Olefin polymerization catalyst composition, preparation method and application thereof

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, 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' is as described above; the carrier is fluorinated silica gel particles; the third component is selected from the compound represented by chemical formula (III): MR 11 3(III) The present invention also relates to a preparation method and application of the above olefin polymerization catalyst composition.

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 composition in ethylene 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 ethylene or propylene. 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 ethylene or propylene (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 ethylene 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 ethylene 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 primary object of the present invention is to provide an olefin polymerization catalyst composition and a method for preparing the same. Another object of the present invention is to provide the use of the catalyst composition in ethylene polymerization. The olefin polymerization catalyst composition provided by the present invention exhibits significantly improved catalytic activity compared to existing catalysts.

[0009] In order to achieve the purpose of the present invention, 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-C 20Alkyl, 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 Alkyl 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 fluorinated silica gel particles;

[0017] The third component is selected from the compound represented by chemical formula (III): MR 113(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 Alkyl 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 R1 to R 5 、R x and R y 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, heptene, octene, nonene, decene, 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 one of benzyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl and p-tert-butylphenyl; the alkyl group, aryl group, aralkyl group and its derivatives containing heteroatoms from Group IIIA to Group VIIA in 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 groups (including undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, the same below), vinyl, propenyl, allyl, butenyl, pentenyl, octenyl, heptenyl, octenyl, nonenyl, decenyl, C 11~C 20 Long chain alkenyl (including undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosyl, the same below), 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, chloromethylphenyl 1-Hydroxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,1-dimethylenedioxy-1,

[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 carrier is prepared by reacting fluoride with silica gel, followed by heating in an oxygen atmosphere.

[0033] In the catalyst composition of the present invention, it is preferred that the fluoride is dialkylaluminum fluoride.

[0034] In the catalyst composition of the present invention, it is preferred that the fluoride is diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride.

[0035] In the catalyst composition of the present invention, it is preferred that the feeding ratio of the fluoride to the silica gel is 1-50 mmol / g.

[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 structural formula (III) to the main catalyst is 0.1 / 1 to 100000 / 1.

[0038] In the catalyst composition of the present invention, it is preferred that the molar ratio of the compound represented by chemical formula (III) to the main catalyst is 10 / 1 to 50000 / 1.

[0039] The catalyst composition of the present invention is preferably such that the compound represented by the chemical 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.

[0040] To this end, the present invention also provides a method for preparing the above-mentioned olefin polymerization catalyst composition, comprising the following steps:

[0041] (1) reacting fluoride with silica gel, and then heating under an oxygen atmosphere to prepare a carrier;

[0042] (2) dissolving the main catalyst in an organic solvent;

[0043] (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.

[0044] The method for preparing the olefin polymerization catalyst composition of the present invention is preferably characterized in that step (1) comprises dispersing dehydrated silica gel in an organic solvent at a dispersion temperature of -30°C to 120°C, contacting the solution with a fluoride at the same temperature for 0.5 to 10 hours, filtering the solid, washing it with an organic solvent, and drying it, followed by heating it at 200 to 500°C for 1 to 6 hours under an oxygen atmosphere to obtain the support.

[0045] In the method for preparing the olefin polymerization catalyst composition of the present invention, preferably, the dehydration condition is vacuuming at 200-700°C.

[0046] In the method for preparing the olefin polymerization catalyst composition of the present invention, preferably, the organic solvent is toluene, hexane or heptane.

[0047] In the method for preparing the olefin polymerization catalyst composition of the present invention, it is preferred that the fluoride is dialkylaluminum fluoride.

[0048] In the method for preparing the olefin polymerization catalyst composition of the present invention, it is preferred that the fluoride is diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride.

[0049] In the method for preparing the olefin polymerization catalyst composition of the present invention, it is preferred that the feeding ratio of the fluoride to the silica gel is 1-50 mmol / g.

[0050] In the method for preparing the olefin polymerization catalyst composition of the present invention, preferably, the weight / molar ratio of the carrier to the main catalyst is 1 kg / mole to 50 kg / mole.

