Olefin polymerization catalyst composition and its preparation method and application

Abstract

The present invention relates to an olefin polymerization catalyst composition, which comprises a main catalyst, a carrier and a third component. The main catalyst is a rare earth metal complex represented by the general formula (I): CpLnL 1 L 2 (I), wherein Cp is a substituent formed by removing hydrogen from the carbon atom connected to R from the compound represented by general formula (II), and Ln is a transition metal element of Group IIIB; L 1 and L 2 The same or different components are independently selected from one of H, halogen, hydrocarbon group (R'), silicon hydrocarbon group (SiR'3), alkoxy group (OR'), thiol group (SR'), carboxyl group (OCOR'), amine group (NR'2), and phosphine group (PR'2), with R' being as described above; the support is a clay-silica gel composite support; and the third component is selected from the compound represented by chemical formula (III). The present invention also relates to a method for preparing an olefin polymerization catalyst composition and its application.

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization, in particular to a rare earth metal catalyst composition and a preparation method thereof, and application of the catalyst in propylene polymerization. Background Art

[0002] Indeno[1,2-b]indole is a class of electron-rich cyclopentadiene derivatives that are widely used in the synthesis of Group IV transition metal organic compounds. Group IV transition metal organic compounds stabilized by indeno[1,2-b]indole derivatives (such as KR2015015791, KR 2015015789, WO 2015016423, WO 2015016422, WO 2002092647, WO9924446, CN1249756A, CN1805980A, WO2009 / 032048A1, WO2009 / 032051A1, WO2015 / 016423A1) have C2 symmetry or C s The catalytic system can be used to synthesize polyolefin products with different properties for the polymerization of propylene or ethylene. Patents (CN 105985368, CN 105985383, PCT CN2016073644) describe organic compounds of indeno[1,2-b]indolyl derivatives and Group IV transition metals, which exhibit quasi-C2 symmetry and demonstrate excellent catalytic performance for the polymerization of ethylene or propylene, enabling the structure of homoblock polymers to be regulated.

[0003] However, there are relatively few reports on the application of organic compounds of indeno[1,2-b]indolyl derivatives and rare earth metals in the polymerization of propylene or ethylene (CN108218901A, CN108341903A). Indeno[1,2-b]indolyl rare earth metal catalysts are primarily used in the preparation of olefin rubbers, particularly cis-polybutadiene rubber. Compared to ternary neodymium-based catalysts, homogeneous single-site rare earth metal catalysts offer higher activity, narrower molecular weight distribution, and easier control of polymer molecular weight and stereoisotacticity.

[0004] In the prior art, indeno[1,2-b]indole-based rare earth metal catalysts (CN108218901A, CN108341903A) are rarely used in propylene polymerization. One reason is that their activity is less than ideal. When used in olefin polymerization, they often need to be cationized with expensive borate reagents, just like most homogeneous single-site rare earth metal catalysts, and their catalytic polymerization activity is difficult to control. In addition, as homogeneous catalysts, the polymer products they produce have poor morphology, which can easily cause blockage of polymerization kettles and equipment during polymerization and product transportation. They have poor adaptability to industrial equipment, making them difficult to use in industry.

[0005] CN108218901A discloses an indeno[1,2-b]indolyl rare earth metal complex for use in the preparation of high-cis olefin rubbers. The defects of this technology or the shortcomings of the present invention are as follows: the catalytic system used for the preparation of high-cis olefin rubbers is not suitable for olefin polymerization, especially ethylene polymerization; the system does not contain a carrier and is a homogeneous polymerization, which is not suitable for most current ethylene polymerization industrial devices, and requires the use of an expensive borate reagent as an activator.

[0006] CN108341903A discloses an indeno[1,2-b]indolyl rare earth metal complex for use in the preparation of high-cis olefin rubbers. The defects of this technology or the shortcomings of the present invention are as follows: the catalytic system used for the preparation of high-cis olefin rubbers is not suitable for olefin polymerization, especially ethylene polymerization; the system does not contain a carrier and is a homogeneous polymerization, which is not suitable for most current ethylene polymerization industrial devices, and requires the use of an expensive borate reagent as an activator.

