CN107840906B - 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 PDFInfo
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- CN107840906B CN107840906B CN201610839238.2A CN201610839238A CN107840906B CN 107840906 B CN107840906 B CN 107840906B CN 201610839238 A CN201610839238 A CN 201610839238A CN 107840906 B CN107840906 B CN 107840906B
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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); r1Is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl groups of (1), etc.; r2Selected from hydrogen, halogen, C1～C10Alkyl of (C)1～C10Ester groups of (a); r3Is C2～C8Straight chain alkyl, C5～C10Cycloalkyl groups and the like; r4～R7Each is selected from hydrogen, halogen, C3～C10Branched alkyl groups, 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
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 solid titanium catalyst components based on magnesium, titanium, halogen and an electron donor can be used for the polymerization of ethylene and/or alpha-olefins, and in particular for 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. Currently, a variety of internal electron donor compounds are disclosed in a large number, such as polycarboxylic acids, monocarboxylic acid esters or polycarboxylic acid esters, anhydrides, ketones, monoethers or polyethers, alcohols, amines, etc., and derivatives thereof, among which dibasic aromatic carboxylic acid esters, such as di-n-butyl phthalate or diisobutyl phthalate, etc., are more commonly used (see 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 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.
Most of the electron donors reported at present 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 excellent overall properties such as stereospecificity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention uses the 1, 3-cyclohexane dicarboxylic acid ester compound with special positions and the phthalic acid ester compound to be compounded as an internal electron donor, so that the catalyst with excellent comprehensive performance can be obtained. 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 being a first internal electron donor compound represented by formula (i) and a second internal electron donor compound represented by formula (ii), and a molar ratio of the first internal electron donor compound to the second internal electron donor compound being (1-100): 100-1;
in the formula (I), R1Is 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 group of (1), C1～C10Amide group of (A) or (C)1～C10An amino group of (a);
in the formula (II), R3Is selected from C2～C8Straight chain alkyl group of (1), C3～C10Branched alkyl of C5～C10Cycloalkyl of, C6～C15Aryl of (C)7～C15Alkylaryl or C of7～C15Aralkyl group of (1);
R4～R7same or different, each selected from hydrogen, halogen, C1～C6Straight chain alkyl group of (1), C3～C10Branched alkyl of C5～C10Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20And wherein the hydrogen on the alkyl, aryl, alkaryl or aralkyl group is optionally substituted with an alkyl or halogen.
According to a second aspect of the present invention, there is provided a catalyst system for the polymerisation of olefins, said 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; preferred general formula is 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, the prepolymerization ratio of the prepolymer being 0.1 to 1000g of the olefin polymer per g of the solid catalyst component.
The catalyst comprising the solid catalyst component of the present invention has an excellent combination of 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;
in the formula (I), R1Is 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 formula (II), R3Is selected from C2～C8Straight chain alkyl group of (1), C3～C10Branched alkyl of C5～C10Cycloalkyl of, C6～C15Aryl of (C)7～C15Alkylaryl or C of7～C15Aralkyl group of (1); preferably, R3Is selected from C3～C8Straight chain alkyl group of (1), C3～C10Branched alkyl of C6～C10Aryl of (C)7～C10Alkylaryl or C of7～C10Aralkyl group of (1);
R4～R7same or different, each selected from hydrogen, halogen, C1～C6Straight chain alkyl group of (1), C3～C10Branched alkyl of C5～C10Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20And wherein the hydrogen on the alkyl, aryl, alkaryl or aralkyl group is optionally substituted with an alkyl group or a halogen atom; preferably, R4～R7Same or different, each selected from hydrogen, halogen, C1～C6Straight chain alkyl or C3～C8And wherein the hydrogen on the alkyl group is optionally substituted with alkyl or halogen.
In the present invention, C1～C10Alkyl of (2)Specific examples 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) 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) include, but are not limited to: phenyl, naphthyl.
C7～C20Examples of alkaryl groups of (a) include, but are not limited to: 4-methylphenyl and 4-ethylphenyl.
C7～C20Examples of aralkyl groups of (a) include, but are not limited to: benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl and phenyl n-butyl.
Specifically, the first internal donor compound represented by formula (i) is selected from, but not limited to, 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 formula(I) The internal electron donor compound can be obtained commercially, or obtained by reacting a dibasic acid represented by the formula (III) with a compound represented by the general formula R1And (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.