[0051] To this end, the present invention also provides an application of the above-mentioned olefin polymerization catalyst composition in ethylene polymerization.

[0052] The olefin polymerization catalyst composition employed in the present invention differs from the prior art in that the R substituent on the catalyst ligand of the indeno[1,2-b]-substituted pyrrole described by the general formula (II) or the indeno[1,2-b]-substituted indole described by the general formula (IV) is not hydrogen, and fluorinated silica gel is used in combination with a third component as a carrier and activator. The R group and the N atom are located relative to each other in the centerline of the ligand structure. The inventors unexpectedly discovered that when R is selected from a non-hydrogen group, especially when R is a relatively large sterically hindered group, the catalytic activity is significantly improved compared to when R is hydrogen. Based on this improvement, the use of fluorinated silica gel as a carrier transforms the homogeneous catalytic system into a heterogeneous catalytic system, further improving the polymer product morphology, increasing the product's bulk density and fluidity, and largely preventing clogging of the polymerization apparatus. More importantly, the fluorinated silica gel provides sufficient acidic sites, eliminating the need for expensive borate reagents as activators, reducing production costs and facilitating industrial applications.

[0053] The present invention provides significantly improved catalytic activity. The reason or mechanism for this beneficial effect is that the R substituent on the catalyst ligand of the indeno[1,2-b]-substituted pyrrole of the general formula (II) or the indeno[1,2-b]-substituted indole of the general formula (IV) is not hydrogen, and the R group and the nitrogen atom are located relative to the centerline of the ligand structure. When R is selected from a group other than hydrogen, especially when R is a relatively large steric group, the catalytic activity is significantly improved compared to when R is hydrogen.

[0054] The catalyst provided by the present invention increases the bulk density of the product when used in ethylene polymerization. This beneficial effect is attributed to the following mechanism: using fluorinated silica gel as a carrier transforms the homogeneous catalytic system into a heterogeneous one, further improving the polymer product morphology, increasing its bulk density and fluidity, and largely preventing clogging of the polymerization apparatus.

[0055] The catalyst provided by the present invention avoids the use of expensive borate reagents as activators, thus reducing production costs and facilitating industrial applications. The reason or mechanism for this beneficial effect is that the fluorinated silica gel provides sufficient acidic sites, eliminating the need for expensive borate reagents as activators. DETAILED DESCRIPTION

[0056] 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.

[0057] The operations for preparing the catalysts in the examples were all carried out under the protection of high-purity nitrogen.

[0058] Bulk density of polymer: in accordance with GB / T1636-2008.

[0059] Example 1

[0060]

[0061] N-methyl-dimethylpyrroloindene (5mmol) was added to a 50ml Schlenk flask 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 constant-pressure-displaced into trimethylsilyl chloride and reacted at room temperature for 8h. Filtered, the filtrate was spin-dried, quenched with ice, and extracted three times with saturated brine. 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.

[0062] 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.

[0063] 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 (2.4mol / L, 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 to stir and react at 25°C for 2 hours. After the reaction is complete, remove the solvent under vacuum to obtain crystals, which are the lithium salt intermediates. Weigh the above lithium salt intermediates and dissolve them in anhydrous THF to make a solution. Then, at -25°C, slowly add it dropwise to YCl3(THF) 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%.

[0064] 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.

[0065] Preparation of catalyst composition

[0066] (1) Grace 955 silica gel was vacuumed at 400°C for 4 hours and then cooled naturally to room temperature under inert gas. 5 g of the above dehydrated silica gel was added to a 500 mL three-necked flask containing 200 mL of hexane. 15 mL of a 1 M AlEt2F toluene solution was added at room temperature and stirred for 2 hours. The mixture was filtered, washed with hexane, and vacuum dried. The above-obtained support was heated from room temperature to 100°C within 1 hour and maintained for 1 hour. The temperature was then raised to 400°C and maintained for 3 hours. The support was then cooled naturally to room temperature. During this temperature change, the support remained fluidized in oxygen.

