CN111234070B - Catalyst component, catalyst system and prepolymerized catalyst for olefin polymerization, use thereof and olefin polymerization process - Google Patents
Catalyst component, catalyst system and prepolymerized catalyst for olefin polymerization, use thereof and olefin polymerization process Download PDFInfo
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- CN111234070B CN111234070B CN201811450946.2A CN201811450946A CN111234070B CN 111234070 B CN111234070 B CN 111234070B CN 201811450946 A CN201811450946 A CN 201811450946A CN 111234070 B CN111234070 B CN 111234070B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
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Abstract
The invention belongs to the field of olefin polymerization catalysts, and provides a catalyst component for olefin polymerization, a catalyst system, a pre-polymerization catalyst, application of the pre-polymerization catalyst and an olefin polymerization method. The catalyst component is prepared by a method comprising the following steps: dissolving a magnesium compound in a solvent system containing an organic alcohol compound to form a uniform solution, adding a precipitating agent in the presence of a precipitating aid to precipitate a solid, and treating the solid with an internal electron donor to obtain a catalyst component; the auxiliary agent is at least one compound shown as a formula (I), wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9And R10Each independently selected from hydrogen and substituted or unsubstituted C1‑C20Straight chain alkyl, C3‑C20A branched alkyl group. When the catalyst system is used for propylene polymerization, the catalyst system has high activity and proper orientation capability, and is particularly suitable for producing polymers with moderate isotacticity.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst system, a pre-polymerization catalyst and application thereof, and an olefin polymerization method.
Background
The preparation of supported magnesium chloride catalysts usually involves chemically activating magnesium chloride and then treating the highly active magnesium chloride with a titanium compound. The chemical method for activating magnesium chloride is to dissolve magnesium chloride in a solvent system, then to precipitate magnesium chloride from the solution again by heat treatment to remove the solvent or adding a precipitating agent, etc., and to precipitate magnesium chloride from the solution again by using the technique of adding a precipitating agent, etc., a precipitating agent is often added to obtain a solid with uniform particle size.
The auxiliary agents used in the reports include mainly organic acid anhydrides, organic acids, ketones, ethers and other compounds, and patent documents CN200910091115.5, CN201010204493.2, CN201010294618.5, CN200910083987.7, CN 103201135576. x, CN201010283061.5, cn98101108.x, CN98126383.6, CN200810117895.1, CN98126385.2, CN98111780.5 and the like disclose the auxiliary agents. The widely used auxiliary agent in industry is phthalic anhydride, the activity of the catalyst prepared by using the compound as the auxiliary agent is not high, and when the catalyst is used for propylene polymerization, the isotacticity of the obtained polymer is very high and is not easy to adjust. When producing polymers with not very high isotacticity, such as special BOPP materials, the process conditions are harsh and complex.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a catalyst component, a catalyst system and a prepolymerized catalyst for olefin polymerization and use thereof, and a process for olefin polymerization. The catalyst system has high activity and proper orientation capability when being used for olefin polymerization, particularly propylene polymerization, and is particularly suitable for producing polymers with moderate isotacticity, such as special BOPP materials.
A first aspect of the present invention provides a catalyst component for the polymerization of olefins, the catalyst component being prepared by a process comprising the steps of:
dissolving a magnesium compound in a solvent system containing an organic alcohol compound to form a uniform solution, adding a precipitating agent in the presence of a precipitating aid to precipitate a solid, and treating the solid with an internal electron donor to obtain the catalyst component; the auxiliary agent is selected from at least one of compounds shown in a formula (I);
in the formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen and substituted or unsubstituted: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Alkenyl or C10-C20A condensed ring aryl group of (4); r1、R2、R3、R4、R5、R6、R7、R8、R9And R10Optionally bonded to form a ring or not.
According to a second aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
a component A: the above-mentioned catalyst component;
b, component B: an alkyl aluminum compound;
optionally, a component c: an external electron donor.
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 in the range of 0.1 to 1000g of the olefin polymer per g of the catalyst component.
According to a fourth aspect of the present invention there is provided the use of at least one of the above catalyst component, the above catalyst system and the above prepolymerised catalyst in the polymerisation of olefins.
According to a fifth aspect of the present invention, there is provided a process for the polymerization of olefins carried out in the presence of the above catalyst system or prepolymerized catalyst.
