Anthracene bridged metallocene complex catalyst, preparation method thereof and application of anthracene bridged metallocene complex catalyst in catalyzing olefin polymerization reaction

Abstract

The invention discloses an anthracene bridged metallocene complex catalyst, a preparation method thereof and application of the anthracene bridged metallocene complex catalyst in catalyzing olefin polymerization reaction. The catalyst has a structural expression as shown in the specification. The synthetic method of the anthracene bridged metallocene complex catalyst is simple and high in synthetic efficiency; the catalyst can be used for catalyzing copolymerization of ethylene and alpha-olefin or cycloolefin monomers, and has the properties of high catalytic activity, adjustable molecular weight distribution in a wider range, high temperature resistance and the like. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a complex catalyst for olefin polymerization, in particular to an anthracene-bridged metallocene complex catalyst and a preparation method thereof and application thereof in catalyzing olefin polymerization reactions. Background Art

[0002] Polyolefin materials have the advantages of excellent comprehensive performance, wide monomer sources, low density, low processing temperature, etc., and are important materials indispensable to human life. In olefin polymerization, the catalyst determines the olefin polymerization behavior, polymer particle morphology, structure and performance. Currently, industrialized polyethylene catalysts include Ziegler-Natta catalysts, Phillips catalysts and metallocene catalysts, as well as transition metal complex-type high-efficiency ethylene homopolymerization and copolymerization catalysts developed in recent years.

[0003] Polymers synthesized by metallocene catalysts generally have a narrow molecular weight distribution, which is beneficial to improve polymer performance indicators, but also leads to poor processing performance. The solution is to use two different metallocenes to form a complex catalytic system or use a binuclear metallocene catalyst to appropriately broaden the molecular weight distribution of the polymer by utilizing the difference between the two active centers. For example, Chinese patent CN113087825A provides an anthracene skeleton bimetallic catalyst that catalyzes ethylene homopolymerization and ethylene and α-olefin or cycloolefin copolymerization, and has the characteristics of high activity and high temperature resistance.

[0004] Changing the structure of the bridge chain of binuclear metallocene catalyst is an effective method to change the molecular weight distribution and microscopic properties of polymers. Studies have shown that when the length of the bridging group is closely related to the molecular weight of the polymer and the polymerization activity, when the bridge is greater than 5 atoms, the activity will be improved compared with the mononuclear metallocene catalyst (J. Organomet. Chem., 2003, 667: 53); the introduction of heteroatoms is conducive to the improvement of the catalytic activity of the metal center, however, excessive heteroatoms will poison the metal center and deactivate it. By rationally designing the bridging group and the structure of the single active center metallocene catalyst, the two active centers have appropriate spacing, coordination space and electron distribution, and the synergistic catalytic effect of the dual active centers can be effectively exerted (Chemical Reviews, 2011, 111 (3): 2450-2485.), thereby obtaining an excellent catalyst with high catalytic activity, adjustable molecular weight distribution and high temperature resistance. The heterometallic catalyst constructed by bridging a restricted geometry titanium catalyst and an ethylene oligomerization chromium catalyst catalyzes ethylene polymerization to produce a polyethylene product with a high degree of branching (J.Am.Chem.Soc.2014,136,10460-10469). The methylene benzene bridge, biphenyl bridge and thiophene bridge binuclear metallocene catalyst, the bridging group structure in the catalyst structure weakens the conjugation between the benzene ring and the metallocene ring, the polymerization activity is greater than that of the mononuclear catalyst, the synthesis route is long, and the cost is relatively high ((Euro Polym Jnl,41(2005):1519-1524.).