Specifically, the second internal electron donor compound represented by formula (ii) is selected from, but not limited to, the following compounds: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, dibenzyl phthalate, dimethyl tetramethyl phthalate, diethyl tetramethyl phthalate, di-n-propyl tetramethyl phthalate, diisopropyl tetramethyl phthalate, di-n-butyl tetramethyl phthalate, diisobutyl tetramethyl phthalate, di-n-pentyl tetramethyl phthalate, diisopentyl tetramethyl phthalate, di-n-hexyl tetramethyl phthalate, diisohexyl tetramethyl phthalate, di-n-octyl tetramethyl phthalate, diisohexyl tetramethyl phthalate, di-n-hexyl tetramethyl phthalate, di-n-octyl phthalate, di-n-hexyl phthalate, di-n-octyl phthalate, di-isooctyl tetramethyl phthalate, di-benzyl tetramethyl phthalate, dimethyl tetrabromophthalate, diethyl tetrabromophthalate, di-n-propyl tetrabromophthalate, diisopropyl tetrabromophthalate, di-n-butyl tetrabromophthalate, diisobutyl tetrabromophthalate, di-n-pentyl tetrabromophthalate, diisopentyl tetrabromophthalate, di-n-hexyl tetrabromophthalate, di-isohexyl tetrabromophthalate, di-n-octyl tetrabromophthalate, di-isooctyl tetrabromophthalate, di-benzyl tetrabromophthalate, 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 an 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.
In the present invention, the alcoholate of magnesium dihalide can be represented by MgX2pR' OH, X is halogen, preferably Cl; p represents a number selected from 0.1 to 6, preferably 2 to 3.5; r' is typically selected from C1～C18A hydrocarbon group of (1).
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 one embodiment of the invention, the solid catalyst component is prepared by a process comprising the steps of:
firstly, mixing an alcohol with a magnesium dihalide in the presence of an inert hydrocarbon immiscible with the adduct to obtain an emulsion of an alcoholate of the magnesium dihalide; rapidly cooling the emulsion by using a cooling liquid to solidify the alcoholate in the form of spherical particles so as to prepare the alcoholate carrier of the magnesium dihalide;
subsequently, treating said alcoholate support of magnesium dihalide with said titanium compound, adding said internal donor compound during the treatment, obtaining a solid precipitate;
finally, the solid precipitate is washed and dried to prepare the solid catalyst component.
In this embodiment, the alcoholate support of the magnesium dihalide can be reacted directly with the titanium compound or, before the reaction, can be subjected to a thermal controlled dealcoholation (80 to 130 ℃) in order to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.7. The reaction of the components can be carried out by suspending the carrier of the above alcoholate (dealcoholated or as such) in a cold titanium compound (generally 0 ℃) and by heating the resulting mixture to a temperature of 80 to 130 ℃ and maintaining it at this temperature for 0.1 to 2 hours.
In this embodiment, the titanium compound treatment may be performed one or more times. The treatment with the internal electron donor compound may be carried out one or more times during the treatment with the titanium compound.
According to another preferred embodiment of the present invention, the solid catalyst component can be prepared by a process comprising the steps of:
1) mixing the alcoholate of magnesium dihalide with a dispersant system to prepare emulsion; rapidly cooling the emulsion by using cooling liquid to prepare a spherical carrier;
2) reacting the spherical carrier with a titanium compound and an internal electron donor compound to obtain a solid precipitate;
3) washing and drying the solid precipitate to obtain the solid catalyst component;
in particular, with reference to CN1040379A, the solid catalyst component can be prepared by the following method:
firstly, heating magnesium dihalide and alcohol according to a certain proportion to react (90-140 ℃) to generate an alcohol compound melt of the magnesium dihalide, stirring and dispersing the mixture at a high speed in a dispersing agent system, rapidly cooling the mixture to form microspherical solid particles of the alcohol compound of the magnesium dihalide, and washing and drying the microspherical solid particles to obtain a spherical carrier; the particle size of the carrier is 10-300 mu m, preferably 30-150 mu m; wherein the molar ratio of the alcohol to the magnesium dihalide is (2-3): 1, preferably (2-2.5): 1;
then, treating the spherical carrier at low temperature (preferably for multiple times) by using excessive titanium compound, gradually raising the temperature, and adding the electron donor compounds shown in the formulas (I) and (II) in the treatment process; wherein the molar ratio of the titanium compound to the carrier is (20-150): 1, preferably (30-85): 1, in terms of titanium and magnesium; the initial treatment temperature is-30 ℃ to 0 ℃, preferably-25 ℃ to-20 ℃, and the final treatment temperature is 80-136 ℃, preferably 100-130 ℃;
and finally, washing the treated catalyst component for multiple times by using an inert solvent, and drying to obtain a solid powdery spherical solid catalyst component.
