CN107840915B - 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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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 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)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20Aralkyl group of (1); r3And R4Each selected from hydrogen, halogen, etc., R5And R6Each is selected from halogen and C1～C10Alkyl of (e), R7And R8Are each selected from C3～C20Cycloalkyl groups of (i), 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, many internal electron donor compounds are disclosed, such as polycarboxylic acids, monocarboxylic acid esters or polycarboxylic acid esters, acid anhydrides, ketones, monoethers 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 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.
Therefore, it is necessary to develop an olefin polymerization catalyst having high activity and good stereoregularity and excellent overall properties.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention uses a 1, 4-cyclohexanedicarboxylate compound with a special position and a diol ester compound to be compounded as an internal electron donor to obtain the catalyst with excellent comprehensive performance. When the catalyst is used for olefin polymerization reaction, the activity is higher, and the prepared polymer has good stereospecificity and wide molecular weight distribution. 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;
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 R4Identical or different, are each selected from hydrogen, halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C10Aryl of (C)7～C10Alkyl of (2)Aryl or C7～C10Aralkyl of (2), R3、R4Optionally bonded to form a ring;
R5and R6Identical or different, are each selected from halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C10Aryl of (C)7～C10Alkylaryl or C of7～C10Wherein the hydrogen on the alkyl, aryl, alkaryl or aralkyl group may be optionally substituted with an alkyl or halogen;
R7and R8Identical or different, are each selected from C3～C20Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20Wherein hydrogen on cycloalkyl, aryl, alkaryl or aralkyl is optionally substituted by alkyl or halogen, and R7And R8Is not simultaneously C3～C20A cycloalkyl group.
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 polymerization activity, but also the prepared polymer has high stereoregularity and wider molecular weight distribution.
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), R1And R2Are the same or different and are each selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C20Aryl or C of7～C20An aralkyl group of (2).
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 R4Identical or different, are each selected from hydrogen, halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C10Aryl of (C)7～C10Alkylaryl or C of7～C10Aralkyl of (2), R3、R4Optionally bonded to form a ring; preferably, R3And R4Identical or different, are each selected from hydrogen and C1～C8Alkyl or halogen of (a); more preferably, R3And R4Each selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, chlorine atom or bromine atom.
R5And R6Identical or different, are each selected from halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C6～C10Aryl of (C)7～C10Alkylaryl or C of7～C10And wherein the hydrogen on the alkyl, aryl, alkaryl or aralkyl group may be optionally substituted with an alkyl or halogen; preferably, R5And R6Are each selected from C1～C10And hydrogen atoms on the alkyl group are optionally substituted with halogen; more preferably, R5And R6Each selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, the hydrogen atoms of the aforementioned alkyl groups being optionally substituted by halogen.
R7And R8Identical or different, are each selected from C3～C20Cycloalkyl of, C6～C20Aryl of (C)7～C20Alkylaryl or C of7～C20Wherein hydrogen on cycloalkyl, aryl, alkaryl or aralkyl is optionally substituted by alkyl or halogen, and R7And R8Cannot be simultaneously C3～C20A cycloalkyl group; preferably, R7And R8Identical or different, are each selected from C6～C20Aryl of (C)7～C20Aralkyl or C7～C20The alkylaryl group of (a), the hydrogen atoms on the foregoing groups are optionally substituted with alkyl or halogen; more preferably, R7And R8Are each selected from C6～C15Aryl or C of7～C20An aralkyl group of (2).
The inventionIn, C1～C10Alkyl of (A) means C1～C10Straight chain alkyl of (2) and C3～C10Specific examples of the branched 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～C20Examples 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, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-n-butylphenyl and 4-tert-butylphenyl.