[0005] In summary, currently, existing bridged bimetallic catalysts have great difficulties: such as difficulty in catalyst structure modification, inappropriate metal center distance, complex synthesis process, low synthesis efficiency, etc. It is necessary to develop new binuclear metallocene catalysts that have excellent properties such as high catalytic activity, adjustable molecular weight distribution in a wide range, and high temperature resistance. Summary of the invention

[0006] In order to solve the above technical problems, the present invention proposes an anthracene-bridged metallocene complex catalyst and its preparation method and application in catalyzing olefin polymerization reaction. The anthracene-bridged metallocene complex catalyst has a simple synthesis method and high synthesis efficiency; it can be used to catalyze the copolymerization of ethylene and α-olefin or cycloolefin monomers, and has the properties of high catalytic activity, adjustable molecular weight distribution in a wide range, high temperature resistance, etc.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] According to the first aspect of the present invention, an anthracene-bridged metallocene complex catalyst is first provided, which has the following structural expression of formula I:

[0009]

[0010] in:

[0011] M is selected from Group IV metals, preferably titanium, zirconium or hafnium;

[0012] Cp is selected from substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl;

[0013] Y is selected from elements of Groups VA-VIA, preferably N, O or S;

[0014] R 1 Selected from C1-C6 alkyl, C1-C6 alkoxy, and optionally substituted or unsubstituted C3-C10 cycloalkyl, C6-C14 aryl, C6-C14 aryloxy, preferably C1-C6 alkyl, C6-C14 alkylaryl, C6-C14 halogenated aryl;

[0015] R 2 , R 3 , R 4 , R 5 The same as or different from each other, each independently selected from hydrogen, halogen or the following groups: C1-C6 alkyl and optionally substituted or unsubstituted C1-C6 alkoxy, C3-C10 cycloalkyl, C6-C14 aryl, C6-C14 aryloxy, C4-C9 silyl;

[0016] X is selected from halogen, C1-C20 alkyl, C7-C20 substituted or unsubstituted benzyl, and C2-C20 alkylamino.

[0017] In some preferred embodiments, Cp is selected from cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, 1-tert-butyl-2-trimethylsilylcyclopentadienyl, 1,3-bis(trimethylsilyl)cyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2-diethylcyclopentadienyl, Cyclopentadienyl, 1,2-diphenylcyclopentadienyl, cyclohexylcyclopentadienyl, 2,2′-biphenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 1,3-dimethylindenyl, 4,7-dimethylindenyl, benzoindenyl, 2-methylbenzoindenyl, 3-methylindenyl, 3-benzylindenyl, 3-phenylindenyl, 2-methyl-4-phenylindenyl, fluorenyl, octahydrofluorenyl, 2,7-di-tert-butylfluorenyl.

[0018] According to the second aspect of the present invention, there is also provided a method for preparing the anthracene-bridged metallocene complex catalyst as described above, comprising the following steps:

[0019] In anhydrous, oxygen-free and inert atmosphere, the compound of formula II is dissolved in an ultra-dry organic solvent to obtain a solution or suspension thereof; an alkyl metal reagent is added at low temperature, and then a metal salt MX is added 4 or its ether complex to obtain a compound of formula III;

[0020] The compound of formula IV is mixed with an alkyl metal reagent, and then added to the reaction solution of the compound of formula III, and the anthracene-bridged metallocene complex catalyst is obtained after the reaction;

[0021]

[0022] Among them, R 1 , R 2 , R 3 , R 4 , R 5 The definitions of , Cp, M, X, and Y are the same as in the previous text.

[0023] In some preferred embodiments, the alkyl metal reagent is one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, and lithium diisopropylamide.

[0024] After the reaction is completed, the present invention may further include post-treatment and purification processes such as recrystallization and silica gel column chromatography, which are not specifically limited.

[0025] The source of the compound of formula II is not limited in the present invention, and can be obtained through commercial customization or prepared according to existing known methods. The following is only a feasible example of the preparation method of the compound of formula II provided by the present invention:

[0026]

[0027] Among them, R 2 , R 3 , R 4 , R 5 , the definition of Cp is the same as the definition of Cp in any one of claims 1 and 2;

[0028] (1) dissolving compound V in an organic reagent, adding an alkyl metal reagent to react, and filtering after the reaction to obtain its lithium salt or sodium salt, i.e., compound VI. Preferably, the reaction conditions are: reaction temperature -80°C to 25°C, reaction time 1-8h;

[0029] (2) dissolving compound VII in an organic reagent and adding compound VI to react to generate a compound of formula II. Preferably, the reaction conditions are: reaction temperature -20°C to 45°C, reaction time 1-8h;

[0030] Furthermore, in step (1), the alkyl metal reagent is one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, and lithium diisopropylamide;

[0031] Preferably, the molar ratio of compound V to the alkyl metal reagent is 1:(1 to 1.5);

[0032] Preferably, compound V is selected from one or more of cyclopentadiene, 2-methylcyclopentadiene, indene, 2-methylindenyl, 4,7-dimethylindene, fluorene, and 2,7-di-tert-butylfluorene.

