CN114426606B - Catalyst for olefin polymerization, preparation method and application thereof - Google Patents
Catalyst for olefin polymerization, preparation method and application thereof Download PDFInfo
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- CN114426606B CN114426606B CN202011181956.8A CN202011181956A CN114426606B CN 114426606 B CN114426606 B CN 114426606B CN 202011181956 A CN202011181956 A CN 202011181956A CN 114426606 B CN114426606 B CN 114426606B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a catalyst for olefin polymerization, which comprises the following components or the reaction product of the following components: (1) a magnesium compound; (2) a nickel compound; (3) a nitroxide compound; (4) an organoaluminum compound; (5) an electron donor compound; (6) An inorganic oxide support, wherein the nickel compound is selected from compounds represented by formula (I). The catalyst of the invention has simple and convenient loading and forming, is convenient for industrial production, has good product particle shape and spontaneous induced branching capability, and can obtain resin products with medium and low density without adding comonomer. In addition, the catalyst has high activity and high bulk density, and is particularly advantageous in gas phase polymerization.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst for olefin polymerization, a preparation method thereof, a composite catalyst containing the catalyst and an application of the composite catalyst.
Background
In the polymerization of ethylene or the copolymerization of ethylene with alpha-olefins, the properties of the catalyst influence the properties of the polymer. The production of linear low density polyethylene by the low pressure process has been one of the core competitiveness in the polyolefin industry. However, as the density of polyethylene decreases, the solubility of polyethylene in the solvent will increase substantially, resulting in that linear low density polyethylene cannot be produced by slurry process, but only by gas phase polymerization process or solution polymerization process. But the solution polymerization process has harsh conditions and high cost, and a solution polymerization process device which runs very stably is not provided at home. At present, a large number of gas-phase polymerization process devices are available in China, and are mainly used for producing linear low-density polyethylene.
In the gas phase polymerization process, when the traditional high-activity nickel-based catalyst is adopted, when lower-density resin production is carried out, the powder is sticky, and is easy to agglomerate and stick to the wall, so that the production cannot be stably carried out for a long time, and even when the treatment is not proper, malignant production accidents such as implosion and the like can occur. The metallocene catalyst can produce products with lower density through loading treatment, but the catalytic activity of the metallocene catalyst is reduced greatly after the metallocene catalyst is subjected to conventional loading treatment, and meanwhile, due to the characteristics of the metallocene catalyst, the metallocene catalyst is very sensitive to hydrogen, a device needs to be modified in a targeted manner, and the process operation difficulty is higher. However, other single-site transition metal catalysts have not been reported in practical industrial application.
CN100368440 discloses a spray-dried polymerization catalyst and a polymerization process using the same, the catalyst comprising a spray-dried composition of an inert porous filler and the reaction product of: magnesium halide, solvent, electron donor compound, transition metal compound mixture or reaction product. The filler is substantially spherical and has an average particle size of 1 to 12um. Although the catalyst is suitable for producing linear low density polyethylene, the copolymerization performance is general, the activity of the catalyst is not high enough, and the amount of oligomers in the polymer is large.
CN201710399926.6 discloses a method for thermally activating a porous carrier for metallocene, which can prepare a silica gel carrier with better pore characteristics and particle shape, but the method is still more complicated and cannot obtain a catalyst product in one step.
EP99955006 discloses a metallocene catalyst composition which gives high-transparency polyethylene with a low ratio of aluminium to metal and a low ash content. It cannot be used in a gas phase process unit.
US08644764 discloses a method for supporting metallocene catalysts, where heating of the alumoxane before supporting can increase the catalyst activity, but this method uses a large amount of MAO and the final activity of the catalyst is still low.
CN201010293624.9 discloses a method for treating a silica gel support with a silica coated alumina activator-support to improve catalytic activity. However, this method is complicated in operation, and can be carried out only in a laboratory, and it is difficult to scale up the industrial scale production, and the activity of the obtained catalyst is far from that of the nickel-based catalyst which is commonly used in the gas phase process in the industry at present.
CN100408603C discloses a catalyst for ethylene polymerization prepared by a spray drying process, which has better activity, but the copolymerization performance is still not improved in gas phase polymerization.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a single-site olefin polymerization catalyst, a preparation method thereof and a composite catalyst containing the catalyst. The catalyst of the invention has simple preparation, good particle shape and high polymerization activity, can directly obtain industrial production scale, can be directly used on a gas phase polymerization process device without modifying the device, and simultaneously shows the performance which is not possessed by the conventional nickel catalyst.
The present invention provides, in a first aspect, a catalyst for olefin polymerization, comprising (1) a magnesium compound; (2) a nickel compound; (3) an nitroxide compound; (4) an organoaluminum compound; (5) an electron donor compound; (6) an inorganic oxide support;
the nickel compound is selected from compounds shown in a formula (I),
wherein R is 1 -R 6 The same or different, each independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl and hydrocarbyloxy, preferably from hydrogen, fluorine, chlorine, bromine, iodine, substituted or unsubstituted C 1 -C 20 Alkyl of (C) 2 -C 20 Alkenyl of (C) 2 -C 20 Alkynyl of (A), C 1 -C 20 Alkoxy group of (C) 2 -C 20 Alkenyloxy of (C) 2 -C 20 Alkynyloxy of (a), C 6 -C 20 Aryl radical, C 7 -C 20 Aralkyl and C 7 -C 20 An alkaryl group, the alkyl group being a straight chain alkyl group, a branched chain alkyl group or a cycloalkyl group, the alkoxy group being a straight chain alkoxy group, a branched chain alkoxy group or a cycloalkoxy group;
x is a halogen, preferably selected from fluorine, chlorine, bromine and iodine.