The catalyst (catalyst system/prepolymerized catalyst) comprising the catalyst component of the present invention has high activity and suitable orientation ability when used in olefin polymerization, especially propylene polymerization, and is particularly suitable for producing polymers with moderate isotacticity, such as BOPP specialty materials.
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 catalyst component for the polymerisation of olefins, the catalyst component being obtainable by a process comprising the steps of:
dissolving a magnesium compound in a solvent system containing an organic alcohol compound to form a uniform solution, adding a precipitating agent in the presence of a precipitating aid to precipitate a solid, and treating the solid with an internal electron donor to obtain the catalyst component; the auxiliary agent is selected from at least one of compounds shown in a formula (I);
in the formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen and substituted or unsubstituted: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Alkenyl or C10-C20A condensed ring aryl group of (4); r1、R2、R3、R4、R5、R6、R7、R8、R9And R10Optionally bonded to form a ring or not.
In the present invention, the following groups are substituted: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Alkenyl or C10-C20By fused ring aryl is meant that the carbon or hydrogen atoms in each group are optionally substituted with one or more heteroatoms selected from nitrogen, oxygen, sulfur, silicon, phosphorus orA halogen atom. In the present invention, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10When bonded to form a ring, the ring may contain a double bond or a hetero atom.
Preferably, in the formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen, substituted or unsubstituted: c1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl of, C7-C15Aralkyl of (2), C2-C10Alkenyl or C10-C15A condensed ring aryl group of (4); r1、R2、R3、R4、R5、R6、R7、R8、R9And R10Optionally bonded to form a ring or not.
Further preferably, R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen and C1-C4Substituted or unsubstituted straight-chain alkyl or C3-C4Substituted or unsubstituted branched alkyl groups of (a).
According to the present invention, specific examples of the precipitation aid include, but are not limited to: benzoic anhydride, 2-methylbenzoic anhydride, 3-methylbenzoic anhydride, 4-methylbenzoic anhydride, 3, 4-dimethylbenzoic anhydride, 2, 5-dimethylbenzoic anhydride, 2,3,4, 5-tetramethylbenzoic anhydride, 2-ethylbenzoic anhydride, 3-ethylbenzoic anhydride, 4-ethylbenzoic anhydride, 3, 4-diethylbenzoic anhydride, 2, 5-diethylbenzoic anhydride, 2,3,4,5, 6-pentaethylbenzoic anhydride, 2-n-propylbenzoic anhydride, 3-n-propylbenzoic anhydride, 4-n-propylbenzoic anhydride, 3, 4-di-n-propylbenzoic anhydride, 2, 5-di-n-propylbenzoic anhydride, 2,3,4, 5-tetra-n-propylbenzoic anhydride, 2-isopropylbenzoic anhydride, 3-isopropylbenzoic anhydride, 4-isopropylbenzoic anhydride, 3, 4-diisopropylbenzoic anhydride, 2, 5-diisopropylbenzoic anhydride, 2,3,4, 5-tetraisopropylbenzoic anhydride, 2-n-butylbenzoic anhydride, 3-n-butylbenzoic anhydride, 4-n-butylbenzoic anhydride, 3, 4-di-n-butylbenzoic anhydride, 2, 5-di-n-butylbenzoic anhydride, 2,3,4, 5-tetra-n-butylbenzoic anhydride, 2-isobutylbenzoic anhydride, 3-isobutylbenzoic anhydride, 4-isobutylbenzoic anhydride, 3, 4-diisobutylbenzoic anhydride, 2, 5-diisobutylbenzoic anhydride, 2,3,4, 5-tetraisobutylbenzoic anhydride, 3-methyl-4-ethylbenzoic anhydride, 3-methyl-4-n-propylbenzoic anhydride, 3-methyl-4-isopropylbenzoic anhydride, 3-methyl-4-n-butylbenzoic anhydride, 3-methyl-4-isobutylbenzoic anhydride, 2-methyl-5-ethylbenzoic anhydride, 2-methyl-5-n-propylbenzoic anhydride, 2-methyl-5-isopropylbenzoic anhydride, 2-methyl-5-n-butylbenzoic anhydride, 2-methyl-5-isobutylbenzoic anhydride, 3-ethyl-4-ethylbenzoic anhydride, 3-ethyl-4-n-propylbenzoic anhydride, 3-ethyl-4-isopropylbenzoic anhydride, 3-ethyl-4-n-butylbenzoic anhydride, 3-methyl-4-isopropylbenzoic anhydride, 3-methyl-4-n-butylbenzoic anhydride, 3-methyl-4-n-propylbenzoic anhydride, 3-methyl-4-ethylbenzoic anhydride, 3-methyl-4-butylbenzoic anhydride, 3-butylbenzoic anhydride, and mixtures thereof, 3-ethyl-4-isobutyl benzoic anhydride, 3-n-propyl-4-ethyl benzoic anhydride, 3-n-propyl-4-n-propyl benzoic anhydride, 3-n-propyl-4-isopropyl benzoic anhydride, 3-n-propyl-4-n-butyl benzoic anhydride, 3-n-propyl-4-isobutyl benzoic anhydride.