[0033] In step (1), the organic reagent is one or more of diethyl ether, tetrahydrofuran, methyl tert-butyl ether, and dibutyl ether;

[0034] In step (2), the organic reagent is one or more of acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and toluene;

[0035] In step (2), the molar ratio of compound VII to compound VI is 1:(2-2.5);

[0036] Preferably, compound VII is selected from one or more of 1,5-dibromoanthracene, 1,5-dibromo-2,6-dimethoxyanthracene, and 1,5-dibromo-2,3,5,6-tetramethylanthracene.

[0037] According to the third aspect of the present invention, there is also provided a catalyst composition, comprising the anthracene-bridged metallocene complex catalyst and a co-catalyst as described above;

[0038] The co-catalyst is selected from at least one of alkyl aluminum, aluminoxane, modified aluminoxane, or a mixture of at least one of them and a boron salt;

[0039] Preferably, the alkylaluminum is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum;

[0040] Preferably, the aluminoxane is one or more of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane;

[0041] Preferably, the boron salt is one or more of triphenylcarbon tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and tetrakis(pentafluorophenyl)borate-methyldi-(octadecyl)ammonium salt.

[0042] In some preferred embodiments, the amount ratio of the co-catalyst to the anthracene-bridged metallocene complex catalyst is (10-6000):1, preferably (200-2000):1, calculated as the molar ratio of metal Al to metal M;

[0043] Preferably, the amount of the boron salt used is 0-4 times the molar amount of the element B as much as the metal M in the anthracene-bridged metallocene complex catalyst.

[0044] According to a fourth aspect of the present invention, there is also provided an olefin polymerization method, comprising: polymerizing ethylene and α-olefin in the presence of the catalyst composition as described above;

[0045] Preferably, the α-olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene, norbornene, alkyl-substituted norbornene, alkoxy-substituted norbornene, vinyl-substituted norbornene, ester-substituted norbornene, phenyl-substituted norbornene, phenoxy-substituted norbornene, and amino-substituted norbornene.

[0046] In some preferred embodiments, the polymerization reaction temperature is 70-200° C., the pressure is 0.3-8 MPa, and the reaction time is 0.5-200 min.

[0047] The beneficial effects of the present invention are:

[0048] Provided is a dual-active-center metallocene complex (having a structure of formula I), in which two single metallocene complexes are bridged by anthracene, so that the two metal active centers have a suitable spacing, coordination space and electron distribution, and can effectively exert the synergistic catalytic effect of the dual active centers. Compared with the relatively narrow molecular weight distribution of the polymerization product catalyzed by the single-active-center metallocene complex, in the present invention, the catalytic composition can adjust the molecular weight distribution of the cycloolefin polymerization product within a wider range while maintaining high catalytic activity and thermal stability, thereby improving the processing performance of the polymer. DETAILED DESCRIPTION

[0049] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0050] Unless otherwise specified, the raw materials in the following examples of the present invention can be purchased from commercial sources.

[0051] [Example 1] Preparation of complex Cat.1

[0052]

[0053] (1) In N 2Under a 37°C atmosphere, in a 200mL Schlenk bottle, 1,5-dibromoanthracene (3.36g, 10mmol) was dissolved in 100mL anhydrous THF and placed in an ice-water bath; 10ml of cyclopentadienyl sodium (2.0mol / L tetrahydrofuran solution) was added dropwise to the above reaction solution at 0°C (gradually changed from a colorless solution to a dark red solution), then reacted at room temperature for 3h, and the solvent was removed in vacuo to obtain 2.06g of intermediate II-1 with a yield of 85%.