According to some embodiments of the invention, the substituent is selected from halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy group.
In the present invention, the substitution may be a substitution of a carbon on the main chain or a substitution of a hydrogen on a carbon.
According to some embodiments of the invention, the substituent is fluorine, chlorine, bromine or iodine.
According to some embodiments of the invention, in formula (I), R 1 -R 6 The same or different, each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C with or without substituent 1 -C 10 Alkyl of (C) 2 -C 10 Alkenyl of, C 2 -C 10 Alkynyl of, C 1 -C 10 Alkoxy group of (1), C 2 -C 10 Alkenyloxy of (C) 2 -C 10 Alkynyloxy of (a), C 6 -C 15 Aryl radical, C 7 -C 15 Aralkyl and C 7 -C 15 An alkaryl group.
According to some embodiments of the invention, R in formula (I) 1 -R 6 The same or different, each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C with or without substituent 1 -C 6 Alkyl of (C) 2 -C 6 Alkenyl of, C 2 -C 6 Alkynyl of, C 1 -C 6 Alkoxy group of (C) 2 -C 6 Alkenyloxy of (C) 2 -C 6 Alkynyloxy of (C) 6 -C 10 Aryl radical, C 7 -C 10 Aralkyl and C 7 -C 10 An alkaryl group.
According to some embodiments of the invention, C 1 -C 6 The alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3, 3-dimethylbutyl.
According to some embodiments of the invention, C is 1 -C 6 The alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy.
According to some embodiments of the invention, the nickel compound is selected from one or more of the following compounds:
1) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝H，X＝Br；
2) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝H，X＝Br；
3) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝iPr，R 2 ＝R 5 ＝H，X＝Br；
4) A nickel complex of the formula (I), wherein R 1 ＝R 2 ＝R 3 ＝R 4 ＝R 5 ＝R 6 ＝Me，X＝Br；
5) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Br，X＝Br；
6) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Et，X＝Br
7) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Me，X＝Br；
8) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Br，X＝Br；
9) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝H，X＝Cl；
10 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝H，X＝Cl；
11 A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝iPr，R 2 ＝R 5 ＝H，X＝Cl；
12 A nickel complex represented by the formula (I) wherein R 1 ＝R 2 ＝R 3 ＝R 4 ＝R 5 ＝R 6 ＝Me，X＝Cl；
13 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Br，X＝Cl；
14 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Et，X＝Cl；
15 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Me，X＝Cl；
16 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Br，X＝Cl。
According to some embodiments of the invention, the nitroxide compound is a morpholino compound, preferably morpholine and/or 4-cyanomorpholine.
According to some embodiments of the invention, the inorganic oxide support has a particle size of 0.01 to 10 μm, preferably 0.02 to 5 μm, more preferably 0.05 to 1 μm.
According to some embodiments of the invention, the inorganic oxide support is an oxide of silicon and/or aluminum, preferably silica.
According to some preferred embodiments of the present invention, the inorganic oxide support is a silica support of 0.05 to 1 μm, and the catalyst particles formed using the support have good shape, high strength, and are not easily crushed.
According to some embodiments of the invention, the organoaluminum compound is selected from compounds of the general formula A1R n X 3-n Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is more than 0 and less than or equal to 3.
According to some embodiments of the invention, the general formula A1R n X 3-n Wherein R is hydrogen or alkyl with 1-20 carbon atoms.
According to some embodiments of the invention, the compound of formula A1R n X 3-n Wherein R is hydrogen or alkyl with 1-10 carbon atoms.
According to some embodiments of the invention, the compound of formula A1R n X 3-n Wherein X is fluorine, chlorine, bromine or iodine.
Specific examples of the organoaluminum compounds, according to some embodiments of the present invention, include, but are not limited to, one or more of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum monochloride.
According to some embodiments of the invention, the magnesium compound is a magnesium halide, preferably at least one selected from the group consisting of magnesium dichloride, magnesium dibromide and magnesium diiodide.
According to some preferred embodiments of the present invention, the electron donor compound is selected from C 1 -C 4 Alkyl esters of saturated fatty carboxylic acids, C 7 -C 8 Alkyl esters of aromatic carboxylic acids, C 2 -C 6 Fatty ethers, C 3 -C 4 Cyclic ethers and C 3 -C 6 At least one saturated aliphatic ketone.
In some preferred embodiments, the electron donor compound is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone, wherein preferably is selected from one or more of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone, and most preferably tetrahydrofuran.
According to the present invention, the electron donor compounds may be used alone or in any combination.
According to some embodiments of the invention, the magnesium content is 1 to 10wt%, based on the total weight of the catalyst; preferably 3 to 8wt%, more preferably 4 to 8wt%. In some embodiments, the magnesium content is 6 to 7.5wt%.
According to some embodiments of the invention, the nickel content is 0.05 to 4 wt.%, based on the total weight of the catalyst; preferably 0.1 to 2wt%, more preferably 0.1 to 1.5wt%, such as 0.1wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt% and any value in between.
According to some embodiments of the invention, the amount of the nitroxide compound is 0.05-5wt%, preferably 0.1-3wt%, more preferably 0.3-3wt%, such as 0.3wt%, 0.4wt%, 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, and any value in between, based on the total weight of the catalyst.
According to some embodiments of the present invention, the amount of organoaluminum compound is 1 to 10 wt.%, preferably 2 to 8 wt.%, more preferably 3 to 8 wt.%, based on the total weight of the catalyst.
According to some embodiments of the present invention, the electron donor compound is present in an amount of 5 to 40wt%, based on the total weight of the catalyst; preferably 10 to 35wt%, more preferably 15 to 30wt%.
According to some embodiments of the invention, the inorganic oxide support is present in an amount of 5 to 50wt%, based on the total weight of the catalyst; preferably 10 to 40wt%, more preferably 15 to 35wt%.