Preferably, the precipitation assistant is at least one of benzoic anhydride, 3, 4-dimethylbenzoic anhydride, 2-methylbenzoic anhydride, 3-methylbenzoic anhydride, 4-methylbenzoic anhydride and 3-ethylbenzoic anhydride.
In the present invention, the magnesium compound is selected from the group consisting of magnesium dihalides, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one of the halogen atoms in the formula is replaced by hydrocarbyloxy or halohydrocarbyloxy; preferred are magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
In the present invention, the organic alcohol compound-containing solvent system refers to a solvent system comprising an organic alcohol compound and another conventional solvent, and the solvent may be, for example, a hydrocarbon-based inert solvent such as decane.
Preferably, the organic alcohol compound is used in an amount of 1 to 15 moles, more preferably 2 to 5 moles, per mole of magnesium.
The organic alcohol compound in the invention has a general formula of R 'OH, wherein R' is a substituted or unsubstituted group as follows: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl or C2-C20The alkylene group of (1). For example, the organic alcohol compound may be ethanol, butanol, isooctanol, etc., and preferably isooctanol.
In the present invention, the precipitating agent can be selected from the precipitating agents conventional in the art, for example, the precipitating agent can be metal halide, metal alkoxide, etc., wherein the metal can be titanium, iron, zinc, etc. The precipitating agent is preferably a titanium compound with the general formula of TiXm(OR”)4-mWherein R' is C1-C20X is halogen, m is 1-4; specifically, the precipitating agent may be titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, etc., and titanium tetrachloride is more preferable.
According to the present invention, the internal electron donor may be selected from at least one of a nitrogen-containing compound, an oxygen-containing compound, a phosphorus-containing compound, a sulfur-containing compound and a silicon-containing compound, and the nitrogen-containing compound, the oxygen-containing compound, the phosphorus-containing compound, the sulfur-containing compound and the silicon-containing compound, which are used as the internal electron donor in the prior art, may be used in the present invention. The internal electron donor is preferably selected from oxygen-containing compounds, more preferably from ester compounds and/or ether compounds.
Specific examples of the internal electron donor include, but are not limited to: ethyl benzoate, di-n-butyl phthalate, diisobutyl phthalate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene, 1, 2-phenylene dibenzoate, diethyl diisobutyl malonate, diethyl di-n-butylmalonate, diethyl di-t-butylmalonate, dipropyl diisobutyl malonate, dipropyl di-n-butylmalonate, dipropyl di-t-butylmalonate, dibutyl diisobutyl malonate, dibutyl di-n-butylmalonate, 1, 3-bis (dimethylamino) -2, 2-dimethylpropane.
In the invention, the precipitation assistant is used in an amount of 0.01-30 mol, preferably 0.5-15 mol, per mol of magnesium; the dosage of the precipitating agent is 5-60 mol, preferably 10-40 mol; the amount of the internal electron donor is 0.005 to 15 mol, preferably 0.05 to 5 mol.
According to a specific embodiment of the present invention, first, the magnesium compound and the organic alcohol compound are mixed with an inert solvent in a molar ratio of 1: 2-5, heated to 120 ℃. (150 ℃) and reacted for 1-5 hours in a molar ratio of the compound of the general formula (I)/magnesium of 0.01-30. Then adding the alcohol compound cooled to room temperature into the titanium tetrachloride solution precooled to the temperature of minus 15 ℃ to minus 40 ℃ according to the molar ratio of titanium to magnesium of 20-50, heating to the temperature of 90-110 ℃, adding the alcohol compound into the titanium tetrachloride solution at the temperature of 100 ℃ and 130 ℃ according to the molar ratio of magnesium to the internal electron donor of 1-10, reacting for 1-3 hours, and filtering to separate solid particles. Then adding the solid particles into the titanium tetrachloride solution according to the titanium/magnesium molar ratio of 20-50, stirring and reacting at the temperature of 100 ℃ and 130 ℃ for 1.5-3 hours, and filtering to separate the solid particles. Finally, washing the solid particles by using an inert solvent with the temperature of 50-80 ℃, and drying to obtain the catalyst component.
