is selected from C2～C8Alkyl of (C)3～C8Cycloalkyl of, C6～C15Aryl or C of7～C15An aralkyl group of (2).
R2Selected from hydrogen, halogen, C1～C10Alkyl of (C)1～C10Alkoxy group of (C)6～C20Aryl of (C)7～C20Aralkyl of (2), C1～C10Acyl group of (1), C1～C10Ester group of (1), C1～C10Amide group of (A) or (C)1～C10An amino group of (a); preferably, R2Selected from hydrogen, halogen, C1～C6Alkyl of (C)1～C6Alkoxy group of (C)6～C15Aryl of (C)7～C15Aralkyl of (2), C1～C6Acyl group of (1), C1～C9Ester group of (1), C1～C8Amide group of (A) or (C)1～C8An amino group of (a); more preferably, R2Is hydrogen or C1～C9Ester group of (a).
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-ethylcyclohexyl4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, and cyclooctyl.
C1～C10Examples of alkoxy groups of (a) may include, but are not limited to: methoxy group, isopropoxy group.
C6～C20Examples of aryl groups of (a) may include, but are not limited to: phenyl, naphthyl.
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 internal electron donor compound may be selected from, but not limited to, one or more of the following compounds: methyl 1, 3-cyclohexanedicarboxylate, ethyl 1, 3-cyclohexanedicarboxylate, n-propyl 1, 3-cyclohexanedicarboxylate, isopropyl 1, 3-cyclohexanedicarboxylate, n-butyl 1, 3-cyclohexanedicarboxylate, isobutyl 1, 3-cyclohexanedicarboxylate, tert-butyl 1, 3-cyclohexanedicarboxylate, n-pentyl 1, 3-cyclohexanedicarboxylate, isoamyl 1, 3-cyclohexanedicarboxylate, n-hexyl 1, 3-cyclohexanedicarboxylate, cyclohexyl 1, 3-cyclohexanedicarboxylate, cyclohexylmethyl 1, 3-cyclohexanedicarboxylate, phenylmethyl 1, 3-cyclohexanedicarboxylate, 2-ethyl-hexyl 1,3, 5-cyclohexanedicarboxylate, methyl 1,3, 5-cyclohexanedicarboxylate, ethyl 1,3, 5-cyclohexanedicarboxylate, isopropyl 1, 3-cyclohexanedicarboxylate, isobutyl 1, 3-cyclohexanedicarboxylate, isoamyl 1, 3-cyclohexanedicarboxylate, n-hexyl 1, 3-cyclohexanedi, N-propyl 1,3, 5-cyclohexanetricarboxylate, isopropyl 1,3, 5-cyclohexanetricarboxylate, n-butyl 1,3, 5-cyclohexanetricarboxylate, isobutyl 1,3, 5-cyclohexanetricarboxylate, tert-butyl 1,3, 5-cyclohexanetricarboxylate, n-pentyl 1,3, 5-cyclohexanetricarboxylate, isopentyl 1,3, 5-cyclohexanetricarboxylate, n-hexyl 1,3, 5-cyclohexanetricarboxylate, 2-ethyl hexyl 1,3, 5-cyclohexanetricarboxylate, and the like.
In the invention, the internal electron donor compound shown in the formula (I) can be obtained commercially, or the dibasic acid shown in the formula (II) and the general formula R can be used1And (3) carrying out condensation reaction on monohydric alcohol of OH to remove small molecular water to obtain the product. In addition, the specific conditions for the condensation reaction can be selected with reference to the prior art, and the present invention is not described herein in detail.
Figure BDA0001118088050000051
According to a preferred embodiment, 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 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.
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 the invention, the order of addition of the reactants may be: dissolving the magnesium compound in a solvent system containing an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, mixing the uniform solution with a titanium compound, and finally adding the internal electron donor compound; or dissolving the magnesium compound in the solvent system also containing the internal electron donor compound to form a uniform solution, and mixing the uniform solution with the titanium compound.
According to a preferred embodiment of the present invention, the solid catalyst component is prepared by a process comprising the steps of:
1) dissolving the magnesium compound in a solvent system containing an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution;
2) and mixing the titanium compound with the uniform solution in the presence of a precipitation assistant to obtain a solid, and adding the internal electron donor compound to react before or after the solid is precipitated.
The organic epoxy compound may be selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.
The organic phosphorus compound may be at least one selected from trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite.
The precipitation aid can be selected from at least one of organic acid anhydride, organic acid, ether and ketone, preferably 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.
In the solvent system, the amount of the organic epoxy compound may be 0.2 to 5 mol per mol of magnesium, and the molar ratio of the organic epoxy compound to the organic phosphorus compound may be (0.9 to 1.6): 1.
The inert diluent may be selected from C6～C10Alkane and C6～C10Preferably at least one aromatic hydrocarbon selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene and xylene.