[0054] 1 H NMR (400 MHz, CDCl 3 )δ8.45(d,J=2.9Hz,2H),7.99–7.85(m,2H),7.51–7.08(m,4H),6.77(dt,J=12.4,1.8Hz,2H) ,6.27(dd,J=21.9,12.4Hz,2H),5.71(dt,J=21.7,13.9Hz,2H),3.31(dd,J=13.9,2.0Hz,4H).

[0055] (2) In N 2 Under atmosphere, in a 200mL Schlenk bottle, intermediate II-1 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml of n-butyl lithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain a lithium salt solution of intermediate III-1; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-1 with a yield of 75%.

[0056] 1 H NMR (400 MHz, C 6 D 6 )δ8.69(d,J=2.5Hz,2H),7.86(ddd,J=7.6,2.3,1.2Hz,2H),7.37(t,J=7.8Hz,2H),7 .32(dd,J=7.8,1.3Hz,2H),6.47–6.39(m,4H),6.39–6.33(m,2H),4.12–4.05(m,2H).

[0057] (3) In N 2Under atmosphere, in a 200mL Schlenk bottle, 2,6-diisopropylphenol (2.27g, 12.75mmol) was dissolved in 100mL toluene, and intermediate III-1 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the orange-yellow suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain an orange-yellow solid powder, which was the complex Cat.1 with a yield of 69%.

[0058] 1 H NMR (400 MHz, C 6 D 6 ): δ9.13(d,J=2.3Hz,2H),8.08(ddd,J=7.8,2.3,1.2Hz,2H),7.72(dd,J=7.8,1.2Hz,2H),7.67–7.61(m,4H),7.57(t,J=7.8Hz, 2H),7.43(dd,J=7.4,1.6Hz,2H),7.15–7.09(m,4H),7.06–6.99(m,2H),3.24–3.12(m,4H),1.22(tdd,J=6.1,2.9,1.4Hz,24H).

[0059] [Example 2] Preparation of complex Cat.2

[0060]

[0061] (1) In N 2 Under atmospheric pressure, in a 200mL Schlenk bottle, 1,5-dibromoanthracene (3.36g, 10mmol) was dissolved in 100mL anhydrous THF and placed in an ice-water bath; 10ml of cyclopentadienyl sodium (2.0mol / L tetrahydrofuran solution) was added dropwise to the above reaction solution at 0°C (gradually changed from a colorless solution to a dark red solution), then reacted at room temperature for 3h, and the solvent was removed in vacuo to obtain 2.06g of intermediate II-2 with a yield of 85%.

[0062] (2) In N 2Under atmosphere, in a 200mL Schlenk bottle, intermediate II-2 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml of n-butyl lithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain a lithium salt solution of intermediate III-2; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-2 with a yield of 75%.

[0063] (3) In N 2 Under atmosphere, in a 200mL Schlenk bottle, 2,6-dichlorophenol (2.08g, 12.75mmol) was dissolved in 100mL toluene, and intermediate III-2 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the orange-yellow suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain an orange-yellow solid powder, which was the complex Cat.2, with a yield of 66%.

[0064] 1H NMR (400MHz, C 6 D 6 ): δ9.16(d,J=2.3Hz,2H),8.11–8.04(m,2H),7.72(dd,J=7.8,1.2Hz,2H),7.67–7.61(m,4H),7.57( t,J=7.8Hz,2H),7.43(dd,J=7.4,1.6Hz,2H),7.29–7.23(m,4H),7.04(ddd,J=8.2,7.4,0.7Hz,2H).

[0065] [Example 3] Preparation of complex Cat.3

[0066]

[0067] (1) In N 2 Under atmospheric pressure, in a 200mL Schlenk bottle, 1,5-dibromoanthracene (3.36g, 10mmol) was dissolved in 100mL anhydrous THF and placed in an ice-water bath; 10ml of cyclopentadienyl sodium (2.0mol / L tetrahydrofuran solution) was added dropwise to the above reaction solution at 0°C (gradually changed from a colorless solution to a dark red solution), then reacted at room temperature for 3h, and the solvent was removed in vacuo to obtain 2.06g of intermediate II-3 with a yield of 85%.