[0067] (2) Compound a1 was dissolved in toluene to prepare a solution with a concentration of 10 mM.

[0068] (3) 50 mg of the fluorinated silica gel prepared in step (1) was added to a 50 mL flask containing 10 mL of hexane, and 2 mL of a 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.

[0069] Examples 2 to 6

[0070] 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.

[0071] Comparative Examples 1 and 2

[0072] The preparation method refers to Example 1, and N-methyl-dimethylpyrroloindene, YCl3, o-dimethylaminobenzyl lithium, etc. are replaced with ligand raw materials having corresponding substituents. The resulting catalysts are shown in d1 and d2 in Table 1, and the corresponding catalyst compositions D1 and D2.

[0073]

[0074] Table 1

[0075]

[0076] Example 7

[0077]

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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. 3.5After 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 a small amount of n-hexane to obtain a light yellow powder solid with a yield of approximately 80%.

[0082] 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.

[0083] The preparation method of the catalyst composition is as described in Example 1, and a catalyst composition A7 is prepared.

[0084] Examples 8 to 19

[0085] 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.

[0086] Comparative Examples 3 to 5

[0087] The preparation method refers to Example 7, replacing crotonic acid, 1,1-diphenylhydrazine hydrochloride, YCl3, o-dimethylaminobenzyl lithium, etc. with raw materials having corresponding substituents. The obtained compounds are shown in Table 2, and catalysts d3~d5 and catalyst compositions D3~D5 are obtained.

[0088]

[0089] Table 2

[0090]

[0091]

[0092] Example 20

[0093] The preparation method is similar to that of Example 7, except that, during the preparation of the catalyst composition, the AlEt2F toluene solution in step (1) is added and dispersed at a temperature of 50°C, and stirred for 0.5 hour; the carrier obtained above is heated from room temperature to 150°C within 1 hour and maintained for 0.5 hour, then heated to 450°C and maintained for 3 hours, and naturally cooled to room temperature. During this temperature change, the carrier remains fluidized in oxygen.

[0094] Example 21

[0095] The preparation method is similar to that of Example 7, except that during the preparation of the catalyst composition, the compound in step (2) is prepared into a 20 mmol / L solution.

[0096] Example 22

[0097] The preparation method is similar to that of Example 7, except that, during the preparation of the catalyst composition, 1 mL of a 1 mol / L triisobutylaluminum-hexane solution is added in step (3).

[0098] Comparative Example 6

[0099] The catalyst preparation method is the same as in Example 1, except that the catalyst composition preparation steps are as follows:

[0100] (1) Compound a1 was dissolved in toluene to prepare a solution with a concentration of 10 mM.

[0101] (2) 20 μmol of [PhNHMe2] + [B(C6F5)4] - To a 50 mL flask containing 10 mL of hexane, 2 mL of 1 M triisobutylaluminum-hexane solution was added, and after stirring for five minutes, 2 mL of the catalyst solution of step (1) was added to obtain catalyst composition D6.

[0102] Comparative Examples 7 to 10

[0103] The steps for preparing the catalyst composition were similar to those of Comparative Example 6, except that compound a1 was replaced with a2, a7, a8, and a12, respectively, to obtain catalyst compositions D7 to D10.

[0104] Test Example 1

[0105] polymerization

[0106] To a 2L polymerization kettle purged with nitrogen, 1L of hexane, 1mL of a 1mM triisobutylaluminum-hexane solution, and the aforementioned catalyst composition were added sequentially. Hydrogen and ethylene 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 carried out at this temperature for 2 hours. After the reaction was completed, the reactor was cooled, the product was discharged, and dried to obtain a polymer.

[0107] Table 3

[0108]

[0109]

[0110] In Table 3, the activity unit Kg / mol M refers to a rare earth metal.

[0111] Table 4

[0112]

[0113] In Table 4: nd means not tested.