[0007] Therefore, developing the application of rare earth metal catalysts with indeno[1,2-b]indolyl and similar substituents in propylene polymerization, improving polymerization activity, improving polymer morphology, reducing the amount of borate reagents or even avoiding the use of borate reagents are technical issues that need to be urgently addressed in the industrial application of this type of catalyst. Summary of the Invention

[0008] Based on the foregoing, the present invention primarily aims to provide an olefin polymerization catalyst composition and a method for preparing the same. The composition comprises an indeno[1,2-b]indolyl derivative of a specific structure and an organic compound of a rare earth metal, and exhibits excellent polymerization activity. Another object of the present invention is to provide the use of the catalyst composition in ethylene polymerization.

[0009] To this end, the present invention provides an olefin polymerization catalyst composition, which comprises a main catalyst, a carrier and a third component, wherein the main catalyst is a rare earth metal complex represented by the general formula (I):

[0010] LqCy 1 L 2 (I)

[0011] Wherein, Cp is a substituent formed by removing the hydrogen from the carbon atom connected to R in the compound represented by general formula (II):

[0012]

[0013] Among them, R 1 to R 5 、R x and R y The same or different, each independently selected from H, halogen, C1-C20 Alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl and its derivatives, C7-C 30 Aralkyl and its derivatives, C7-C 30 Alkaryl and its derivatives, C1-C 30 Alkyl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C6-C 30 Aryl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C7-C 30 One of an aralkyl group containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table and its derivatives, a silicon hydrocarbon group - SiR'3, an alkoxy group - OR', a mercapto group - SR', a carboxyl group - OCOR', an amino group - NR'2 and a phosphine group - PR'2, wherein R' is selected from C1-C 20 Alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl and its derivatives, C7-C 30 Aralkyl and its derivatives, C1-C 30 Alkyl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C6-C 30 Aryl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C7-C 30 One of the group consisting of arylalkyl and its derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table; R and R 1 to R 5 、R x and R y One of the groups is the same, but not H;

[0014] Ln is a transition metal element of Group IIIB;

[0015] L 1 and L 2 the same or different, each independently selected from one of H, halogen, hydrocarbon group (R'), silicon hydrocarbon group (SiR'3), alkoxy group (OR'), mercapto group (SR'), carboxyl group (OCOR'), amino group (NR'2) and phosphine group (PR'2), R' being as described above;

[0016] The carrier is clay-silica gel particles;

[0017] The third component is selected from the compound represented by chemical formula (III): MR11 3(III), wherein M is Al, Zn, or Mg; R 11 For hydrogen, halogen, C1-C 20 an alkyl group or a halogenated alkyl group.

[0018] In one embodiment, R in formula (II) x and R y Connected to each other into a ring.

[0019] In one preferred embodiment of the general formula (II), Cp is a substituent formed by removing the hydrogen from the carbon atom connected to R from the compound represented by the general formula (IV):

[0020]

[0021] Among them, R 1 to R 9 The same or different, each independently selected from H, halogen, C1-C 20 Alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl and its derivatives, C7-C 30 Aralkyl and its derivatives, C7-C 30 Alkaryl and its derivatives, C1-C 30 Alkyl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C6-C 30 Aryl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C7-C 30 One of an aralkyl group containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table and its derivatives, a silicon hydrocarbon group - SiR'3, an alkoxy group - OR', a mercapto group - SR', a carboxyl group - OCOR', an amino group - NR'2 and a phosphine group - PR'2, wherein R' is selected from C1-C 20 Alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 30 Aryl and its derivatives, C7-C 30 Aralkyl and its derivatives, C1-C 30 Alkyl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C6-C 30 Aryl groups and their derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table, C7-C 30One of the group consisting of arylalkyl and its derivatives containing heteroatoms of elements from Group IIIA to Group VIIA of the periodic table; R and R 1 to R 9 One of the groups is the same, but not H.

[0022] The catalyst composition of the present invention is preferably 20 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 One of the long chain alkyl groups; the C2-C 20 The alkenyl group is selected from vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptenyl, octenyl, nonenyl, decenyl, C 11 ~C 20 One of the long chain alkenyl groups; the C 3- C 20 The cycloalkyl group is selected from one of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; the C6-C 30 The aryl group and its derivatives are selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl; the C7-C 30 The aralkyl group and its derivatives are selected from benzyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-tert-butylphenyl; the C1-C 30 The alkyl, aryl, aralkyl and derivatives thereof containing heteroatoms from Group IIIA to Group VIIA of the periodic table are selected from one of chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl and p-dimethylaminophenyl.