[0068] (2) In N2 Under atmosphere, in a 200mL Schlenk bottle, intermediate II-3 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml n-butyllithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain intermediate III-3 lithium salt solution; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for reaction for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-3 with a yield of 75%.

[0069] (3) In N 2 Under atmosphere, in a 200mL Schlenk bottle, 2,4,6-trifluorophenol (1.89g, 12.75mmol) was dissolved in 100mL toluene, and its intermediate III-3 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the orange-yellow suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain an orange-yellow solid powder, which was the complex Cat.3, with a yield of 66%.

[0070] 1H NMR (400MHz, C 6 D 6 ): δ9.12(d,J=2.4Hz,2H),8.11–8.04(m,2H),7.72(dd,J=7.8,1.2Hz,2H),7.67–7.61(m,4 H),7.57(t,J=7.8Hz,2H),7.43(dd,J=7.4,1.6Hz,2H),6.60(ddt,J=8.1,6.8,1.6Hz,4H).

[0071] [Example 4] Preparation of complex Cat.4

[0072]

[0073] (1) In N 2 Under atmospheric pressure, in a 200mL Schlenk bottle, 1,5-dibromoanthracene (3.36g, 10mmol) was dissolved in 100mL anhydrous THF and placed in an ice-water bath; 10ml of cyclopentadienyl sodium (2.0mol / L tetrahydrofuran solution) was added dropwise to the above reaction solution at 0°C (gradually changed from a colorless solution to a dark red solution), then reacted at room temperature for 3h, and the solvent was removed in vacuo to obtain 2.06g of intermediate II-4 with a yield of 85%.

[0074] (2) In N2 Under atmosphere, in a 200mL Schlenk bottle, intermediate II-4 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml n-butyllithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain a lithium salt solution of intermediate III-4; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-4 with a yield of 75%.

[0075] (3) In N 2 Under atmosphere, in a 200mL Schlenk bottle, 2,2,4,4-tetramethylpentane-3-imine (1.80g, 12.75mmol) was dissolved in 100mL toluene, and its intermediate III-4 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the purple-red suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain a purple-red needle-shaped solid, which was the complex Cat.4 with a yield of 69%.

[0076] 1 H NMR (400 MHz, C 6 D 6 ): δ8.69(d,J=2.2Hz,2H),7.86(ddd,J=7.8,2.3,1.4Hz,2H),7.38(t,J=7.8Hz,2H),7.32(dd,J=8. 0,1.3Hz,2H),6.47–6.40(m,4H),6.38(d,J=9.1Hz,2H),4.07(t,J=6.7Hz,2H),1.23–1.18(m,36H).

[0077] [Example 5] Preparation of complex Cat.5

[0078]

[0079] (1) In N 2 Under a 3-(4-nitro-2-oxo-4-yl)-2-nitropropene-2 ​​...

[0080] (2) In N 2 Under atmosphere, in a 200mL Schlenk bottle, intermediate II-5 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml of n-butyl lithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain intermediate III-5 lithium salt solution; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-5 with a yield of 75%.

[0081] (3) In N 2 Under atmosphere, in a 200mL Schlenk bottle, 3,3-dimethylbutane-2-imine (1.26g, 12.75mmol) was dissolved in 100mL toluene, and its intermediate III-5 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the purple-red suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain a purple-red needle-shaped solid, which was the complex Cat.5 with a yield of 64%.

[0082] 1 H NMR (400 MHz, C 6 D 6 ): δ9.13(d,J=2.3Hz,2H),8.08(ddd,J=7.9,2.4,1.3Hz,2H),7.75–7.65(m,6H),7.61–7.52(m,4H),2.08(s,6H),1.22–1.18(m,16H).

[0083] [Example 6] Preparation of complex Cat.6

[0084]

[0085] (1) In N 2 Under a 3-(4-nitro-2-oxo-1-yl)-2-nitropropene-2 ​​...