In the present invention, the dispersant system comprises a hydrocarbon inert solvent, and optionally a surfactant or an organosilicon compound; preferably, the dispersant system is a silicone oil and a white oil.
In the present invention, the cooling liquid is selected from hydrocarbon inert solvents with low boiling points, and is specifically selected from petroleum ether, pentane, hexane or heptane.
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:
component a, the solid catalyst component described above;
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.
The external electron donor compound may be at least one selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane, and the like; 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, there is provided a prepolymerized catalyst for olefin polymerization, comprising a prepolymer obtained by prepolymerizing the above 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.
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.
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
Adding 36.5mL of absolute ethyl alcohol and 21.3g of anhydrous magnesium chloride into a 250mL reactor which is provided with a reflux condenser, a mechanical stirrer and a thermometer and is fully replaced by nitrogen, heating while stirring, adding 75mL of white oil and 75mL of silicone oil after the magnesium chloride is completely dissolved, and stirring and mixing for 1 hour at 120 ℃ to obtain a mixture; adding 112.5mL of white oil and the same volume of silicone oil into another reaction flask with a high-speed stirrer and a volume of 500mL, preheating to 120 ℃, quickly pressing the mixture into a second reactor, and stirring at 3500rmp for 3 minutes while maintaining the temperature at 120 ℃; transferring the material into a third reactor, in which 1600mL of hexane is added in advance and cooled to-25 ℃ under stirring until the material is transferred, and the final temperature is not more than 0 ℃; filtering, washing with hexane, vacuum drying to obtain 41g of spherical particle magnesium chloride alcoholate, sieving to obtain 100-400 mesh carrier, analyzing and testing the composition of the carrier to MgCl2·2.38C2H5OH。
Taking the above MgCl2·2.38C2H5Slowly adding 7g of OH spherical carrier into a reaction bottle filled with 150mL of titanium tetrachloride and precooled to-20 ℃, gradually heating to 40 ℃, and adding 6mmol of compound internal electron donor compound in the table 1; continuously heating to 130 ℃, maintaining for 2 hours, filtering to obtain solid particles, and adding 120mL of TiCl into the solid particles4Gradually heating to 130 ℃, and maintaining for 2 hours;
the solid catalyst component a of examples 1 to 5 and comparative example 1 was obtained by washing the filtrate with 60mL of hexane several times until no chloride ion appeared in the filtrate and drying the filter cake under vacuum.
(2) Experiment on propylene polymerization
The solid catalyst component a obtained above was subjected to propylene polymerization, respectively. The propylene polymerization procedure was: a stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and 2.5mmol of AlEt is added3And lmmol external electron donor compound cyclohexyl methyl dimethoxy silane, adding 8-10 mg of solid catalyst component a and 1.2NL hydrogen, introducing 2.3L of liquid propylene, heating to 70 ℃, and maintaining the temperature for 1 hour; and (5) cooling and decompressing to obtain the PP powder. The properties of the respective catalysts are shown in Table 1.