[0023] The catalyst composition of the present invention is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 Long chain fatty alkyl, vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptene, octene, nonene, decene, C 11 ~C 20Long-chain alkenyl, benzyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-tert-butylphenyl, p-methoxyphenyl, p-chlorophenyl, m-chlorophenyl, o-chlorophenyl, chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl, p-dimethylaminophenyl.

[0024] In the catalyst composition of the present invention, preferably, the Ln is selected from scandium, yttrium, praseodymium, neodymium, samarium, gadolinium, dysprosium or holmium.

[0025] The catalyst composition of the present invention is preferably: 1 and L 2 Each of the following groups is independently selected from the group consisting of hydrogen, 1,3-propenyl, trimethylsilylmethyl, bis(trimethylsilyl)methyl, tris(trimethylsilyl)methyl, o-(N,N-dimethylamino)benzyl, and N,N-bis(trimethylsilyl)amino.

[0026] In the catalyst composition of the present invention, preferably, the rare earth metal complex of the ligand represented by general formula (II) in Cp can be prepared according to the following route:

[0027]

[0028] The route is to prepare an indenopyrrole derivative containing an R substituent by reacting an indenopyrrole derivative with butyl lithium and a halide, and then further react the indenopyrrole derivative with a homocoordinate trisubstituted rare earth metal compound to obtain an indenopyrrole-based rare earth metal complex containing a monocyclopentadiene.

[0029] In the catalyst composition of the present invention, preferably, the rare earth metal complex of the ligand represented by general formula (IV) in Cp can be prepared according to the following route:

[0030]

[0031] The route is to prepare an R-group-substituted alkenyl carboxylic acid by reacting it with a substituted benzene to obtain an R-group-containing substituted indanone, which is then reacted with a substituted phenylhydrazine hydrochloride to obtain an R-group-containing indenoindole, which is then further reacted with a homo-coordinate trisubstituted rare earth metal compound to obtain a monocyclopentadienyl indenoindole-based rare earth metal complex.

[0032] In the catalyst composition of the present invention, preferably, the clay in the clay-silica gel composite carrier is one or more of montmorillonite, vermiculite, kaolin, sepiolite, attapulgite, glauconite, talc, saponite, chrysotile and phylloxetine.

[0033] In the catalyst composition of the present invention, preferably, the average particle size of the clay is 0.1 to 50 μm.

[0034] In the catalyst composition of the present invention, it is preferred that the silica sol particle size in the clay-silica gel composite carrier is 5 to 30 nm and the pH value is 3 to 7.

[0035] In the catalyst composition of the present invention, it is preferred that the ratio of clay to silica sol in the clay-silica gel composite carrier is 0.1 to 20 mol of silica sol per gram of clay.

[0036] The catalyst composition of the present invention preferably has a weight / molar ratio of the carrier to the main catalyst of 1 kg / mole to 50 kg / mole.

[0037] In the catalyst composition of the present invention, preferably, the molar ratio of the compound represented by the chemical formula (III) to the main catalyst is 0.1 / 1 to 100,000 / 1, more preferably 10 / 1 to 50,000 / 1.

[0038] The catalyst composition of the present invention is preferably such that the compound represented by the chemical structural formula (III) is selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum.

[0039] To this end, the present invention also provides a method for preparing the above-mentioned olefin polymerization catalyst composition, comprising the following steps:

[0040] (1) washing clay with an inorganic acid solution and then with distilled water until neutral, drying and grinding the clay to obtain acid-modified clay; mixing the prepared acid-modified clay with silica sol, and spray drying the mixture to obtain a clay-silica gel composite carrier;

[0041] (2) dissolving the main catalyst in an organic solvent;

[0042] (3) The solution of the main catalyst prepared in step (2) and the third component are mixed with the support prepared in step (1) simultaneously or in any order.

[0043] In the method for preparing the catalyst composition of the present invention, preferably, the inorganic acid is sulfuric acid, hydrochloric acid or nitric acid; and the organic solvent is toluene, hexane or heptane.

[0044] In the method for preparing the catalyst composition of the present invention, it is preferred that the ratio of the clay to the inorganic acid is 0.1 to 1 mol of inorganic acid per gram of layered clay.

[0045] In the method for preparing the catalyst composition of the present invention, preferably, the concentration of the inorganic acid solution is 0.1 mol / L to 2.0 mol / L.

