CN111234072B - 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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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 comprises magnesium, titanium, halogen and a compound shown as a formula (I); (I) in R1、R2、R3、R4、R5And R6Each independently selected from hydrogen and substituted or unsubstituted C1‑C20Straight chain alkyl, C3‑C20Branched alkyl radical, C3‑C20A cycloalkyl group. When the catalyst system is used for propylene polymerization, the safety coefficient is higher, the catalyst has better catalytic activity, and the hydrogen regulation sensitivity of the catalyst is good.
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 prior art shows that phthalic anhydride is a preferred example as a precipitation aid, but part of phthalic anhydride or phthalic anhydride reacts with other substances in the system during the preparation of the catalyst to form phthalate compounds which remain in the catalyst. Such compounds tend to be of limited use due to safety and hygiene issues, such as the potential for fertility. There are documents disclosing the use of other ester compounds as a precipitation aid, such as cyclohexane dicarboxylic acid ester compounds as a precipitation aid for the preparation of catalysts, which have large particle size, are easily broken during the polymerization process, and the resulting polymers have low melt index and low bulk density, which are not conducive to packaging and transportation. CN101864009A discloses that diol ester compounds are used as a precipitation aid to prepare a catalyst, and in the process of preparing the catalyst by the method, catalyst particles are not easy to settle, the final catalyst has poor fluidity and is easy to aggregate into blocks, and when the catalyst is used for olefin polymerization, the hydrogen regulation sensitivity is poor.
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. When the catalyst system is used for olefin polymerization, particularly propylene polymerization, the safety coefficient is higher, the catalyst has better catalytic activity, and the hydrogen regulation sensitivity of the catalyst is good.
A first aspect of the present invention provides a catalyst component for olefin polymerization comprising magnesium, titanium, halogen and a compound of formula (I);
in the formula (I), R1、R2、R3、R4、R5And R6The 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、R5And R6Optionally 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.
In the preparation process of the catalyst component, the compound shown in the general formula (I) is added to prepare the catalyst, so that the catalyst has good fluidity, good particle form, uniform particle size distribution and excellent comprehensive performance, and shows a certain synergistic effect. The catalyst is used for olefin polymerization, and particularly has high activity when propylene is polymerized, and the obtained polymer has good stereoregularity and good hydrogen regulation sensitivity, and has wide application prospect.
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 olefin polymerization comprising magnesium, titanium, halogen and a compound of formula (I);
in the formula (I), the compound is shown in the specification,R1、R2、R3、R4、R5and R6The 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、R5And R6Optionally 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, or halogen atoms. In the present invention, R1、R2、R3、R4、R5And R6When 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、R5And R6The 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、R5And R6Optionally bonded to form a ring or not.
Further preferably, R1、R2、R3、R4、R5And R6The same or different, each independently selected from hydrogen and C1-C6Substituted or unsubstituted straight-chain alkyl or C3-C6Substituted or unsubstituted branched alkyl of R1、R2、R3、R4、R5And R6Optionally bonded to form a ring or not.
According to the present invention, specific examples of the compound represented by the formula (I) include, but are not limited to: 4-cyclohexene-1, 2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-ethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-propyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isopropyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-butyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isobutyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-pentyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isopentyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-cyclohexyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-dimethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-di-n-propyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diisopropyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-di-n-butyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diisobutyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride.
Preferably, the compound represented by the formula (I) is at least one of 4-cyclohexene-1, 2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-dimethyl-4-cyclohexene-1, 2-dicarboxylic anhydride and 5-norbornene-2, 3-dicarboxylic anhydride.
According to one embodiment of the invention, the catalyst component is prepared by the following method:
contacting an organic solution containing magnesium with the compound shown in the formula (I) and a compound containing Ti, separating out a solid, treating titanium, washing, and optionally adding an internal electron donor in the process to obtain the catalyst component.
Preferably, the organic solution containing magnesium is a homogeneous solution formed by dissolving a magnesium compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound.
Specifically, the magnesium compound may be selected from magnesium dihalides, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one of the halogen atoms is replaced by a hydrocarbyloxy or halohydrocarbyloxy group; preferred are magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
The solvent system containing the organic epoxy compound and the organic phosphorus compound means a solvent system composed of the organic epoxy compound, the organic phosphorus compound and other conventional solvents, and for example, the solvent may be a hydrocarbon solvent such as toluene.
Preferably, the organic epoxy compound is used in an amount of 0.2 to 10 moles and the organic phosphorus compound is used in an amount of 0.1 to 3 moles per mole of magnesium.
The organic epoxy compounds and organic phosphorus compounds in the present invention can be found in patent document CN85100997, the relevant contents of which are incorporated herein by reference.
Specifically, the organic epoxy compound includes at least one of an oxide, a glycidyl ether and an internal ether of an aliphatic olefin having 2 to 8 carbon atoms, a diolefin or a halogenated aliphatic olefin or a diolefin. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
Wherein the organophosphorus compound comprises hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and trityl phosphite.