According to some embodiments of the invention, the molar ratio of magnesium to nickel in the catalyst is (5-300): 1, preferably (10-250): 1, more preferably (15-200): 1.
In a second aspect, the present invention provides a method for preparing a catalyst according to the first aspect of the present invention, comprising the steps of:
(1) Mixing a magnesium compound, a nickel complex, an electron donor compound, an organic aluminum compound, an inorganic oxide carrier and a nitrogen-oxygen heterocyclic compound to form slurry;
(2) And spray drying the obtained slurry to obtain the solid catalyst.
According to some embodiments of the invention, the temperature of said mixing in step (1) is 60 ℃ to 80 ℃, preferably 60 ℃ to 70 ℃. In some embodiments, the temperature of the mixing is 65 ℃, 66 ℃, 67 ℃.
According to some embodiments of the invention, the pressure of the mixing in step (1) is ≦ 0.2MPa.
According to the present invention, the mixing in step (1) is preferably carried out for a time period sufficient to completely dissolve the magnesium compound, and is usually not less than 2 hours. In some embodiments, the time of mixing is 2h, 3h, 4h, 6h, or 8h.
According to some embodiments of the invention, in step (2), the slurry is first cooled to 30-55 ℃ and then spray-dried. In some embodiments, the resulting slurry is cooled to 35 ℃. In other embodiments, the resulting slurry is cooled to 50 ℃.
According to some embodiments of the invention, the inlet temperature of the spray drying is 80-240 ℃; preferably 120-180 deg.c, and in some embodiments the inlet temperature is 140 deg.c, and in other embodiments the inlet temperature is 150 deg.c.
According to some embodiments of the invention, the outlet temperature of the spray drying is 60-130 ℃, preferably 90-120 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃ and any value in between.
According to some embodiments of the present invention, the magnesium compound is added in an amount of 3 to 10wt%, preferably 3wt% to 7wt%, based on the total amount of the raw materials added.
According to some embodiments of the present invention, the nickel compound is added in an amount of 0.01 to 3wt%, preferably 0.1 to 2wt%, and more preferably 0.1 to 1wt%, based on the total amount of the raw materials added.
According to some embodiments of the present invention, the nitroxide compound is added in an amount of 0.05 to 1.5wt%, preferably 0.1 to 1.0wt%, based on the total amount of feed added.
According to some embodiments of the present invention, the electron donor compound is present in an amount of 70 to 90 wt.%, preferably 75 to 88 wt.%, based on the total charge of starting materials.
According to some embodiments of the present invention, the inorganic oxide support is added in an amount of 3 to 10wt%, preferably 4wt% to 8wt%, based on the total amount of the raw materials added.
According to some embodiments of the present invention, the organoaluminum compound is added in an amount of 1 to 3 wt.% based on the total amount of the raw materials added
According to some embodiments of the present invention, in the step (1), the magnesium compound, the nickel compound, the electron donor compound, the organoaluminum compound, and the nitrogen-oxygen heterocyclic compound may be reacted first, and then the reaction product is supported on the inorganic oxide support, or the electron donor compound, the organoaluminum compound, and the inorganic oxide support may be mixed first, and then the magnesium compound and the nitrogen-oxygen heterocyclic compound are added to be mixed, and then the obtained mixed product is mixed with the nickel compound to react, so as to obtain the slurry.
According to some preferred embodiments of the present invention, in the step (1), the electron donor compound, the organoaluminum compound and the inorganic oxide support are first mixed, and then the magnesium compound and the nitrogen-oxygen heterocyclic compound are added to the first mixed product to be second mixed with the nickel compound to obtain the slurry.
According to some embodiments of the present invention, the temperature of the first mixing is selected from a wide range, and can be performed at normal temperature, for example, 20 ℃ to 50 ℃, preferably 25 ℃ to 45 ℃.
According to some embodiments of the invention, the temperature of the second mixing is 60-80 ℃, preferably 60-70 ℃, in some embodiments 65 ℃, 66 ℃, 67 ℃.
In a third aspect, the present invention provides a composite catalyst for olefin polymerization comprising the reaction product of:
component a, a catalyst according to the first aspect of the invention or a catalyst prepared according to the process of the second aspect of the invention;
a component b, an organoaluminum compound,
according to some embodiments of the invention, the organoaluminum compound has the formula A1R n X 3-n Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, preferably chlorine, bromine or iodine, and n is more than 0 and less than or equal to 3.
Specific examples of the organoaluminum compounds, according to some embodiments of the present invention, include, but are not limited to, one or more of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum monochloride.
According to some embodiments of the invention, the ratio of component b to component a, in terms of mole ratio of aluminum to nickel, is from 5 to 1, preferably from 10 to 1. In some embodiments, the ratio of component b to component a is 100 in terms of aluminum to nickel molar ratio.
According to the present invention, the catalyst is treated with an activator component, an organoaluminum compound, to render it suitable for use in the production of ethylene polymers. Generally, the solid catalyst obtained is reacted with an activator component in a hydrocarbon solvent to obtain a catalyst; the resulting catalyst may also be reacted with an activator component during the polymerization process to initiate olefin polymerization.
According to the present invention, the hydrocarbon solvent is a hydrocarbon solvent which can dissolve reaction components without affecting the reaction, and may be, for example, isopentane, hexane, heptane, toluene, xylene, naphtha, mineral oil, and the like.
In a fourth aspect, the present invention provides a process for the polymerisation of olefins comprising polymerising olefins in the presence of a catalyst according to the first aspect of the present invention and/or a catalyst prepared according to the process of the second aspect of the present invention and/or a composite catalyst according to the third aspect of the present invention.