According to a second aspect of the present invention, there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
a component A: the above-mentioned catalyst component;
b, component B: an alkyl aluminum compound;
optionally, a component c: an external electron donor.
According to the invention, the alkylaluminum compound has the general formula A1RnX3-nWherein R is hydrogen or C1-C20X is halogen, n is more than 0 and less than or equal to 3.
In particular, the alkylaluminum compound can be selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum sesquichloride, ethylaluminum dichloride. The alkyl aluminium compound is preferably triethylaluminium and/or triisobutylaluminium.
In the catalyst system, the molar ratio of the component A to the component B is as follows: the aluminum can be 1 to (5-1000), preferably 1 to (25-100).
In the present invention, the "optionally, a component c: the term "external electron donor" means that the external electron donor is optionally added or not added, as desired. For the application of olefin polymers with high stereoregularity, an external electron donor is required.
According to the present invention, the external electron donor may be selected from conventional external electron donors in the art, preferably organosilicon compounds. The organosilicon compound has the general formula R1 kSi(OR2)4-kWhere k is 0-3, R1Selected from halogen, hydrogen, C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)1-C20Haloalkyl or amino of (a); r2Is selected from C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)1-C20A haloalkyl or amino group.
Specifically, the organosilicon compound may be selected from trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, or methyl-t-butyldimethoxysilane; preferably cyclohexylmethyldimethoxysilane and/or diphenyldimethoxysilane;
in the catalyst system, the molar ratio of the component C to the component A is as follows: the titanium may be present in an amount of (0-500) to 1, preferably (25-100) to 1.
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.
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 prepolymerized 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.
In the present invention, the pre-polymerization factor of the prepolymer may be 0.1 to 1000g of the olefin polymer per g of the catalyst component, and preferably 0.2 to 500g of the olefin polymer per g of the 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 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.
According to a fourth aspect of the present invention there is provided the use of at least one of the above catalyst component, the above catalyst system and the above prepolymerised catalyst in the polymerisation of olefins.
According to a fifth aspect of the present invention, there is provided a process for the polymerization of olefins carried out in the presence of the above catalyst system or the above prepolymerized catalyst.
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.
In the present invention, the olefin has the general formula CH2Where R may be hydrogen or C1～C12A hydrocarbon group of (1). The catalyst system of the present invention is suitable for the production of homopolymers of polyethylene, polypropylene and the like, as well as copolymers of ethylene with other alpha-olefins, such as propylene, 1-butene, pentene, 1-hexene, octene, 4-methyl-1-pentene. Preferably the olefin is ethylene and/or propylene.
The 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 or gas phase, or may be carried out in a combination of liquid 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 can be 0-150 ℃, and preferably 60-90 ℃; the polymerization pressure may be 0.01 to 10 MPa.
The catalyst system of the invention has high activity and proper orientation capability when used for olefin polymerization, particularly propylene polymerization, and is particularly suitable for producing polymers with moderate isotacticity, such as special BOPP materials.
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 II 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) Melt index MI: measured using a melt index apparatus at 230 ℃ under a pressure of 2.16kg according to ASTM D1238-99 Standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.
Example 1
Under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent into a 500mL reactor provided with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 12mmol of benzoic anhydride, and continuously maintaining the temperature at 130 ℃ for reacting for 1 hour to obtain an alcohol compound; the alcohol hydrate was cooled to room temperature. Under the protection of nitrogen, the alcohol compound is added into 120mL titanium tetrachloride solution precooled to minus 22 ℃, the temperature is slowly increased to 100 ℃, and solid is gradually separated out in the process of temperature increase. Then, 10mmol of 3, 5-heptanediol dibenzoate compound was added to the solid, the mixture was heated to 110 ℃ and maintained for 2 hours, and then filtered while it was still hot, 120ml of titanium tetrachloride was added, the mixture was heated to 110 ℃ and reacted for 1 hour, and then filtered. The filtered solid particles were washed 4 times with anhydrous hexane and dried to obtain the catalyst component.