[0086] (2) In N 2 Under atmosphere, in a 200mL Schlenk bottle, intermediate II-6 (2.06g, 8.5mmol) was dissolved in 100mL anhydrous ether and placed in an ice-water bath; 10.63ml n-butyllithium (1.6mol / L hexane solution) was added dropwise to the above reaction solution at 0°C (gradually changing from a colorless solution to a dark red solution), and then reacted at room temperature for 3h to obtain intermediate III-6 lithium salt solution; titanium tetrachloride (3.22g, 17.00mmol) was added to the above solution, slowly heated to room temperature and stirred for 12h, the red suspension was drained, and then the residue was washed with toluene (30mL×3), the filtrate was collected, and the solvent was removed in vacuo to obtain intermediate III-6 with a yield of 75%.

[0087] (3) In N 2 Under atmosphere, in a 200mL Schlenk bottle, 2,6-diisopropylbenzenethiophenol (2.48g, 12.75mmol) was dissolved in 100mL toluene, and its intermediate III-6 (3.89g, 6.37mmol) was added to the solution. After heating to 90℃ for 12h, the orange-yellow suspension was filtered, the filtrate was collected, concentrated, and a small amount of n-hexane was added. It was placed at -18℃ for precipitation to obtain an orange-yellow solid powder, which was the complex Cat.6 with a yield of 65%.

[0088] 1 H NMR (400 MHz, C 6 D 6 ): δ9.12(d,J=2.5Hz,2H),8.08(ddd,J=7.8,2.3,1.2Hz,2H),7.92(t,J=1.5Hz,2H),7.71(dd,J=7.8,1.2Hz,2H),7.67–7.58(m, 4H),7.57(t,J=7.8Hz,2H),7.20–7.15(m,4H),7.15–7.08(m,2H),3.12–3.00(m,4H),1.29(dddd,J=5.9,3.7,1.9,0.9Hz,24H).

[0089] [Comparative Example 1]

[0090] The complex Cat.7 (structure as follows) was prepared according to the scheme in patent WO2004044018A2.

[0091]

[0092] [Comparative Example 2]

[0093] Prepare complex Cat.8 (structure as follows) with reference to the literature "acromolecules, 1998, 31, 7588-7597".

[0094]

[0095] The following comparative application examples and application examples prepare ethylene copolymers using different complex catalysts, and the main test methods involved are:

[0096] Polymer molecular weight (M w ) and molecular weight distribution (PDI, M w / M n ) was determined by high temperature gel permeation chromatography (PL-GPC220) with 1,2,4-trichlorobenzene as the mobile phase and polystyrene as the standard at 150°C. The standard concentration was 0.1 mg / mL, the solvent flow rate was 1.0 mL / min, the standard parameters were K=59.1, α=0.69, and the sample parameters were K=14.1, α=0.70.

[0097] The melting point of the polymer (T m ) and glass transition temperature (T g ) was measured by differential scanning calorimeter (METTLER, DSC-1). The measurement procedure is as follows: take 5.0-7.0 mg of polymer sample, heat it to 250℃ at a rate of 30℃ / min and maintain it for 5 minutes to eliminate the thermal history, then cool it to 0℃ at a rate of 10℃ / min and keep it constant for 3 minutes, then heat it to 250℃ again, and use the cooling curve to obtain the crystallization peak temperature, and calculate the melting point or glass transition temperature of the polymer from the curve of the second heating process.

[0098] The comonomer insertion rate in ethylene copolymers is 13 C NMR (Bruker ADVANCEⅢ400M) was used for determination. The polymer was dissolved in deuterated 1,2-o-dichlorobenzene at 130°C with a concentration of about 100 mg / mL. Instrument test parameters: pulse angle of 30 degrees, full decoupling, pulse delay time of 3s, and sample scanning times of more than 3000 times. 13 After assigning the peaks of the C NMR spectrum, the sequence distribution and comonomer insertion rate of the copolymer were obtained.