According to some embodiments of the invention, the alkene may be of the formula CH 2 = CHR, wherein R is hydrogen or C 1 -C 6 The alkyl group of (1).
According to some embodiments of the invention, the olefin is selected from one or more of ethylene, propylene, butene, pentene, hexene, octene and 4-methylpentene-1.
According to the invention, the catalyst of the invention is suitable for the homopolymerization and copolymerization of olefins, in particular for the homopolymerization of ethylene or the copolymerization of ethylene and other alpha-olefins, and in particular, low density polyethylene can be prepared by only simple ethylene polymerization without adding alpha-olefins.
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. Conventional techniques such as slurry, gas-phase fluidized bed, solution, etc. are more suitable for gas-phase polymerization.
According to some embodiments of the invention, the temperature of the polymerization is from 65 ℃ to 90 ℃.
A fifth aspect of the invention provides the use of a catalyst according to the first aspect of the invention and/or a catalyst prepared according to the process of the second aspect of the invention and/or a composite catalyst according to the third aspect of the invention and/or a process according to the fourth aspect of the invention in the polymerisation of olefins.
Compared with the prior art, the invention has the following obvious advantages:
1. the catalyst for olefin polymerization is prepared by using superfine inorganic oxide as a carrier, performing organic aluminum treatment, dissolving magnesium halide by using an electron donor compound solvent, adding a nickel complex with a proper structure, and generating a high-activity catalyst by using a spray forming mode.
2. The catalyst of the present invention has high activity, specific polymerization performance, and is suitable for preparing low density polyethylene product, various polymerization processes, especially gas phase polymerization, and the obtained powder has no stickiness and high flowability.
3. The catalyst of the invention is especially suitable for ethylene homopolymerization, and can prepare low-density polyethylene products.
4. The catalyst of the invention has high polymerization activity at lower polymerization temperature, high powder melt index and excellent comprehensive performance.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given in conjunction with the examples which are given for purposes of illustration only and are not to be construed as limiting the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used are conventional products which are commercially available or can be obtained by conventional methods, without being indicated by the manufacturer.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The test method comprises the following steps:
1. activity: expressed as the weight of resin obtained per gram of catalyst.
2. Polymer Melt Index (MI): the melt index was measured using a melt index apparatus model 6932, CEAST, italy.
3. Polymer apparent density (BD): the measurement was carried out in accordance with ASTM D1895-69.
4. Nickel, magnesium, titanium content: the measurement analysis was carried out by using 7500cx ICP-MS element analyzer of Aglient, USA.
5. THF content: the measurement was carried out by Rayleigh P-300 gas chromatograph.
6. Density of polymer: the determination is carried out by a density gradient tube method according to the national standard 1033.2.
Example 1
(1) Preparation of the catalyst
1) Preparation of the ligand (R in formula (I)) 1 、R 3 、R 4 And R 6 Is methyl, R 2 And R 5 Is hydrogen, X is Br):
11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-dimethylaniline): 9, 10-dihydro-9, 10-ethyleneanthracene-11, 12-dione (1.14kg, 4.8mol) and 2, 6-methylaniline (1.3L, 10.4mol), 2L acetic acid as a catalyst were refluxed in 100L of ethanol for 1 day, the solvent was removed after filtration, the residue was dissolved with methylene chloride, fractionation was performed by a preparative separation column, the product was separated as a second stream, and the solvent was removed to obtain 1.97kg of a yellow solid at a yield of 92%. 1 H NMR(CDCl 3 δ, ppm) 1.88 (s, 12H), 4.85 (s, 2H), 7.05-7.24 (m, 14H). Elemental analysis (C) 32 H 28 N 2 ) Theoretical value (%): C,87.36; h,6.54; n,6.27; the experimental value (%): C,87.24; h,6.41; and N,6.36.
2) Preparation of nickel complex 1:
brominated [11,12- (9, 10-dihydro-9, 10-ethylene anthracene) bis (2, 6-dimethylaniline)]Preparation of nickel (II): adding 10L (DME) NiBr 2 (277g, 0.9mol) was added dropwise to 10L of a solution of 11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-dimethylaniline) ligand (443g, 0.9mol) in dichloromethane, and the mixture was stirred at room temperature for 6 hours to precipitate, and after the precipitate was filtered, washed with ether and dried, a dark red powder solid was obtained in a yield of 90%. Elemental analysis (C) 32 H 28 Br 2 N 2 Ni): c,58.32; h,4.28; n,4.25; experimental values (%): c,58.38; h,4.07; and N,4.06.
150L of tetrahydrofuran, 6kg of silica gel (Cabot Corporation TS-610, particle size 0.05 to 0.5 μm) and 10L of a diethylaluminum monochloride THF solution (15% by mass) were added successively to a 300-liter reaction vessel, stirred for one hour, and then 1.4kg of nickel complex 1,4kg of anhydrous MgCl was added 2 0.15kg of morpholine was added, and the temperature was raised to 66 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours. The temperature is reduced to 35 ℃.
The slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 140 ℃ and the outlet temperature was 102 ℃ to obtain a solid catalyst component in which the nickel content was 0.58Wt%.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen, simultaneously adding 10mL of 1mmol of triethyl aluminum and 0.02 g of catalyst, heating to 70 ℃, adding 0.05Mpa of hydrogen, adding 0.75Mpa of ethylene after hydrogenation, heating to 85 ℃, reacting for 2 hours, cooling and discharging. The contents of the catalyst elements are shown in Table 1, and the polymerization results are shown in Table 2.