The obtained catalyst component is subjected to propylene polymerization reaction. 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 0.1mmol of methylcyclohexyldimethoxysilane (CHMMS), adding 8-10 mg of the catalyst component and 1.2NL of hydrogen (standard state), 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 respective performance data are shown in Table 1.
Example 2
The process was the same as in example 1, except that 3, 4-dimethylbenzoic anhydride was used instead of benzoic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 3
The process is the same as in example 1, except that 2-methylbenzoic anhydride is used instead of benzoic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 4
The process was the same as in example 1 except that 3-methylbenzoic anhydride was used instead of benzoic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 5
The process was the same as in example 1 except that 4-methylbenzoic anhydride was used instead of benzoic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 6
The procedure is as in example 1, except that 3-ethylbenzoic anhydride is used instead of benzoic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Comparative example 1
Under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent into a 500mL reactor provided with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 10mmol of phthalic anhydride, and continuously maintaining the temperature of 130 ℃ for reacting for 1 hour to obtain an alcohol compound; the alcohol hydrate was cooled to room temperature. Under the protection of nitrogen, the alcohol compound is added into 120mL titanium tetrachloride solution precooled to minus 22 ℃, the temperature is slowly increased to 100 ℃, and solid is gradually separated out in the process of temperature increase. Then, 10mmol of DIBP was added to the solid, the temperature was raised to 110 ℃ and maintained for 2 hours, and the mixture was filtered while it was hot, and 120ml of titanium tetrachloride was added thereto, the mixture was raised to 110 ℃ and reacted for 1 hour, followed by filtration. The filtered solid particles were washed 4 times with anhydrous hexane and dried to obtain the catalyst component.
The catalyst component obtained in comparative example 1 was subjected to propylene polymerization in the same manner as in example 1 to obtain PP powder. The respective performance data are shown in Table 1.
TABLE 1
| Numbering | Polymerization Activity/(kgPP/gcat/hr) | Isotactic index/% | Melt index/(g/10 min) |
| Example 1 | 52.0 | 96.3 | 3.4 |
| Example 2 | 50.8 | 97.0 | 2.9 |
| Example 3 | 50.9 | 96.8 | 3.2 |
| Example 4 | 51.2 | 96.7 | 3.1 |
| Example 5 | 51.5 | 96.7 | 3.0 |
| Example 6 | 52.0 | 97.1 | 2.9 |
| Comparative example 1 | 38.3 | 98.9 | 2.1 |
As can be seen from Table 1, the catalyst system provided by the present invention has high activity and suitable orientation ability when used for propylene polymerization, compared with the prior art (comparative example 1), and is particularly suitable for producing polymers with moderate isotacticity, such as special BOPP materials.
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 (28)
1. A catalyst component for the polymerization of olefins, characterized in that it is obtained by a process comprising the steps of:
dissolving a magnesium compound in a solvent system containing an organic alcohol compound to form a uniform solution, adding a precipitating agent in the presence of a precipitating aid to precipitate a solid, and treating the solid with an internal electron donor to obtain the catalyst component; the auxiliary precipitation agent is selected from at least one of compounds shown in a formula (I);
in the formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen and unsubstituted: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Alkenyl orC10-C20A condensed ring aryl group of (4); r1、R2、R3、R4、R5、R6、R7、R8、R9And R10Not forming a ring;
the precipitating agent is a titanium compound; the internal electron donor is selected from ester compounds and/or ether compounds.
2. The catalyst component according to claim 1 in which in formula (I), R is1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen, unsubstituted: c1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl of, C7-C15Aralkyl of (2), C2-C10Alkenyl or C10-C15A condensed ring aryl group of (4); r1、R2、R3、R4、R5、R6、R7、R8、R9And R10No ring is formed.
3. The catalyst component according to claim 2 in which in formula (I), R1、R2、R3、R4、R5、R6、R7、R8、R9And R10The same or different, each independently selected from hydrogen and C1-C4Unsubstituted straight-chain alkyl or C3-C4Unsubstituted branched alkyl.