[0046] The preparation method of the catalyst composition described in the present invention is preferably that, in step (1), the washing temperature is 0°C to 100°C, the washing conditions of the inorganic acid solution are stirring for 2 to 10 hours, and the conditions for drying the product after filtration with distilled water are: 200°C to 800°C for 2 to 8 hours.

[0047] The method for preparing the catalyst composition of the present invention is preferably such that, in step (1), the acid-modified clay and the silica sol are mixed and uniformly dispersed using an ultrasonic disperser; the clay-silica gel composite carrier in particle form obtained by spray drying is heated to 600-800° C. under nitrogen fluidization and dried for 2-10 hours, and then stored under inert gas atmosphere protection conditions.

[0048] To this end, the present invention also provides a use of the above olefin polymerization catalyst composition in propylene polymerization.

[0049] The beneficial effects of the present invention are as follows:

[0050] (1) The catalytic activity is significantly improved because the R substituent on the indeno[1,2-b]-substituted pyrrole described in the general formula (II) or the indeno[1,2-b]-substituted indole described in the general formula (IV) is not hydrogen, and a clay-silica gel composite support is used in combination with the third component as a support and activator. The R group and the N atom are located in relative positions on the centerline of the ligand structure. When R is selected from a group other than hydrogen, especially when R is a larger steric group, the catalytic activity is significantly improved compared to when R is hydrogen;

[0051] (2) The catalyst is used in propylene polymerization to produce uniform polymer particles with a narrow molecular weight distribution. This is because the use of a clay-silica composite support transforms the homogeneous catalytic system into a heterogeneous one, resulting in high polymerization activity and uniform polymer particles with a narrow molecular weight distribution. More importantly, the clay-silica composite support provides sufficient acidic sites, eliminating the need for expensive borate reagents as activators, reducing production costs and facilitating industrial applications. DETAILED DESCRIPTION

[0052] The following is a detailed description of the embodiments of the present invention: This embodiment is implemented based on the technical solution of the present invention, and provides detailed implementation methods and processes. However, the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments where specific conditions are not specified are generally based on conventional conditions.

[0053] The cis-1,4 selectivity of the polymer was determined by 13 The molecular weight and molecular weight distribution of the polymer were determined by PL-GPC50 gel permeation chromatograph.

[0054] The operations for preparing the catalysts in the following examples were all carried out under the protection of high-purity nitrogen.

[0055] Example 1

[0056]

[0057] N-methyl-dimethylpyrroloindene (5mmol) was added to a 50ml Schlenk bottle and vacuumed in an oil bath for 1.5h. 20ml of methyl tert-butyl ether was added in portions and stirred for 10min to completely dissolve the reactants. The solution was cooled to below 0°C using an ice-alcohol bath. Under N2 protection, n-BuLi (3.75ml, 1.6mol / L) was slowly added and reacted for 3.5h. 8.9ml of trimethylsilyl chloride (7.6g, 7mmol) was prepared and cooled to below 0°C using an ice-alcohol bath. Under N2 protection, the reaction solution was replaced with trimethylsilyl chloride at constant pressure and reacted at room temperature for 8h. Filter, spin-dry the filtrate, quench with ice, and extract with saturated brine three times. The upper organic phase was dried with a desiccant for 8h. The solution was filtered to remove the desiccant, and the solvent was removed by rotary evaporation to obtain a crude product that was passed through a column and slurried with n-hexane to obtain 0.54g of solid.

[0058] 0.98 g of anhydrous YCl3 (Fw = 195.26, 5 mmol) was weighed into a 100 mL Schlenk flask, 30 mL of tetrahydrofuran (dehydrated) was added, and the mixture was heated and stirred at 60°C for 10 hours. The THF was then removed in vacuo to obtain a powdered solid YCl3 (THF) 3.5 , used directly in the next step.

[0059] Weigh N-methyl-dimethylpyrrolotrimethylsilyl indene (5mmol) in a 100mL Schlenk bottle and add 40mL of anhydrous ether. Cool it to -25°C, then slowly add n-BuLi hexane solution (2.4M, 2.3mL, 5.5mmol) dropwise, accompanied by the formation of insoluble matter. After the addition is complete, let it rise to 25°C naturally, and continue stirring at 25°C for 2 hours. After the reaction is complete, remove the solvent under vacuum to obtain crystals, which are lithium salt intermediates. Weigh the above lithium salt intermediate and dissolve it in anhydrous THF to make a solution. Then slowly add it dropwise to YCl3(THF) at -25°C. 3.5 After the addition is complete, the temperature is allowed to rise naturally to 25°C and the reaction is continued at 25°C with stirring for 12 hours. After the reaction is complete, the THF is removed under vacuum, and the residue is extracted with anhydrous toluene. The filtrate is filtered and collected, and the toluene is removed under vacuum to obtain a yellow oil. Subsequently, 20 mL of n-hexane is added to precipitate the solid, which is filtered and washed twice with small amounts of n-hexane to obtain a light yellow powder with a yield of approximately 80%.