In the present invention, the Ti-containing compound may be selected from conventional Ti compounds in the art, preferably Ti-containing compounds having the general formula of TiXm(OR”)4-mIn the formula, R' isC1-C20X is halogen, m is 1-4; specifically, the Ti-containing compound 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 present invention, the compound represented by the formula (I) is used in an amount of 0.001 to 30 moles, preferably 0.05 to 15 moles, per mole of magnesium; the amount of the Ti-containing compound is 3 to 40 mol, preferably 5 to 30 mol; the amount of the internal electron donor is 0.005 to 15 mol, preferably 0.05 to 5 mol.
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 AlRnX3-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 can be 1 to (5-1000), preferably 1 to (25-100) calculated by titanium to aluminum.
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 of the invention, the molar ratio of the component C to the component A can be (0-500) to 1, preferably (25-100) to 1 in terms of silicon to titanium.
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 higher safety factor when being used for olefin polymerization, especially propylene polymerization, and the catalyst has better catalytic activity and good hydrogen regulation sensitivity.
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
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 pure nitrogen, the temperature is raised to 50 ℃ under stirring, the temperature is maintained for 2.5 hours, the solid is completely dissolved, 10mmol of 4-cyclohexene-1, 2-dicarboxylic anhydride is added, and the temperature is maintained for 1 hour continuously. Cooling the solution to below-29 ℃, and dripping TiCl into the solution within 1h456mL, after the dropwise addition, the temperature is raised to 80 ℃ at a constant speed, and solids are gradually separated out in the temperature raising process. 6mmol of 3, 5-heptanediol dibenzoate was added to the solid, the temperature was maintained for 1 hour, and after filtration, the solid was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. Then, 60mL of toluene and TiCl were added to the precipitate440mL, heating to 110 ℃, maintaining for 2h, and filtering; the same operation is repeated once. Thereafter, the precipitate was further washed with 70mL of toluene three times at 110 ℃ for 10min each, and 60mL of hexane was further added thereto, followed by washing twice to obtain a 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 catalyst component was prepared as in example 1, except that 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride was used instead of 4-cyclohexene-1, 2-dicarboxylic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 3
The catalyst component was prepared as in example 1, except that 4, 4-dimethyl-4-cyclohexene-1, 2-dicarboxylic anhydride was used instead of 4-cyclohexene-1, 2-dicarboxylic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 4
The catalyst component was prepared as in example 1, except that 5-norbornene-2, 3-dicarboxylic anhydride was used instead of 4-cyclohexene-1, 2-dicarboxylic anhydride.
The propylene polymerization process was the same as in example 1. The respective performance data are shown in Table 1.
Example 5
The catalyst components were prepared in the same manner as in example 1.
The propylene polymerization process was the same as in example 1, except that the amount of hydrogen added was 7.2L in the propylene polymerization.
Comparative example 1
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 pure nitrogen, the temperature is raised to 50 ℃ under stirring, the temperature is maintained for 2.5 hours, the solid is completely dissolved, 10mmol of phthalic anhydride is added, and the temperature is maintained for 1 hour. Cooling the solution to below-29 ℃, and dripping TiCl into the solution within 1h456mL, after the dropwise addition, the temperature is raised to 80 ℃ at a constant speed, and solids are gradually separated out in the temperature raising process. 6mmol of DIBP was added to the solid, the temperature was maintained for 1 hour, and after filtration, the solid was washed twice with 70mL of toluene to obtain a solid precipitate. Then, 60mL of toluene and TiCl were added to the precipitate440mL, heating to 110 ℃, maintaining for 2h, and filtering; the same operation is repeated once. Thereafter, the precipitate was further washed with 70mL of toluene three times at 110 ℃ for 10min each, and 60mL of hexane was further added thereto, followed by washing twice to obtain a 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.
Comparative example 2
The catalyst component was prepared in the same manner as in comparative example 1.
The propylene polymerization process was the same as comparative example 1 except that: during the polymerization of propylene, the amount of hydrogen added was 7.2L. 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 | 48.3 | 96.7 | 4.3 |
| Example 2 | 45.4 | 96.4 | 5.0 |
| Example 3 | 50.1 | 96.6 | 4.7 |
| Example 4 | 51.8 | 96.9 | 4.5 |
| Example 5 | 54.7 | 94.0 | 39.5 |
| Comparative example 1 | 38.5 | 98.0 | 2.2 |
| Comparative example 2 | 43.8 | 96.3 | 28.6 |
As can be seen from Table 1, when the catalyst system provided by the invention is used for propylene polymerization, compared with the prior art (comparative examples 1-2), the safety coefficient is higher, the catalyst has better catalytic activity, and the hydrogen regulation sensitivity of the catalyst is good.
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 (30)
1. A catalyst component for the polymerization of olefins, comprising magnesium, titanium, halogen and a compound of formula (i);
in the formula (I), R1、R2、R3、R4、R5And R6The 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 or C10-C20A condensed ring aryl group of (4); r1、R2、R3、R4、R5And R6No ring is formed.
2. The catalyst component according to claim 1 in which in formula (I), R is1、R2、R3、R4、R5And R6The 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、R5And R6No ring is formed.