[0114] Table 5

[0115]

[0116]

[0117] Table 3 shows that the catalyst ligands in Examples 1 and 2 were respectively selected from compounds wherein R in the general formula (II) is not hydrogen, and the catalyst ligands in Examples 7 to 9 were respectively selected from compounds wherein R in the general formula (IV) is not hydrogen. Compared with Comparative Examples 1 to 2 and Comparative Examples 3 to 5, the only difference being whether the R substituent is H. The activities of Examples 1 to 5 are significantly higher than those of Comparative Examples 1 to 5.

[0118] Table 4 shows that Examples 1, 2, 7, 8, and 12 use fluorinated silica gel as an activator and carrier. Comparative Examples 6 to 10 do not use fluorinated silica gel but use [PhNHMe2] + [B(C6F5)4] - The polyethylene obtained in Examples 1, 2, 7, 8, and 12 was granular, with a bulk density of 0.32 to 0.34 and good fluidity. Comparative Examples 6 to 10, while having comparable or slightly higher activity than Examples 1, 2, 7, 8, and 12, did not form granules but rather agglomerates, exhibiting poor fluidity and making it impossible to determine the bulk density. This demonstrates that fluorinated silica gel can replace borate activators while improving polymer morphology.

[0119] Table 5 shows that under the same conditions, the activities of Examples 7 to 22 are generally higher than those of Examples 1 to 6, and the activities of catalysts with indole substituents are generally higher than those of pyrrole catalysts.

[0120] 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): CpLnL 1 L 2 (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-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 Alkyl 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; Ln is a rare earth metal element; 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; The carrier is fluorinated silica gel particles; The third component is selected from the compound represented by chemical formula (III): MR 11 3 (III) Wherein, M is Al, Zn or Mg; R 11 For hydrogen, halogen, C1-C 20 Alkyl or C1-C 20 of a haloalkyl group; R is 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, heptenyl, nonenyl, decenyl, C 11 ~C 20 Long-chain alkenyl, benzyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-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, 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 Alkyl 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; R is 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, heptenyl, nonenyl, decenyl, C 11 ~C 20 Long-chain alkenyl, benzyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl, p-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-C 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, 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 one of benzyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesitylene, o-diisopropylphenyl and p-tert-butylphenyl; the alkyl group, aryl group, aralkyl group and its derivatives containing heteroatoms from Group IIIA to Group VIIA in 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 L 1 and L 2 Each of the following groups is independently selected from the group consisting 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 carrier is prepared by reacting fluoride with silica gel and then heating in an oxygen atmosphere.

8. The catalyst composition according to claim 7, characterized in that The fluoride is dialkylaluminum fluoride.

9. The catalyst composition according to claim 8, characterized in that The fluoride is diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride.

10. The catalyst composition according to claim 7, characterized in that The feeding ratio of the fluoride to the silica gel is 1-50 mmol / g.

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 any one of claims 1 to 13, characterized in that: The following steps are involved: (1) Fluoride is reacted with silica gel, and then heated under an oxygen atmosphere to prepare a 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 an olefin polymerization catalyst composition according to claim 14, wherein: Step (1) is to disperse the dehydrated silica gel in an organic solvent at a dispersion temperature of -30°C to 120°C, contact the solution with fluoride at the temperature for 0.5 to 10 hours, filter the solid, wash it with an organic solvent, dry it, and then heat it at 200-500°C for 1-6 hours under an oxygen atmosphere to obtain the carrier.

16. The method for preparing an olefin polymerization catalyst composition according to claim 15, wherein: The dehydration condition is vacuuming at 200-700°C.

17. The method for preparing an olefin polymerization catalyst composition according to claim 14 or 15, characterized in that: The organic solvent is toluene, hexane or heptane.

18. The method for preparing an olefin polymerization catalyst composition according to claim 14, wherein: The fluoride is dialkylaluminum fluoride.

19. The olefin polymerization catalyst composition according to claim 18, characterized in that The fluoride is diethylaluminum fluoride, diisopropylaluminum fluoride or dibutylaluminum fluoride.

20. Use of the olefin polymerization catalyst composition according to any one of claims 1 to 13 in ethylene polymerization.

Images