(3) Gas phase polymerization of ethylene
Taking 1 kg of the obtained catalyst, adding the catalyst into a catalyst feeding preparation kettle, preparing the catalyst feeding preparation kettle and 10L of hexane into suspension, and feeding the suspension into a reactor through a peristaltic pump
And (3) adding triethyl aluminum into the gas-phase fluidized bed to adjust the molar ratio of aluminum to nickel to be 80, adjusting the reaction temperature to be 85 ℃, adjusting the partial pressure ratio of hydrogen to ethylene to be 0.05, and homopolymerizing and continuously polymerizing ethylene for 72 hours without adding a comonomer. The polymerization results are shown in Table 3.
Example 2
(1) Preparation of the catalyst
The catalyst was prepared as in example 1. Except that 10L of a diethylaluminum chloride THF solution was changed to a triisobutylaluminum THF solution, the concentration was the same, and the nickel content of the obtained solid catalyst was 0.56Wt%.
(2) The ethylene slurry polymerization process was the same as in example 1, the contents of elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
(3) The ethylene gas phase polymerization process was the same as in example 1, and the polymerization results are shown in Table 3.
Example 3
(1) Preparation of the catalyst
To a 250ml four-necked flask purged with nitrogen, 130m1 tetrahydrofuran, 6g of silica gel (Cabot Corporation TS-610, particle size 0.05 to 0.5 μm), 10ml of triethylaluminum THF solution (10%) were added, followed by stirring at room temperature for one hour, and then 0.37 g of nickel complex 1,4 g of anhydrous MgCl 2 0.2g of 4-cyano morpholine is heated to 66 ℃ with stirring, and the reaction is carried out for 3 hours at the constant temperature. Then the temperature is reduced to 35 ℃.
The obtained slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 140 ℃ and the outlet temperature was 102 ℃ to obtain a solid catalyst component in which the nickel content was 0.16Wt%.
(2) Evaluation of slurry polymerization of ethylene As in example 1, the contents of elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
Example 4
(1) Preparation of the catalyst:
to a 300L reaction vessel were added 170L of tetrahydrofuran, 5kg of silica gel (Cabot Corporation TS-610, particle diameter 0.05 to 0.5 μm), 8L of a THF solution of diethylaluminum monochloride (10% by mass), and stirred at room temperature for one hour, after which 1.1 kg of nickel complex 1, 200g of 4-cyanomorpholine and 5kg of anhydrous MgCl were added 2 The temperature was raised to 67 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at a constant temperature. And (3) cooling to 35 ℃, and starting spray drying the obtained slurry by using a centrifugal spray dryer, wherein the spray conditions are as follows: the inlet temperature was 150 ℃ and the outlet temperature was 94 ℃ to obtain 30 kg of a solid catalyst having a Ni content of 0.37Wt%.
(2) The ethylene slurry polymerization was carried out in the same manner as in example 1, and the contents of the elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
(3) The ethylene gas phase polymerization process was the same as in example 1, and the polymerization results are shown in Table 3.
Example 5
(1) Preparation of the catalyst
To a 250ml four-necked flask purged with nitrogen, 130M1 tetrahydrofuran, 7g of silica gel (Cabot Corporation TS-610, particle size 0.05-0.5 μ M), 2ml of a THF solution of diethylaluminum monochloride (1M) were added successively, stirred at room temperature for two hours, after which 2.7 g of nickel complex 1,3.5 g of anhydrous MgCl 2 0.3g of 4-cyanomorpholine, and the temperature is raised to 65 ℃ with stirring, and the reaction is carried out for 2 hours at constant temperature. The obtained slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the nickel content was 1.22Wt%.
(2) The ethylene slurry polymerization process was the same as in example 1, the contents of elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
Example 6
(1) Preparation of the catalyst
1) Preparation of the ligand (R in formula (I)) 1 、R 3 、R 4 And R 6 Is different fromPropyl radical, R 2 And R 5 Is hydrogen, X is Br):
11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-diisopropylaniline): 9, 10-dihydro-9, 10-ethyleneanthracene-11, 12-dione (2.10 g,9.0 mmol) and 2, 6-diisopropylaniline (4.0 mL,19.7 mmol), 2mL of acetic acid as a catalyst, refluxed in 100mL of ethanol for 1 day, filtered, and the solvent was removed, the residue was dissolved with dichloromethane, passed through an alkaline alumina column, rinsed with petroleum ether/ethyl acetate (20). 1 H NMR(CDCl 3 δ, ppm) 1.02 (d, 12H, J =6.9 Hz), 1.15 (d, 12H, J =6.9 Hz), 2.49 (m, 4H), 4.966 (s, 2H), 7.02-7.21 (m, 14H). Elemental analysis (C) 36 H 36 N 2 ) Theoretical value (%): C,86.91; h,8.02; n,5.07; the experimental value (%) is C,87.04; h,8.21; and N,5.30.
2) Preparation of nickel complex 2: brominated [11,12- (9, 10-dihydro-9, 10-ethylene anthracene) bis (2, 6-diisopropylaniline)]Nickel (II) complex: 10ml of (DME) NiBr 2 (506mg, 1.6mmol) of a dichloromethane solution was added dropwise to 10ml of a dichloromethane solution of 11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-diisopropylaniline) ligand (912mg, 1.6mmol), and stirred at room temperature for 6 hours to precipitate, which was filtered, washed with ether, and dried to give a dark red powder solid in a yield of 92%. Elemental analysis (C) 40 H 44 Br 2 N 2 Ni): c,62.29; h,5.75; n,3.63; experimental values (%): c,60.37; h,5.84; and N,3.72.
3) Preparation of the catalyst
To a 250ml four-necked flask purged with nitrogen, 130M1 tetrahydrofuran, 7g of silica gel (Cabot Corporation TS-610, particle size 0.05 to 0.5 μ M), 2ml of a THF solution of diethylaluminum monochloride (1M) were added, stirred at room temperature for two hours, after which 3.2 g of nickel complex 2,3.5 g of anhydrous MgCl were added 2 0.3g of 4-cyanomorpholine, and the temperature is raised to 65 ℃ with stirring, and the reaction is carried out for 2 hours at constant temperature. The obtained slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the nickel content was 1.22Wt%.