[0060] The above product was dissolved in toluene and cooled to -25°C. A toluene solution of o-dimethylaminobenzyllithium was slowly added dropwise. After the addition was complete, the temperature was naturally raised to 25°C and the reaction was continued with stirring for 16 hours, resulting in the formation of a white precipitate. After the reaction was completed, the insoluble material was filtered off, the solvent removed from the filtrate under vacuum, and the filtrate was washed twice with n-hexane to obtain Compound a1.

[0061] Preparation of catalyst composition

[0062] (1) 50 g of calcium-based montmorillonite (Ca-MMT) with a particle size of 20 μm and 500 mL of a 10 wt% sulfuric acid solution were placed in a 1 L flask and stirred at 95°C for 4 hours to obtain a solid superacid material with an interlayer spacing of 1-2 nm. After stirring, the mixture was washed with distilled water until neutral. The resulting product was filtered and dried in a muffle furnace at 600°C for 4 hours. After grinding, it was placed in a desiccator for storage. 10 g of the prepared clay material was placed in 500 mL of silica sol with a concentration of 40 wt%, a particle size of 10 nm, and a pH of 4 and dispersed uniformly using an ultrasonic disperser. A centrifugal spray drying apparatus was used to spray dry the mixture at 1500 rpm, 0.5 MPa, and 90°C to obtain a solid superacid composite carrier with uniform particle morphology. The mixture was dried in a 5 L gas phase fluidized drying system at 600°C for 5 hours. The resulting composite carrier was stored under a nitrogen atmosphere for future use.

[0063] (2) Compound a1 was dissolved in toluene to prepare a solution with a concentration of 10 mmol / L.

[0064] (3) 50 mg of the clay-silica gel composite support prepared in step (1) was added to a 50 mL flask containing 10 mL of hexane, and 2 mL of 1 M triisobutylaluminum-hexane solution was added. After stirring for five minutes, 2 mL of the catalyst solution in step (2) was added to obtain catalyst composition A1.

[0065] Examples 2 to 6

[0066] The preparation method refers to Example 1, except that N-methyl-dimethylpyrroloindene, YCl3, o-dimethylaminobenzyllithium, etc. are replaced by ligand raw materials having corresponding substituents. The obtained compounds are shown in a2 to a6 in Table 1, and the corresponding catalyst compositions are A2 to A6.

[0067]

[0068] Table 1

[0069]

[0070] Example 7

[0071]

[0072] In 50mL single-port bottle, add crotonic acid (1.29g, 15mmol) oil bath and vacuumize 1.5h, add 10mL benzene, stir 5min and dissolve completely, slowly add anhydrous aluminum chloride, control bubble rate, back flow reaction 5h after bubble disappears.Spin evaporation removes a large amount of benzene, adds 10mL ethyl acetate, uses glacial hydrochloric acid cancellation, after with the dilute hydrochloric acid extraction 3 times of 3mol / L, saturated common salt water extraction 3 times, saturated NaHCO3 extraction 3 times, finally with saturated common salt water extraction to neutrality, upper organic phase adds desiccant and is dried 8h.Solution is filtered and removed desiccant, obtain crude product and cross post, spin evaporation removes solvent, obtains dark yellow oily 3-methyl-1-indanone 1.358g.

[0073] In a 100 mL single-necked flask, 3-methyl-1-indanone (4.39 g, 30 mmol), 1,1-diphenylhydrazine hydrochloride (8.29 g, 45 mmol), and isopropanol (40 mL) were added sequentially and refluxed for 4.5 hours. Impurities were removed by filtration, and the filtrate was evaporated to remove the isopropanol. The crude product was passed through a column, dried, and then slurried with petroleum ether and filtered to obtain 3.739 g of methyl-N-phenylindole indane as pale yellow crystals.