In the step 1), the temperature for dissolving the magnesium compound can be 0-100 ℃, and the dissolving time can be 1-4 hours.
The process of step 2) may include: in the presence of a precipitation assistant, at a temperature not higher than-15 ℃, dropping the titanium compound into the uniform solution, slowly heating to 50-90 ℃, separating out a solid in the heating process, and then adding the internal electron donor compound to react for 0.5-3 hours to obtain a solid precipitate.
In addition, in order to make the reaction more sufficient and obtain the solid catalyst component of high purity, the method may further include: and (3) carrying out post-treatment on the solid precipitate by using a titanium compound and an inert diluent, and then washing by using the inert diluent. The specific conditions for the work-up and washing are well known in the art.
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.
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 general formula of the alkyl aluminum compound is AlR3 nX3-nIn the formula, 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 one or more of Triethylaluminum (TEA), tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride. Preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
Non-limiting examples of the external electron donor compound may include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, 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～C12Alkyl group of (1). The catalyst system of the present invention is suitable for the production of homopolymers of polyethylene, polypropylene, etc., and copolymers of ethylene with other alpha-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.
In the present invention, the term "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a relatively low degree of conversion. The term "prepolymerized olefin" means ethylene and/or alpha-olefin used in a prepolymerization reaction with the catalyst system according to the invention to obtain a prepolymerized catalyst. Wherein, the olefin is preferably one or more of ethylene, propylene and 1-butene.
In addition, the prepolymerization can be carried out using the same monomers as those used in the subsequent olefin polymerization. According to a preferred embodiment, the prepolymerization is carried out with ethylene and the remainder up to 20 mol% of at least one alpha-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.
In the present invention, the prepolymerization step can be carried out at a temperature of-20 ℃ to 80 ℃, preferably 0 ℃ to 50 ℃, in a liquid or in a gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation. In the prepolymerization, it is preferred to prepolymerize the catalyst system of the present invention with an olefin in a batch operation in order to produce an olefin polymer in an amount of 0.5 to 200g/g of the solid catalyst component. 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 isotactic index of the polymer is measured by adopting a heptane extraction method, and the specific operation method comprises the following steps: 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 6 and comparative example 1
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, andafter 2.5h to completely dissolve the solid, 1.4g phthalic anhydride was added and the reaction was continued for 1 h. The solution was cooled to below-25 ℃ and 56mL of TiCl were added dropwise over 1h4Slowly heating to 80 ℃, gradually precipitating a solid in the heating process, adding 5mmol of an internal electron donor compound shown in table 1, reacting for 1h at 80 ℃, filtering, washing with 70mL of toluene for 2 times respectively to obtain a solid precipitate, and then adding 60mL of toluene and 40mL of TiCl4Heating to 110 ℃, maintaining for 2h, repeating the same operation once, washing with 70mL of toluene at 110 ℃ for 3 times for 10min, adding 60mL of hexane, and washing for 2 times to obtain the solid catalyst component.
(2) Experiment on propylene polymerization
The solid catalyst components obtained above were subjected to propylene polymerization reactions, 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 and 1.2NL of hydrogen, introducing 2.3L of liquid propylene, heating to 70 ℃, and maintaining the temperature for 1 hour; and finally, cooling and relieving pressure to obtain the PP powder. The data are shown in Table 1.
TABLE 1
Figure BDA0001118088050000101
As can be seen from Table 1, the catalyst system provided by the present invention can obtain polymers with higher isotactic index and wider molecular weight distribution while maintaining higher polymerization activity, 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 (11)

1. A solid catalyst component for olefin polymerization, characterized in that it comprises magnesium, titanium, halogen and an internal electron donor compound selected from the group consisting of methyl 1, 3-cyclohexanedicarboxylate, ethyl 1, 3-cyclohexanedicarboxylate, n-propyl 1, 3-cyclohexanedicarboxylate, isopropyl 1, 3-cyclohexanedicarboxylate, n-butyl 1, 3-cyclohexanedicarboxylate, isobutyl 1, 3-cyclohexanedicarboxylate, tert-butyl 1, 3-cyclohexanedicarboxylate, n-pentyl 1, 3-cyclohexanedicarboxylate, isoamyl 1, 3-cyclohexanedicarboxylate, n-hexyl 1, 3-cyclohexanedicarboxylate, cyclohexyl 1, 3-cyclohexanedicarboxylate, cyclohexylmethyl 1, 3-cyclohexanedicarboxylate, 1, at least one of 3-cyclohexanedicarboxylic acid phenylmethyl ester, 1, 3-cyclohexanedicarboxylic acid (2-ethyl) hexyl ester, 1,3, 5-cyclohexanetricarboxylic acid methyl ester, 1,3, 5-cyclohexanetricarboxylic acid ethyl ester, 1,3, 5-cyclohexanetricarboxylic acid n-propyl ester, 1,3, 5-cyclohexanetricarboxylic acid isopropyl ester, 1,3, 5-cyclohexanetricarboxylic acid n-butyl ester, 1,3, 5-cyclohexanetricarboxylic acid isobutyl ester, 1,3, 5-cyclohexanetricarboxylic acid tert-butyl ester, 1,3, 5-cyclohexanetricarboxylic acid n-pentyl ester, 1,3, 5-cyclohexanetricarboxylic acid isoamylester, 1,3, 5-cyclohexanetricarboxylic acid n-hexyl ester, and 1,3, 5-cyclohexanetricarboxylic acid (2-ethyl) hexyl ester;
the solid catalyst component comprises a reaction product of a magnesium compound, a titanium compound and the internal electron donor compound, wherein the molar ratio of the magnesium compound to the titanium compound to the internal electron donor compound is 1: 0.5-150: 0.02-0.5;
the solid catalyst component is prepared by a method comprising the following steps:
1) dissolving the magnesium compound in a solvent system containing an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution;
2) and mixing the titanium compound with the uniform solution in the presence of a precipitation assistant to obtain a solid, and adding the internal electron donor compound to react before or after the solid is precipitated.