(2) Ethylene slurry polymerization process
The contents of elements in the catalyst are shown in Table 1 and the polymerization results are shown in Table 2, as in example 1.
Example 7
(1) Preparation of the catalyst
1) Preparation of the ligand (R in formula (I)) 1 、R 3 、R 4 And R 6 Is methyl, R 2 And R 5 Is bromine, X is Br):
11,12- (9, 10-dihydro-9, 10-ethylene anthracene) bis (2, 6-dimethyl-4-bromo-aniline): 9, 10-dihydro-9, 10-ethyleneanthracene-11, 12-dione (1.20g, 5.1mmol) and 2, 6-dimethyl-4-bromo-aniline (2.3g, 11.3mmol), 2mL of acetic acid as a catalyst, refluxing in 100mL of ethanol for 1 day, removing the solvent after filtration, dissolving the residue with dichloromethane, passing through an alkaline alumina column, rinsing with petroleum ether/ethyl acetate (20. 1 H NMR(CDCl 3 δ, ppm) 1.84 (s, 12H), 4.83 (s, 2H), 7.18-7.25 (m, 8H), 7.27 (s, 4H). Elemental analysis (C) 32 H 26 Br 2 N 2 ) Theoretical value (%): C,64.23; h,4.38; n,4.68; the experimental value (%): C,64.37; h,4.52; and N,5.00.
2) Preparation of nickel complex 3: brominated [11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-dimethyl-4-bromo-aniline)]Nickel (II) complex: 10ml of (DME) NiBr 2 (216mg, 0.7mmol) of a methylene chloride solution was added dropwise to 10ml of a methylene chloride solution of 11,12- (9, 10-dihydro-9, 10-ethyleneanthracene) bis (2, 6-dimethyl-4-bromo-aniline) ligand (418mg, 0.7mmol), and stirred at room temperature for 6 hours to precipitate, which was then filtered, washed with ether and dried to give a dark red powder as a solid, with a yield of 88%. Elemental analysis (C) 32 H 26 Br 4 N 2 Ni): c,47.05; h,3.21; n,3.43; experimental values (%): c,47.26; h,3.62; and N,3.23.
3) Preparation of the catalyst
To a 250ml four-necked flask purged with nitrogen, 130M1 tetrahydrofuran, 7g of silica gel (Cabot Corporation TS-610, particle size 0.05-0.5 μ M), 2ml of a THF solution of diethylaluminum chloride (1M) were added, stirred at room temperature for two hours, and then added3.3 g Nickel Complex 3,3.5 g Anhydrous MgCl 2 0.3g of 4-cyanomorpholine, and the temperature is raised to 65 ℃ with stirring, and the reaction is carried out for 2 hours at constant temperature. The obtained slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the nickel content was 1.22Wt%.
(2) Ethylene slurry polymerization process
In the same manner as in example 1, the contents of the elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
Comparative example 1
(1) Preparation of the catalyst
1.5 g of TiCl were added successively to a 250m1 four-neck flask purged with nitrogen 4 4.0 g of anhydrous MgCl 2 And 100m1 of tetrahydrofuran, and the temperature was raised to 65 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at a constant temperature. The temperature is reduced to 35 ℃.
To a 250ml three-necked flask purged with nitrogen gas was added 6g of silica gel (Cabot Corporation TS-610, particle size 0.02 to 0.1 μm), the mother liquor after cooling was added, the temperature was maintained at 35 ℃ and after stirring for 1 hour, the mother liquor after blending silica gel was spray-dried using a spray dryer under spray conditions: the inlet temperature was 155 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the titanium content was 2.2Wt%.
(2) The ethylene slurry polymerization process was the same as in example 1, the contents of elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
(3) The ethylene gas phase polymerization process was the same as in example 1, and the polymerization results are shown in Table 3.
Comparative example 2
(1) Preparation of the catalyst
1) Preparation of alkylsilyl chloride/silica gel carrier
Under the protection of nitrogen, 10.0 g of dry silica gel carrier is taken out and added into a glass reactor, 100ml of dry hexane is added and dispersed into suspension, 1 ml of SiCl is added 2 (n－Bu) 2 Stirring, heating to 30 deg.C, reacting for 4 hr, and vacuum drying to obtain solid powder with good fluidity.
2) Preparation of organoaluminum/alkylsilylchloride/silica gel support
Under the protection of nitrogen, 5.0 g of the solid powder obtained above is taken and added into a glass reactor, 60 ml of dried toluene is added to be dispersed into suspension, 18 ml of 10wt% MAO (methylaluminoxane) toluene solution is added, the temperature is raised to 50 ℃, the stirring reaction is carried out for 4 hours, then 50ml of toluene multiplied by 3 is used for washing for three times, then hexane is used for washing, and vacuum drying is carried out, thus obtaining solid powder with good fluidity, namely the silica gel carrier containing methylaluminoxane.
3) Preparation of Supported late transition Metal catalyst A
Under the protection of nitrogen, 2.50 g of the silica gel carrier containing methylaluminoxane obtained in the previous step is added into a glass reactor, 35 ml of dried toluene is added to prepare slurry, 0.096 g of nickel complex 1 dissolved in 20 ml of toluene is dropwise added into the reactor to react for 30 minutes at 30 ℃, and then the mixture is washed by 35 ml of toluene and dried in vacuum, so that the supported transition metal catalyst A is obtained. The catalyst A has a nickel content of 0.15 wt% and an Al content of 10.07 wt% according to ICP characterization.