[0074] 0.98 g of anhydrous YCl3 (Fw = 195.26, 5 mmol) was weighed into a 100 mL Schlenk flask, 30 mL of tetrahydrofuran (dehydrated) was added, and the mixture was heated and stirred at 60°C for 10 hours. The THF was then removed in vacuo to obtain a white powdery solid YCl3 (THF) 3.5, used directly in the next step.

[0075] Weigh methyl-N-phenylindole indene (5mmol) in a 100mL Schlenk bottle and add 40mL of anhydrous ether to form a colorless solution. Cool it to -25°C, then slowly add n-BuLi hexane solution (2.4mol / L, 2.3mL, 5.5mmol) dropwise. The solution gradually turns bright yellow, accompanied by the formation of yellow insoluble matter. After the addition is complete, let it rise to 25°C naturally and continue stirring at 25°C for 2 hours. After the reaction is complete, remove the solvent under vacuum to obtain bright yellow crystals, which are the lithium salt intermediates. Weigh the above lithium salt intermediates and dissolve them in anhydrous THF to make a solution. Then slowly add it dropwise to YCl3(THF) at -25°C. 3.5 After the addition is complete, the temperature is allowed to rise naturally to 25°C and the reaction is continued at 25°C with stirring for 12 hours. After the reaction is complete, the THF is removed under vacuum, and the residue is extracted with anhydrous toluene. The filtrate is filtered and collected, and the toluene is removed under vacuum to obtain a yellow oil. Subsequently, 20 mL of n-hexane is added to precipitate the solid, which is filtered and washed twice with small amounts of n-hexane to obtain a light yellow powder with a yield of approximately 80%.

[0076] The above product was dissolved in toluene and cooled to -25°C. A toluene solution of o-dimethylaminobenzyllithium was slowly added dropwise. After the addition was complete, the temperature was naturally raised to 25°C and the reaction was continued with stirring for 16 hours, resulting in the formation of a white precipitate. After the reaction was completed, the insoluble material was filtered off, the solvent removed from the resulting filtrate under vacuum, and the solid product a7 was washed twice with n-hexane to obtain a 70% yield.

[0077] The preparation method of the catalyst composition is as described in Example 1, and a catalyst composition A7 is prepared.

[0078] Examples 8 to 19

[0079] The preparation method is similar to that of Example 7, except that crotonic acid, 1,1-diphenylhydrazine hydrochloride, YCl3, o-dimethylaminobenzyl lithium, etc. are replaced by raw materials having corresponding substituents. The resulting compounds are shown in Table 2, and catalysts a8 to a19 and catalyst compositions A8 to A19 are obtained.

[0080]

[0081] Table 2

[0082]

[0083] Example 20

[0084] The preparation method is similar to that of Example 7, except that, in the catalyst composition preparation process, in step (1) of preparing the clay material, 50 g of kaolin with a particle size of 30 μm and 500 ml of a 30 wt% hydrochloric acid solution are placed in a 1 L flask and stirred at 95 ° C for 4 hours to prepare a layered solid superacid material.

[0085] Example 21

[0086] The preparation method is similar to that of Example 7, except that, during the preparation of the catalyst composition, 10 g of the clay material from step (1) is placed in 500 ml of silica sol with a concentration of 40 wt %, a particle size of 20 nm, and a pH of 5 to prepare a clay-silica gel composite carrier.

[0087] Example 22

[0088] The preparation method is similar to that of Example 7, except that, during the preparation of the catalyst composition, 10 g of the clay material from step (1) is placed in 500 ml of silica sol having a concentration of 40 wt %, a particle size of 30 nm, and a pH of 6 to prepare a clay-silica gel composite carrier.

[0089] Test Example 1

[0090] polymerization

[0091] To a 2L polymerization kettle purged with nitrogen, 1L of hexane, 1mL of a 1mM triisobutylaluminum-hexane solution, and the catalyst compositions prepared in the preceding examples were added in sequence. Hydrogen and propylene were introduced with stirring, maintaining a hydrogen / ethylene partial pressure of 1 / 3 at 1MPa. The temperature was raised to 70°C, and polymerization was allowed to proceed at this temperature for 2 hours. After the reaction was complete, the reactor was cooled, the product was discharged, and dried to obtain a polymer. The reaction results are shown in Table 3.

[0092] Table 3 Catalyst activity and polymer molecular weight distribution

[0093]

[0094]

[0095] In Table 3, the M in the activity unit Kg / mol M refers to a rare earth metal.