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, 4-pentanediol dibenzoate, 2, 4-pentanediol di-p-methylbenzoate, 2, 4-pentanediol di-o-methylbenzoate, 2, 4-pentanediol di-p-ethylbenzoate, 2, 4-pentanediol di-p-propylbenzoate, 2, 4-pentanediol di-p-n-butylbenzoate, 2, 4-pentanediol di-p-tert-butylbenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol di-p-methylbenzoate, 3-ethyl-2, 4-pentanediol di-p-ethylbenzoate, 2, 4-pentanediol di, 3-ethyl-2, 4-pentanediol di-p-propylbenzoate, 3-ethyl-2, 4-pentanediol di-p-butylbenzoate, 3-ethyl-2, 4-pentanediol di-p-tert-butylbenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 3-chloro-2, 4-pentanediol dibenzoate, 3-bromo-2, 4-pentanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-p-ethylbenzoate, 3, 5-heptanediol di-p-propylbenzoate, 3, 5-heptanediol di-p-butylbenzoate, 3, 5-heptanediol di-p-tert-butylbenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol di-p-methylbenzoate, 4-ethyl-3, 5-heptanediol di-p-ethylbenzoate, 4-ethyl-3, 5-heptanediol di-p-propylbenzoate, 4-ethyl-3, 5-heptanediol di-p-butylbenzoate, 4-ethyl-3, 5-heptanediol di-p-tert-butylbenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 4-chloro-3, 5-heptanediol dibenzoate, 4-bromo-3, 5-heptanediol dibenzoate, and the like.
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.
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 may be prepared by a process comprising the steps of:
1) dissolving the magnesium compound in a solvent system comprising an organic epoxy compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution;
2) in the presence of a precipitation assistant, mixing the titanium compound with the uniform solution to obtain a solid, and adding the internal electron donor compound to react before or after the solid is precipitated.
In the step 2), the internal electron donor compounds shown in the formula (I) and the formula (II) can be carried on the solid through reaction, and the solid can be treated again by using a titanium compound and an inert diluent if necessary.
In addition, the specific procedures and operating conditions of the method may be carried out with reference to CN 85100997A.
Wherein the organic epoxy compound can be at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefin with 2-8 carbon atoms, diolefin or halogenated aliphatic olefin or diolefin; specific non-limiting examples are: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, and the like.
The organophosphorus compound may be selected from at least one of a hydrocarbyl ester of orthophosphoric acid, a hydrocarbyl ester of phosphorous acid and a halogenated hydrocarbyl ester; specific non-limiting examples are: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and trityl phosphite.
In the solvent system, the organic epoxy compound is preferably used in an amount of 0.2 to 5 moles per mole of magnesium, and the molar ratio of the organic epoxy compound to the organic phosphorus compound is (0.9 to 1.6): 1.
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. Wherein, the dosage of the precipitation aid can be 0.03-1.0 mol per mol of magnesium.
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.
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～C12Alkyl group of (1). The catalyst system of the present invention is suitable for the production of homopolymers of polyethylene, polypropylene, etc., and of ethylene and other alpha-olefins (e.g., propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene) The copolymer of (1).
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.
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
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, the mixture is maintained for 2.5 hours, the solid is completely dissolved, 1.4g of phthalic anhydride is added, and the mixture is maintained for 1 hour. The solution was cooled to below-25 ℃ and 56mL of TiCl were added dropwise over 1h4Slowly heating to 80 ℃, gradually precipitating solids in the heating process, adding 5mmol of the compound internal electron donor compound shown in the table 1, maintaining the temperature for 1h, filtering, and washing with 70mL of toluene for 2 times respectively to obtain solid precipitates. Then 60mL of toluene, 40mL of TiCl were added4The temperature is raised to 110 ℃ and maintained for 2h, the same operation is repeated once, 70mL of toluene is used for washing at 110 ℃ for 3 times, the time is 10min each, 60mL of hexane is added, and the washing is carried out for 2 times, so as to obtain the solid catalyst component a.
(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 cyclohexylmethyldimethoxysilane, to which 8 to c are addedIntroducing 2.3L of liquid propylene into 10mg of the solid catalyst component a and 1.2NL of hydrogen, heating to 70 ℃, and maintaining the temperature for 1 hour; and (3) cooling and decompressing to obtain the PP powder of the examples 1-5 and the PP powder of the comparative example 1. The performance data for each catalyst are shown in table 1.