(2) The ethylene slurry polymerization process was the same as in example 1, the contents of elements in the catalyst are shown in Table 1, and the polymerization results are shown in Table 2.
TABLE 1 catalyst with contents of components (wt%)
TABLE 2 evaluation results of slurry polymerization of ethylene
As can be seen from the data in Table 2, the catalyst obtained by the invention has higher polymerization activity compared with the titanium catalyst, and the powder melt index is higher under the condition of the same hydrogen-ethylene ratio, which indicates that the new catalyst system has higher hydrogen correspondence. Meanwhile, under the condition of not adding any comonomer at all, the novel catalytic system can obtain the polyethylene resin with medium density, which shows that the polyethylene resin has better spontaneous branching capability. Under the same conditions, the titanium catalyst can only obtain high-density resin. Compared with other supported nickel catalysts, the polymerization activity of the new catalyst system is greatly improved, and the catalyst system has greater advantages in the aspects of melt index and density.
TABLE 3 evaluation results of gas phase polymerization
As can be seen from the data in Table 3, under the pilot gas-phase fluidized bed polymerization conditions and under the same process conditions, the titanium catalyst has lower polymerization activity and high density without adding comonomer. The new catalytic system has better polymerization activity and higher melt index, and the resin density reaches the linear low-density level. The method is the biggest characteristic of a new catalytic system, namely, the method can spontaneously induce branching to complete the production of low-density products.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (34)
1. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises the following components or the reaction product of the following components: (1) a magnesium compound; (2) a nickel compound; (3) an nitroxide compound; (4) an organoaluminum compound; (5) an electron donor compound; (6) an inorganic oxide support;
based on the total weight of the catalyst, the content of magnesium is 1-10wt%; and/or a nickel content of 0.05-4wt%; and/or the amount of the nitroxide compound is 0.05-5wt%; and/or the amount of the organoaluminum compound is 1 to 10wt%; and/or the amount of the electron donor compound is 5-40wt%; and/or the amount of said inorganic oxide support is from 5 to 50wt%;
the nitrogen-oxygen heterocyclic compound is a morpholine compound;
the nickel compound is selected from compounds shown in a formula (I),
wherein R is 1 -R 6 The same or different, each independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl and hydrocarbyloxy;
x is halogen.
2. The catalyst according to claim 1, wherein in the formula (I), R is 1 -R 6 The same or different, each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C with or without substituent 1 -C 20 Alkyl of (C) 2 -C 20 Alkenyl of (C) 2 -C 20 Alkynyl of (A), C 1 -C 20 Alkoxy group of (C) 2 -C 20 Alkenyloxy of (C) 2 -C 20 Alkynyloxy of (a), C 6 -C 20 Aryl radical, C 7 -C 20 Aralkyl and C 7 -C 20 An alkaryl group, the alkyl group being a straight chain alkyl group, a branched chain alkyl group or a cycloalkyl group, the alkoxy group being a straight chain alkoxy group, a branched chain alkoxy group or a cycloalkoxy group;
and/or X is selected from fluorine, chlorine, bromine and iodine;
and/or the substituents are selected from halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy group.
3. The catalyst according to claim 1 or 2, wherein in the formula (I), R is 1 -R 6 The same or different, each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C with or without substituent 1 -C 10 Alkyl of (C) 2 -C 10 Alkenyl of, C 2 -C 10 Alkynyl of (A), C 1 -C 10 Alkoxy group of (C) 2 -C 10 Alkenyloxy of (C) 2 -C 10 Alkynyloxy of (a), C 6 -C 15 Aryl radical, C 7 -C 15 Aralkyl radical and C 7 -C 15 An alkaryl group.
4. The catalyst according to claim 1 or 2, wherein in the formula (I), R is 1 -R 6 The same or different, each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C with or without substituent 1 -C 6 Alkyl of (C) 2 -C 6 Alkenyl of (C) 2 -C 6 Alkynyl of (A), C 1 -C 6 Alkoxy group of (C) 2 -C 6 Alkenyloxy of (2), C 2 -C 6 Alkynyloxy of (a), C 6 -C 10 Aryl radical, C 7 -C 10 Aralkyl and C 7 -C 10 An alkaryl group.
5. The catalyst according to claim 4, wherein C is 1 -C 6 The alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3-dimethylbutyl; said C is 1 -C 6 The alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy.
6. The catalyst according to claim 1 or 2, characterized in that the nickel compound is selected from one or more of the following compounds:
1) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝H，X＝Br；
2) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝H，X＝Br；
3) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝iPr，R 2 ＝R 5 ＝H，X＝Br；
4) A nickel complex represented by the formula (I) wherein R 1 ＝R 2 ＝R 3 ＝R 4 ＝R 5 ＝R 6 ＝Me，X＝Br；
5) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Br，X＝Br；
6) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Et，X＝Br
7) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Me，X＝Br；
8) A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Br，X＝Br；
9) A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝H，X＝Cl；
10 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝H，X＝Cl；
11 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝iPr，R 2 ＝R 5 ＝H，X＝Cl；
12 A nickel complex represented by the formula (I) wherein R 1 ＝R 2 ＝R 3 ＝R 4 ＝R 5 ＝R 6 ＝Me，X＝Cl；
13 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Br，X＝Cl；
14 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Me，R 2 ＝R 5 ＝Et，X＝Cl；
15 A nickel complex represented by the formula (I) wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Me，X＝Cl；
16 A nickel complex of the formula (I), wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝Et，R 2 ＝R 5 ＝Br，X＝Cl。
7. Catalyst according to claim 1 or 2, characterized in that the nitroxide is morpholine and/or 4-cyanomorpholine;
and/or the particle size of the inorganic oxide carrier is 0.01-10 μm.