[0096] As shown in Table 3, under the same conditions, the molecular weight distribution of the polymers obtained is relatively narrow, the activities of Examples 7 to 22 are generally higher than those of Examples 1 to 6, and the catalysts with indole substituents are generally more active than those with pyrrole substituents.

[0097] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the present invention.

Claims

1. An olefin polymerization catalyst composition, characterized in that The catalyst composition comprises a main catalyst, a carrier and a third component, wherein the main catalyst is a rare earth metal complex represented by the general formula (I): CpLnL1L2 (I) Wherein, Cp is a substituent formed by removing the hydrogen from the carbon atom connected to R in the compound represented by general formula (II): (II) Among them, R 1 to R 5 、R x and R y the same or different, each independently selected from H, halogen, C1-C20 alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C6-C30 aryl and derivatives thereof, C7-C30 aralkyl and derivatives thereof, C7-C30 alkylaryl and derivatives thereof, C1-C30 alkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, C6-C30 aryl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, C7-C30 aralkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, silanyl - SiR'3, alkoxy - OR', mercapto ―SR', carboxyl ―OCOR', amino ―NR'2 and phosphino ―PR'2, wherein R' is selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C6-C30 aryl and derivatives thereof, C7-C30 aralkyl and derivatives thereof, C1-C30 alkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the periodic table and derivatives thereof, C6-C30 aryl containing heteroatoms of elements from Group IIIA to Group VIIA in the periodic table and derivatives thereof, C7-C30 aralkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the periodic table and derivatives thereof; R and R 1 to R 5 、R x and R y One of the groups is the same, but not H; Ln is a rare earth metal element; L1 and L2 are the same or different and are independently selected from one of H, halogen, hydrocarbon group (R'), silicon hydrocarbon group (SiR'3), alkoxy group (OR'), mercapto group (SR'), carboxyl group (OCOR'), amino group (NR'2) and phosphine group (PR'2), R' is as described above; The carrier is a clay-silica gel composite carrier; The third component is selected from the compound represented by chemical formula (III): MR113 (III) Wherein, M is Al, Zn or Mg; R11 is hydrogen, halogen, C1-C20 alkyl or C1-C20 haloalkyl; R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C11-C20 long chain aliphatic alkyl, vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptenyl, nonenyl, decenyl, C11-C20 long chain alkenyl, benzyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-methylphenyl, tert-butylphenyl, m-chlorophenyl, o-chlorophenyl, chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl, p-dimethylaminophenyl.

2. The catalyst composition according to claim 1, characterized in that R in the general formula (II) x and R y Connected to each other into a ring.

3. The catalyst composition according to claim 2, characterized in that Cp is a substituent formed by removing the hydrogen from the carbon atom connected to R in the compound represented by general formula (IV): (IV) Among them, R 1 to R 9 the same or different, and each independently selected from H, halogen, C1-C20 alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C6-C30 aryl and derivatives thereof, C7-C30 aralkyl and derivatives thereof, C7-C30 alkylaryl and derivatives thereof, C1-C30 alkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, C6-C30 aryl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, C7-C30 aralkyl containing heteroatoms of elements from Group IIIA to Group VIIA in the Periodic Table and derivatives thereof, silanyl - SiR'3, alkoxy - OR', One of a thiol group (SR'), a carboxyl group (OCOR'), an amino group (NR'2), and a phosphino group (PR'2), wherein R' is selected from the group consisting of a C1-C20 alkyl group, a C2-C20 alkenyl group, a C3-C20 cycloalkyl group, a C6-C30 aryl group and derivatives thereof, a C7-C30 aralkyl group and derivatives thereof, a C1-C30 alkyl group containing heteroatoms of elements from Groups IIIA to VIIA in the Periodic Table and derivatives thereof, a C6-C30 aryl group containing heteroatoms of elements from Groups IIIA to VIIA in the Periodic Table and derivatives thereof, and a C7-C30 aralkyl group containing heteroatoms of elements from Groups IIIA to VIIA in the Periodic Table and derivatives thereof; R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C11-C20 long chain aliphatic alkyl, vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptenyl, nonenyl, decenyl, C11-C20 long chain alkenyl, benzyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-methylphenyl, tert-butylphenyl, m-chlorophenyl, o-chlorophenyl, chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl, p-dimethylaminophenyl.