4. The catalyst component according to claim 2 in which the resolving aid is selected from benzoic anhydride, 2-methylbenzoic anhydride, 3-methylbenzoic anhydride, 4-methylbenzoic anhydride, 3, 4-dimethylbenzoic anhydride, 2, 5-dimethylbenzoic anhydride, 2,3,4, 5-tetramethylbenzoic anhydride, 2-ethylbenzoic anhydride, 3-ethylbenzoic anhydride, 4-ethylbenzoic anhydride, 3, 4-diethylbenzoic anhydride, 2, 5-diethylbenzoic anhydride, 2,3,4,5, 6-pentaethylbenzoic anhydride, 2-n-propylbenzoic anhydride, 3-n-propylbenzoic anhydride, 4-n-propylbenzoic anhydride, 3, 4-di-n-propylbenzoic anhydride, 2, 5-di-n-propylbenzoic anhydride, 2-n-propylbenzoic anhydride, 3, 4-di-n-propylbenzoic anhydride, 2, 5-di-n-propylbenzoic anhydride, 2-n-propylbenzoic anhydride, 3, 4-propylbenzoic anhydride, 2, 5-di-n-propylbenzoic anhydride, 2, 4-n-propylbenzoic anhydride, 3-n-propylbenzoic anhydride, 4-propylbenzoic anhydride, and a-n-propylbenzoic anhydride, 2,3,4, 5-tetra-n-propylbenzoic anhydride, 2-isopropylbenzoic anhydride, 3-isopropylbenzoic anhydride, 4-isopropylbenzoic anhydride, 3, 4-diisopropylbenzoic anhydride, 2, 5-diisopropylbenzoic anhydride, 2,3,4, 5-tetraisopropylbenzoic anhydride, 2-n-butylbenzoic anhydride, 3-n-butylbenzoic anhydride, 4-n-butylbenzoic anhydride, 3, 4-di-n-butylbenzoic anhydride, 2, 5-di-n-butylbenzoic anhydride, 2,3,4, 5-tetra-n-butylbenzoic anhydride, 2-isobutylbenzoic anhydride, 3-isobutylbenzoic anhydride, 4-isobutylbenzoic anhydride, 3, 4-diisobutylbenzoic anhydride, 2, 5-diisobutylbenzoic anhydride, 2,3,4, 5-tetraisobutylbenzoic anhydride, 3-methyl-4-ethylbenzoic anhydride, 3-methyl-4-n-propylbenzoic anhydride, 3-methyl-4-isopropylbenzoic anhydride, 3-methyl-4-n-butylbenzoic anhydride, 3-methyl-4-isobutylbenzoic anhydride, 2-methyl-5-ethylbenzoic anhydride, 2-methyl-5-n-propylbenzoic anhydride, 2-methyl-5-isopropylbenzoic anhydride, 2-methyl-5-n-butylbenzoic anhydride, 2-methyl-5-isobutylbenzoic anhydride, 3-ethyl-4-ethylbenzoic anhydride, 3-ethyl-4-n-propylbenzoic anhydride, 3-methyl-4-ethylbenzoic anhydride, 3-methyl-4-isobutylbenzoic anhydride, 3-methyl-4-isopropylbenzoic anhydride, 3-methyl-4-isobutylbenzoic anhydride, 3-methyl-4-propylbenzoic anhydride, 3-methyl-4-isopropylbenzoic anhydride, 3-methyl-4-isobutylbenzoic anhydride, 3-methyl-4-methyl-ethylbenzoic anhydride, 3-methyl-4-propylbenzoic anhydride, and, 3-ethyl-4-isopropylbenzoic anhydride, 3-ethyl-4-n-butylbenzoic anhydride, 3-ethyl-4-isobutylbenzoic anhydride, 3-n-propyl-4-ethylbenzoic anhydride, 3-n-propyl-4-n-propylbenzoic anhydride, 3-n-propyl-4-isopropylbenzoic anhydride, 3-n-propyl-4-n-butylbenzoic anhydride, and 3-n-propyl-4-isobutylbenzoic anhydride.
5. The catalyst component according to claim 4 in which the resolving aid is at least one of benzoic anhydride, 3, 4-dimethylbenzoic anhydride, 2-methylbenzoic anhydride, 3-methylbenzoic anhydride, 4-methylbenzoic anhydride and 3-ethylbenzoic anhydride.