TABLE 1
| Examples | Compound internal electron donor compound | Polymerization Activity/(kgPP/gcat) | Isotactic index/% | MWD |
| Example 1 | A | 43.7 | 98.0 | 7.1 |
| Example 2 | B | 48.5 | 98.5 | 6.8 |
| Example 3 | C | 47.0 | 98.2 | 6.9 |
| Example 4 | D | 51.2 | 98.6 | 6.8 |
| Example 5 | E | 48.9 | 98.1 | 7.0 |
| Comparative example 1 | 1, 3-Cyclohexanedicarboxylic acid n-butyl ester | 35.3 | 96.0 | 9.0 |
Wherein:
a is 1, 3-cyclohexane dicarboxylic acid phenylmethyl ester, phthalic acid di-n-butyl ester 5:1
B is 1, 3-cyclohexanedicarboxylic acid isobutyl ester, phthalic acid diisobutyl ester 1:7
C is 1,3, 5-cyclohexane-tricarboxylic acid propyl ester, phthalic acid di (2-ethylhexyl) 1:1
D is 1, 3-cyclohexanedicarboxylic acid cyclohexylmethyl ester and phthalic acid di-n-butyl ester is 1:10
E is 1, 3-cyclohexanedicarboxylic acid n-butyl ester, diisobutyl phthalate ═ 3:1
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 high 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 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;
the first internal electron donor compound is selected from 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, benzyl 1, 3-cyclohexanedicarboxylate, 2-ethylhexyl 1, 3-cyclohexanedicarboxylate, methyl 1,3, 5-cyclohexanedicarboxylate, methyl 1, 3-cyclohexanedicarboxylate, ethyl-ethyl 1,3, 5-cyclohexanedicarboxylate, ethyl-n-propyl 1, 3-cyclohexanedicarboxylate, isopropyl 1, 3-cyclohexanedicarboxylate, isobutyl 1, 3-cyclohexanedicarboxylate, At least one of ethyl 1,3, 5-cyclohexanetricarboxylate, 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, isoamyl 1,3, 5-cyclohexanetricarboxylate, n-hexyl 1,3, 5-cyclohexanetricarboxylate, and (2-ethyl) hexyl 1,3, 5-cyclohexanetricarboxylate;
formula (II)
In the formula (II), R3Is selected from C2~C8Straight chain alkyl group of (1), C3~C10Branched alkyl of C5~C10Cycloalkyl or C7~C15Aralkyl group of (1);
R4~R7same or different, each selected from hydrogen and C1~C6Straight chain alkyl group of (1), C3~C10Branched alkyl or C7~C20And wherein the alkyl group or the hydrogen on the aralkyl group is optionally substituted with an alkyl group.
2. The solid catalyst component according to claim 1 in which,
in the formula (II), R3Is selected from C3~C8Straight chain alkyl group of (1), C3~C10Branched alkyl or C7~C10Aralkyl group of (1);
R4~R7same or different, each selected from hydrogen and C1~C6Straight chain alkyl or C3~C8And wherein the hydrogen on the alkyl group is optionally substituted with an alkyl group.
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 an internal electron donor compound, and the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1: 0.5-150: 0.02-0.5.
6. The solid catalyst component according to claim 5 in which the magnesium compound is at least one member selected from the group consisting of magnesium dihalides, alkoxymagnesium, alkylmagnesium, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one of the halogen atoms is replaced by an alkoxy group or haloalkoxy group
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, wherein it is prepared by a process comprising the steps of:
1) mixing the alcoholate of magnesium dihalide with a dispersant system to prepare emulsion; rapidly cooling the emulsion by using cooling liquid to prepare a spherical carrier;
2) reacting the spherical carrier with a titanium compound and an internal electron donor compound to obtain a solid precipitate;
3) washing and drying the solid precipitate to obtain the solid catalyst component;
the dispersant system comprises a hydrocarbon inert solvent, and optionally a surfactant or an organosilicon compound.
9. The solid catalyst component according to claim 8 in which the dispersant system is a silicone oil and a white oil; the cooling liquid is selected from petroleum ether, pentane, hexane or heptane.
10. A catalyst system for the polymerization of olefins, said 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 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; r1Is alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen; r2Is 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 on a titanium: aluminum: silicon basis.
14. A prepolymerized catalyst for olefin polymerization comprising a prepolymer obtained 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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|---|---|---|---|---|
| CN1091748A (en) * | 1993-03-29 | 1994-09-07 | 中国石油化工总公司 | The spherical catalyst of for olefines polymerization |
| 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 |
| JP2009057473A (en) * | 2007-08-31 | 2009-03-19 | Mitsui Chemicals Inc | Original sheet for capacitor film comprising polypropylene resin, capacitor film and method of manufacturing the same |
| KR20110080616A (en) * | 2010-01-06 | 2011-07-13 | 삼성토탈 주식회사 | A method for the preparation of a solid catalyst for olefin polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091748A (en) * | 1993-03-29 | 1994-09-07 | 中国石油化工总公司 | The spherical catalyst of for olefines polymerization |
| 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 |
| JP2009057473A (en) * | 2007-08-31 | 2009-03-19 | Mitsui Chemicals Inc | Original sheet for capacitor film comprising polypropylene resin, capacitor film and method of manufacturing the same |
| KR20110080616A (en) * | 2010-01-06 | 2011-07-13 | 삼성토탈 주식회사 | A method for the preparation of a solid catalyst for olefin polymerization |
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