4. The catalyst composition according to any one of claims 1 to 3, characterized in that The C1-C20 alkyl group is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and C11-C20 long-chain alkyl groups; the C2-C20 alkenyl group is selected from one of vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptenyl, nonenyl, decenyl, and C11-C20 long-chain alkenyl groups; the C3-C20 cycloalkyl group is selected from one of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; the C6-C30 aryl group and its derivatives are selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, and substituted or unsubstituted fluorenyl; the C7-C30 aralkyl group and its derivatives are selected from one of benzyl, p-methyl The present invention relates to one of phenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl and p-tert-butylphenyl; the C1-C30 alkyl, aryl, aralkyl and derivatives thereof containing heteroatoms from Group IIIA to Group VIIA of the periodic table are selected from one of chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl and p-dimethylaminophenyl.

5. The catalyst composition according to claim 1, characterized in that The Ln is selected from scandium, yttrium, praseodymium, neodymium, samarium, gadolinium, dysprosium or holmium.

6. The catalyst composition according to claim 1, characterized in that L1 and L2 are independently selected from one of hydrogen, trimethylsilylmethyl, bis(trimethylsilyl)methyl, tris(trimethylsilyl)methyl, o-(N,N-dimethylamino)benzyl, and N,N-bis(trimethylsilyl)amino.

7. The catalyst composition according to claim 1, characterized in that The clay in the clay-silica gel composite carrier is one or more of montmorillonite, vermiculite, kaolin, sepiolite, attapulgite and glauconite.

8. The catalyst composition according to claim 7, characterized in that The average particle size of the clay is 0.1 to 50 μm.

9. The catalyst composition according to claim 1, characterized in that The silica sol particle size in the clay-silica gel composite carrier is 5-30 nm, and the pH value is 3-7.

10. The catalyst composition according to claim 1, characterized in that The ratio of clay to silica sol in the clay-silica gel composite carrier is 0.1 to 20 mol of silica sol per gram of clay.

11. The catalyst composition according to claim 1, characterized in that The weight / molar ratio of the carrier to the main catalyst is 1 kg / mole to 50 kg / mole.

12. The catalyst composition according to claim 1, characterized in that The molar ratio of the compound represented by the chemical formula (III) to the main catalyst is 0.1 / 1 to 100000 / 1.

13. The catalyst composition according to claim 12, characterized in that The molar ratio of the compound represented by the chemical formula (III) to the main catalyst is 10 / 1 to 50000 / 1.

14. A method for preparing the olefin polymerization catalyst composition according to claim 1, characterized in that: The following steps are involved: (1) washing clay with an inorganic acid solution and then with distilled water until neutral, drying and grinding the clay to obtain acid-modified clay; mixing the prepared acid-modified clay with silica sol, and spray drying the mixture to obtain a clay-silica gel composite carrier; (2) dissolving the main catalyst in an organic solvent; (3) The solution of the main catalyst prepared in step (2) and the third component are mixed with the support prepared in step (1) simultaneously or in any order.

15. The method for preparing the catalyst composition according to claim 14, characterized in that: The inorganic acid is sulfuric acid, hydrochloric acid or nitric acid; the organic solvent is toluene, hexane or heptane.

16. The method for preparing the catalyst composition according to claim 14, wherein: The ratio of the clay to the inorganic acid is 0.1 to 1 mol of the inorganic acid per gram of layered clay.

17. The method for preparing the catalyst composition according to claim 14, wherein: The concentration of the inorganic acid solution is 0.1 mol / L to 2.0 mol / L.

18. The method for preparing an olefin polymerization catalyst composition according to claim 14, wherein: In step (1), the washing temperature is 0°C to 100°C, the washing condition of the inorganic acid solution is stirring for 2 to 10 hours, and the conditions for drying the product after filtration with distilled water are: 200°C to 800°C for 2 to 8 hours.

19. The method for preparing an olefin polymerization catalyst composition according to claim 14, wherein: In step (1), when the acid-modified clay is mixed with the silica sol, it is evenly dispersed using an ultrasonic disperser; the clay-silica gel composite carrier in the form of particles obtained by spray drying is heated to 600-800° C. under nitrogen fluidization and dried for 2-10 hours, and then stored under inert gas atmosphere protection conditions.

20. Use of the olefin polymerization catalyst composition according to claim 1 in propylene polymerization.

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