8. The catalyst of claim 7, wherein the inorganic oxide support has a particle size of 0.02 to 5 μm.
9. The catalyst of claim 7, wherein the inorganic oxide support has a particle size of 0.05 to 1 μm.
10. The catalyst of claim 7, wherein the inorganic oxide support is an oxide of silicon and/or aluminum.
11. The catalyst of claim 7, wherein the inorganic oxide support is silica.
12. The catalyst according to claim 1 or 2, characterized in that the organoaluminum compound is selected from compounds of the general formula A1R n X 3-n Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is more than 0 and less than or equal to 3;
and/or the magnesium compound is a magnesium halide;
and/or said electron donor compound is selected from C 1 -C 4 Alkyl esters of saturated fatty carboxylic acids, C 7 -C 8 Alkyl ester of aromatic carboxylic acid, C 2 -C 6 Fatty ethers, C 3 -C 4 Cyclic ethers and C 3 -C 6 One or more saturated aliphatic ketones.
13. The catalyst of claim 12, wherein the magnesium compound is selected from at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide.
14. The catalyst according to claim 1 or 2, characterized in that the magnesium content is 3-8wt% based on the total weight of the catalyst; and/or a nickel content of 0.1-2wt%; and/or the amount of the nitroxide compound is 0.1-3wt%; and/or the amount of organoaluminum compound is 2-8wt%; and/or the amount of the electron donor compound is 10-35wt%; and/or the amount of the inorganic oxide support is 10 to 40wt%.
15. The catalyst of claim 14 wherein the amount of organoaluminum compound is 3-8 wt.%; and/or the amount of electron donor compound is 15-30wt%; and/or the amount of said inorganic oxide support is from 15 to 35wt%;
and/or the molar ratio of magnesium to nickel in the catalyst is (5-300): 1.
16. The catalyst of claim 14 wherein the molar ratio of magnesium to nickel in the catalyst is (10-250): 1.
17. The catalyst of claim 14 wherein the molar ratio of magnesium to nickel in the catalyst is (15-200): 1.
18. A method of preparing the catalyst of any one of claims 1-17, comprising the steps of:
(1) Mixing a magnesium compound, a nickel compound, an electron donor compound, an organic aluminum compound, an inorganic oxide carrier and a nitrogen-oxygen heterocyclic compound to form slurry;
(2) And spray drying the obtained slurry to obtain the solid catalyst.
19. The method according to claim 18, wherein in the step (2), the slurry is cooled to 30-55 ℃ and then spray-dried.
20. The method of claim 19, wherein the inlet temperature of the spray drying is 80-240 ℃; and/or the outlet temperature of the spray drying is 60-130 ℃.
21. The method of claim 19, wherein the inlet temperature of the spray drying is 120-180 ℃; and/or the outlet temperature of the spray drying is 90-120 ℃.
22. The process of any one of claims 18 to 21, wherein the amount of magnesium compound is 3 to 10wt%, based on 100% total amount of raw material; and/or the amount of nickel compound is 0.01-3wt%; and/or the amount of the nitroxide compound is 0.05-1.5wt%; and/or the amount of the organoaluminum compound is 1 to 3wt%; and/or the amount of electron donor compound is 70-90wt%; and/or the inorganic oxide support is added in an amount of 3 to 10wt%.
23. The method of claim 22, wherein the amount of magnesium compound is 3-7wt%; and/or the amount of nickel compound is 0.1-2wt%; and/or the amount of electron donor compound is 75-88wt%; and/or the inorganic oxide support is added in an amount of 4 to 8wt%.
24. The method according to any one of claims 18-21, 23, wherein the temperature of the mixing in step (1) is 60-80 ℃; and/or the pressure of mixing is less than or equal to 0.2MPa, and/or the time of mixing is more than or equal to 2 hours.
25. The method as claimed in any one of claims 18 to 21 or 23, wherein in the step (1), the electron donor compound, the organoaluminum compound and the inorganic oxide carrier are first mixed, and then the magnesium compound, the nitrogen-oxygen heterocyclic compound and the nickel compound are added to the first mixed product to be mixed, so as to obtain the slurry.
26. The method of claim 25, wherein the temperature of the first mixing is 20-50 ℃; and/or the temperature of the second mixing is 60-80 ℃.
27. A composite catalyst for the polymerization of olefins comprising the reaction product of:
component a, a catalyst according to any one of claims 1 to 17 or a catalyst prepared by a process according to any one of claims 18 to 26;
component b, an organoaluminum compound.
28. The composite catalyst of claim 27, where the organoaluminum compound has the general formula A1R n X 3-n Wherein R is hydrogen or alkyl with 1-20 carbon atoms, X is halogen, n is more than 0 and less than or equal to 3.
29. A process for the polymerisation of olefins comprising polymerising olefins in the presence of a catalyst as claimed in any one of claims 1 to 17 or a catalyst prepared according to the process of any one of claims 18 to 26 or a composite catalyst as claimed in any one of claims 27 to 28.
30. The method of claim 29, wherein the olefin has the formula CH 2 = CHR where R is hydrogen or C 1 -C 6 Alkyl group of (1).
31. The process of claim 29, wherein the olefin is selected from one or more of ethylene, propylene, butene, pentene, hexene, octene, and 4-methylpentene-1.
32. Use of a catalyst according to any one of claims 1 to 17 or a catalyst prepared according to the process of any one of claims 18 to 26 or a composite catalyst according to any one of claims 27 to 28 or a process according to any one of claims 29 to 31 in the polymerisation of olefins.
33. Use according to claim 32, wherein the polymerization is a gas phase polymerization.
34. Use according to claim 32, wherein the polymerization is an ethylene homopolymerization.
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