TABLE 1
| Numbering | Compound internal electron donor compound | Polymerization Activity/(kgPP/gcat) | Isotactic index/% | MWD |
| Example 1 | A | 56.4 | 98.6 | 8.7 |
| Example 2 | B | 53.9 | 98.1 | 9.2 |
| Example 3 | C | 54.3 | 98.0 | 8.8 |
| Example 4 | D | 49.9 | 97.9 | 8.9 |
| Example 5 | E | 63.8 | 98.7 | 8.7 |
| Comparative example 1 | 1, 4-Cyclohexanedicarboxylic acid n-butyl ester | 33.8 | 96.5 | 9.5 |
Wherein:
a is 1, 4-cyclohexanedicarboxylic acid phenylmethyl ester: 2, 4-pentanediol dibenzoate: 1: 10
B is 1, 4-cyclohexanedicarboxylic acid isobutyl ester: 2, 4-pentanediol di-p-tert-butyl benzoate ═ 6: 1
C is 1, 4-cyclohexane propyl diformate: 3, 5-heptanediol di-p-isobutyl benzoate: 1
D is 1, 4-cyclohexanedicarboxylic acid cyclohexylmethyl ester: 3-ethyl-2, 4-pentanediol dibenzoate: 8: 1
E is 1, 4-cyclohexanedicarboxylic acid n-butyl ester: 2, 4-pentanediol di-n-butylbenzoate: 1: 6
As can be seen from Table 1, the catalyst system provided by the present invention can significantly improve the polymerization activity, and at the same time, can obtain a polymer with high isotactic index and wide molecular weight distribution, and the polymer has excellent comprehensive properties, 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 (13)
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;
formula (I) formula (II)
In the formula (I), R1And R2Are the same or different and are each selected from C1~C10Alkyl of (C)3~C10Cycloalkyl or C7~C20Aralkyl group of (1);
in the formula (II), R3And R4Identical or different, are each selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl or C7～C10Aralkyl group of (1);
R5and R6Identical or different, are each selected from C1～C10Alkyl of (C)3～C10Cycloalkyl or C7～C10And wherein the alkyl or hydrogen on the aralkyl is optionally substituted with an alkyl;
R7and R8Identical or different, are each selected from C6～C20Aryl of (C)7～C20Wherein the hydrogen on the aryl or alkylaryl group is optionally substituted with an alkyl group;
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.
2. The solid catalyst component according to claim 1 in which in the formula (I), R is1And R2Are the same or different and are each selected from C2~C8Alkyl of (C)3~C8Cycloalkyl or C7~C15Aralkyl group of (1);
in the formula (II), R3And R4Identical or different, each being selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl;
R5and R6Identical or different, each from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl;
R7and R8Identical or different, are each selected from C6～C20Aryl of (C)7～C20The hydrogen atoms of the aforementioned groups are optionally substituted with alkyl groups.
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 claim 1 in which the magnesium compound is selected from at least one of magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate 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.
6. The solid catalyst component according to claim 5 in which the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide;
the titanium compound is titanium tetrachloride.
7. The solid catalyst component according to claim 1, 5 or 6 in which 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.
8. The solid catalyst component according to claim 7 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.
9. 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 8;
and (b) component b: an alkyl aluminum compound;
optionally, component c: an external electron donor compound.
10. The catalyst system of claim 9, 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.
11. The catalyst system of claim 10, wherein the molar ratio of component a, component b, and component c is 1: 5-1000: 0-500 based on titanium: aluminum: silicon.
12. The catalyst system of claim 11, wherein the molar ratio of component a, component b, and component c is 1: 25-100: 1-100 in terms of titanium: aluminum: silicon.
13. A prepolymerized catalyst for olefin polymerization comprising a prepolymer prepared by prepolymerizing the catalyst system of any one of claims 9 to 12 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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| 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 | A method for the preparation of a solid catalyst for olefin polymerization |
| JP2013095768A (en) * | 2011-10-28 | 2013-05-20 | Sumitomo Chemical Co Ltd | Triether, catalyst for polymerizing olefin and method for producing olefin polymer |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | A method for the preparation of a solid catalyst for olefin polymerization |
| JP2013095768A (en) * | 2011-10-28 | 2013-05-20 | Sumitomo Chemical Co Ltd | Triether, catalyst for polymerizing olefin and method for producing olefin polymer |
| 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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