3. The catalyst component according to claim 2 in which in formula (I), R1、R2、R3、R4、R5And R6The same or different, each independently selected from hydrogen and C1-C6Unsubstituted straight-chain alkyl or C3-C6Unsubstituted branched alkyl of R1、R2、R3、R4、R5And R6No ring is formed.
4. The catalyst component according to claim 1 in which the compound of formula (I) is selected from 4-cyclohexene-1, 2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-ethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-propyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isopropyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-butyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isobutyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-n-pentyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-isopentyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4-cyclohexyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-dimethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diethyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-di-n-propyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diisopropyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-di-n-butyl-4-cyclohexene-1, 2-dicarboxylic anhydride, 4, 5-diisobutyl-4-cyclohexene-1, at least one of 2-dicarboxylic anhydrides.
5. The catalyst component according to claim 4 in which the compound of formula (I) is at least one of 4-cyclohexene-1, 2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride.
6. The catalyst component according to any one of claims 1 to 5, which is prepared by a process comprising:
contacting an organic solution containing magnesium with the compound shown in the formula (I) and a compound containing Ti, separating out a solid, treating titanium, washing, and optionally adding an internal electron donor in the process to obtain the catalyst component.
7. The catalyst component according to claim 6 in which the organic solution comprising magnesium is a homogeneous solution of a magnesium compound dissolved in a solvent system comprising an organic epoxy compound and an organophosphorus compound.
8. The catalyst component according to claim 7 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 general formula of the Ti-containing compound is TiXm(OR”)4-mWherein R' is C1-C20X is halogen, m is 1-4;
the organic epoxy compound is selected from 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;
the organophosphorus compound is selected from hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid.
9. The catalyst component according to claim 8 in which the magnesium compound is a magnesium dihalide or an alcoholate of a magnesium dihalide.
10. The catalyst component according to claim 9 in which the magnesium compound is magnesium dichloride, magnesium dibromide, magnesium diiodide and their alcoholates.
11. The catalyst component of claim 8 in which the Ti-containing compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
12. The catalyst component according to claim 11 in which the Ti-containing compound is titanium tetrachloride.
13. The catalyst component according to claim 6 in which the internal electron donor is selected from at least one of nitrogen containing compounds, oxygen containing compounds, phosphorous containing compounds, sulfur containing compounds and silicon containing compounds.
14. The catalyst component according to claim 13 in which the internal electron donor is selected from oxygenates.
15. The catalyst component according to claim 14 in which the internal electron donor is selected from ester compounds and/or ether compounds.
16. The catalyst component according to any of claims 7 to 15 in which the compound of formula (i) is used in an amount of 0.001 to 30 moles per mole of magnesium; the dosage of the Ti-containing compound is 3-40 mol; the dosage of the internal electron donor is 0.005-15 mol; the dosage of the organic epoxy compound is 0.2-10 mol; the amount of the organic phosphorus compound is 0.1 to 3 mol.
17. The catalyst component according to claim 16 in which the compound of formula (i) is used in an amount of 0.05 to 15 moles per mole of magnesium; the amount of the Ti-containing compound is 5-30 mol; the dosage of the internal electron donor is 0.05-5 mol; the dosage of the organic epoxy compound is 0.2-10 mol; the amount of the organic phosphorus compound is 0.1 to 3 mol.
18. 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 17;
b, component B: an alkyl aluminum compound;
optionally, a component c: an external electron donor.
19. The catalyst system according to claim 18, 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.
20. The catalyst system according to claim 19, wherein the alkyl aluminium compound is triethylaluminium and/or triisobutylaluminium.
21. The catalyst system of claim 19, wherein the molar ratio of the component a to the component b is 1: 25-100 based on titanium: aluminum.
22. According to claim 1The catalyst system of any one of 8 to 21, wherein the external electron donor is an organosilicon compound having a general formula of 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.
23. The catalyst system according to claim 22, wherein the organosilicon compound is cyclohexylmethyldimethoxysilane and/or diphenyldimethoxysilane.
24. The catalyst system of claim 22, wherein the molar ratio of the C component to the A component is (25-100): 1, expressed as Si: Ti.
25. A prepolymerized catalyst for olefin polymerization comprising a prepolymer prepared by prepolymerizing the catalyst system of any one of claims 18 to 24 with a prepolymerized olefin, wherein the prepolymerization ratio of the prepolymer is 0.1 to 1000g of the olefin polymer per g of the catalyst component.
26. The prepolymerized catalyst for olefin polymerization according to claim 25, wherein the prepolymerization multiple of the prepolymer is 0.2 to 500g of the olefin polymer per g of the catalyst component.
27. Use of at least one of the catalyst component of any one of claims 1 to 17, the catalyst system of any one of claims 18 to 24 and the prepolymerised catalyst of claim 25 or 26 in the polymerisation of olefins.
28. A process for the polymerization of olefins in the presence of a catalyst system according to any of claims 18 to 24 or a prepolymerised catalyst according to claim 25 or 26.
29. The process for the polymerization of olefins according to claim 28, wherein the olefin has the general formula CH2R is hydrogen or C1-C12A hydrocarbon group of (1).
30. The process for the polymerization of olefins according to claim 29, wherein the olefin is ethylene and/or propylene.
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