2. The solid catalyst component according to claim 1 in which the magnesium compound is at least one selected from the group consisting of magnesium dihalides, alkoxymagnesium, alkylmagnesium, 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 a haloalkoxy group.
3. The solid catalyst component according to claim 2 in which the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide.
4. The solid catalyst component according to claim 2 in which the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
5. The solid catalyst component according to claim 4 in which the titanium compound is titanium tetrachloride.
6. The solid catalyst component according to claim 1 in which the precipitation aid is at least one of an organic acid anhydride, an organic acid, an ether and a ketone; in the solvent system, the dosage of the organic epoxy compound is 0.2-5 mol per mol of magnesium, and the mol ratio of the organic epoxy compound to the organic phosphorus compound is (0.9-1.6): 1.
7. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
a component a: the solid catalyst component according to any one of claims 1 to 6;
and (b) component b: an alkyl aluminum compound;
optionally, component c: an external electron donor compound.
8. The catalyst system of claim 7, wherein the external electron donor compound 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.
9. The catalyst system of claim 7, wherein the molar ratio of component a, component b, and component c is 1: 5-1000: 0-500 based on titanium: aluminum: silicon.
10. The catalyst system of claim 9, wherein the molar ratio of component a, component b, and component c is 1: 25-100: 1-100 in terms of titanium: aluminum: silicon.
11. A prepolymerized catalyst for olefin polymerization comprising the catalyst system of any one of claims 7 to 10 and a prepolymer obtained by prepolymerizing 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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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1532211A (en) * 2003-03-18 2004-09-29 中国石油化工股份有限公司 Catalyst for ethylene polymerization or copolymerization and its preparing method
CN1771268A (en) * 2003-03-26 2006-05-10 Bp北美公司 Olefin polymerisation catalyst containing a cycloakane dicarboxylate as electron donor
CN101107276A (en) * 2005-01-19 2008-01-16 三井化学株式会社 Process for producing olefin polymer and solid titanium catalyst component and catalyst for olefin polymerization
KR20110080616A (en) * 2010-01-06 2011-07-13 삼성토탈 주식회사 Process for producing solid catalyst for propylene polymerization
CN103626896A (en) * 2012-08-23 2014-03-12 中国石油化工股份有限公司 Catalyst component for alkene polymerization reactions and preparation method of catalyst thereof
CN104053682A (en) * 2011-11-21 2014-09-17 巴斯夫公司 High activity catalyst component for olefin polymerization and method of using the same
WO2016025194A1 (en) * 2014-08-12 2016-02-18 Basf Corporation Combined internal donor system for ziegler-natta polyolefin catalysts and methods of making and using same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1532211A (en) * 2003-03-18 2004-09-29 中国石油化工股份有限公司 Catalyst for ethylene polymerization or copolymerization and its preparing method
CN1771268A (en) * 2003-03-26 2006-05-10 Bp北美公司 Olefin polymerisation catalyst containing a cycloakane dicarboxylate as electron donor
CN101107276A (en) * 2005-01-19 2008-01-16 三井化学株式会社 Process for producing olefin polymer and solid titanium catalyst component and catalyst for olefin polymerization
KR20110080616A (en) * 2010-01-06 2011-07-13 삼성토탈 주식회사 Process for producing solid catalyst for propylene polymerization
CN104053682A (en) * 2011-11-21 2014-09-17 巴斯夫公司 High activity catalyst component for olefin polymerization and method of using the same
CN103626896A (en) * 2012-08-23 2014-03-12 中国石油化工股份有限公司 Catalyst component for alkene polymerization reactions and preparation method of catalyst thereof
WO2016025194A1 (en) * 2014-08-12 2016-02-18 Basf Corporation Combined internal donor system for ziegler-natta polyolefin catalysts and methods of making and using same

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