6. The catalyst component according to claim 1 in which the magnesium compound is selected from magnesium dihalides, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides of which one of the halogen atoms is replaced by hydrocarbyloxy or halohydrocarbyloxy group;
the organic alcohol compound has a general formula of R 'OH, wherein R' is a substituted or unsubstituted group as follows: c1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl of, C7-C20Aralkyl or C2-C20An alkenyl group of (1);
the organic alcohol compound is used in an amount of 1 to 15 moles per mole of magnesium.
7. The catalyst component according to claim 6 in which the magnesium compound is a magnesium dihalide or an alcoholate of a magnesium dihalide.
8. The catalyst component according to claim 7 in which the magnesium compound is magnesium dichloride, magnesium dibromide, magnesium diiodide and their alcoholates.
9. The catalyst component according to claim 6 in which the organic alcohol compound is at least one of ethanol, butanol and isooctanol.
10. The catalyst component according to claim 6 in which the organic alcohol compound is used in an amount of 2 to 5 moles per mole of magnesium.
11. The catalyst component according to claim 1 in which the precipitant has the general formula TiXm(OR”)4-mWherein R' is C1-C20X is halogen, and m is 1-4.
12. The catalyst component of claim 11 in which the precipitation agent is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
13. The catalyst component according to claim 12 in which the precipitating agent is titanium tetrachloride.
14. The catalyst component according to any of claims 1 to 13 in which the precipitant aid is used in an amount of 0.01 to 30 moles per mole of magnesium; the dosage of the precipitating agent is 5-60 mol; the dosage of the internal electron donor is 0.005-15 mol.
15. The catalyst component according to claim 14 in which the precipitant aid is used in an amount of 0.5 to 15 moles per mole of magnesium; the dosage of the precipitating agent is 10-40 mol; the dosage of the internal electron donor is 0.05-5 mol.
16. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
a component A: a catalyst component according to any one of claims 1 to 15;
b, component B: an alkyl aluminum compound;
optionally, a component c: an external electron donor.
17. The catalyst system according to claim 16, wherein the alkylaluminum compound has the general formula AlRnX3-nWherein R is hydrogen or C1-C20X is halogen, n is more than 0 and less than or equal to 3;
the molar ratio of the component A to the component B is 1: 5-1000 in terms of titanium: aluminum.
18. The catalyst system according to claim 17, wherein the alkyl aluminium compound is triethylaluminium and/or triisobutylaluminium.
19. The catalyst system of claim 17, wherein the molar ratio of the component a to the component b is 1: 25-100 based on titanium: aluminum.
20. The catalyst system of any one of claims 16-19, wherein the external electron donor is an organosilicon compound having the general formula R1 kSi(OR2)4-kWhere k is 0-3, R1Selected from halogen, hydrogen, C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)1-C20Haloalkyl or amino of (a); r2Is selected from C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)1-C20Haloalkyl or amino of (a);
the molar ratio of the component C to the component A is (0-500): 1 in terms of silicon: titanium.
21. The catalyst system according to claim 20, wherein the organosilicon compound is cyclohexylmethyldimethoxysilane and/or diphenyldimethoxysilane.
22. The catalyst system of claim 20, wherein the molar ratio of the C component to the A component is (25-100): 1, expressed as Si: Ti.
23. A prepolymerized catalyst for olefin polymerization comprising a prepolymer prepared by prepolymerizing the catalyst system of any one of claims 16 to 22 with a prepolymerized olefin, wherein the prepolymerization ratio of the prepolymer is in the range of 0.1 to 1000g of olefin polymer per g of catalyst component.
24. The prepolymerized catalyst for olefin polymerization according to claim 23, wherein the prepolymerization multiple of the prepolymer is 0.2 to 500g of the olefin polymer per g of the catalyst component.
25. Use of at least one of the catalyst component of any one of claims 1 to 15, the catalyst system of any one of claims 16 to 22 and the prepolymerised catalyst of claim 23 or 24 in the polymerisation of olefins.
26. A process for the polymerization of olefins in the presence of a catalyst system according to any of claims 16 to 22 or a prepolymerised catalyst according to claim 23 or 24.
27. The process for the polymerization of olefins according to claim 26, wherein the olefin has the general formula CH2R is hydrogen or C1-C12A hydrocarbon group of (1).
28. The process for the polymerization of olefins according to claim 27, wherein the olefin is ethylene and/or propylene.
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