[0099]

Application Example 1

[0100] A 1L autoclave was dried continuously at 120°C for 2 hours, evacuated and gradually cooled to 25°C while maintaining a slight positive pressure in the autoclave and a stirring speed of 500rpm. 500mL Isopar E, 125mL 1-octene and 0.91mL triisobutylaluminum (1.1mol / L hexane solution) were added into the autoclave in sequence. The reaction temperature was then raised to 150°C. The pressure in the autoclave (polymerization reaction pressure) was maintained at 1.0MPa by ethylene gas. After the reaction system was stable, 5.0mL of complex Cat.1 solution (0.001mol / L hexane solution) and 1.0mL of triphenylcarbon tetrakis(pentafluorophenyl)borate (0.006mol / L) were pressed into the reaction system by ethylene gas to start the polymerization reaction. After the polymerization reaction is completed, the ethylene gas is stopped, and the reactor is cooled to 100°C, the pressure is released to discharge the unreacted ethylene, and the reaction liquid is discharged into 500 mL of ethanol. The polymerization product is washed with ethanol three times and dried in a vacuum oven at 50°C to constant weight to obtain an ethylene copolymer.

[0101] [Application Examples 2-6, Comparative Application Example 1]

[0102] The ethylene copolymer was prepared according to the method in Application Example 1, except that the reaction conditions were adjusted according to Table 1.

[0103] Table 1. Reaction conditions in Application Examples 1-6 and Comparative Application Example 1

[0104]

[0105]

Application Example 7

[0106] A 250 mL stainless steel reactor equipped with a magnetic stirrer was dried at 130 °C for more than 2 h, evacuated to below 3.0 mbar while hot, and then N 2 And vacuum-N 2 Replace 3 times, and then replace with vacuum-ethylene gas 3 times. Keep the reactor slightly positive pressure and 500rpm stirring speed, add 100mL 2mol / L norbornene / toluene solution and a certain amount of MAO (1.5mol / L toluene solution) into the reactor in sequence, then raise the reaction temperature to 150°C, maintain the pressure in the reactor (polymerization reaction pressure) at 0.4MPa by ethylene gas, and after the reaction system is stable, press 5.0mL of complex Cat.4 (0.001mol / L toluene solution) into the reaction system by ethylene gas to start polymerization. After the polymerization reaction is completed, stop passing ethylene gas, cool the reactor to 100°C, release the pressure to discharge unreacted ethylene, and discharge the reaction solution into 500mL ethanol. After washing the polymerization product with ethanol 3 times, place it in a vacuum oven at 50°C and dry it to constant weight to obtain an ethylene copolymer.

[0107] [Application Examples 8-11, Comparative Application Example 2]

[0108] The ethylene copolymer was prepared according to the method in Application Example 7, except that the reaction conditions were adjusted according to Table 2.

[0109] Table 2, reaction conditions in application examples 7-11 and comparative application example 2

[0110]

[0111] The results of the ethylene copolymers obtained in the above application examples and comparative application examples are shown in Table 3:

[0112] Table 3. Results and characterization

[0113]

[0114] The results in Table 3 show that the dual-active center metallocene complex of the present invention has excellent high temperature stability and good copolymerization ability with large steric hindrance comonomers such as norbornene. At the same time, the molecular weight distribution of cycloolefin copolymers can be adjusted in a wide range without significantly reducing the catalytic activity.

[0115] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. An anthracene-bridged metallocene complex catalyst, characterized in that: It has the following structural expression: in: M is selected from Group IV metals, preferably titanium, zirconium or hafnium; Cp is selected from substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; Y is selected from elements of Groups VA-VIA, preferably N, O or S; R1 is selected from C1-C6 alkyl, C1-C6 alkoxy, and optionally substituted or unsubstituted C3-C10 cycloalkyl, C6-C14 aryl, C6-C14 aryloxy, preferably C1-C6 alkyl, C6-C14 alkylaryl, C6-C14 halogenated aryl; R2, R3, R4, R5 are the same as or different from each other and are independently selected from hydrogen, halogen or the following groups: C1-C6 alkyl and any substituted or unsubstituted C1-C6 alkoxy, C3-C10 cycloalkyl, C6-C14 aryl, C6-C14 aryloxy, C4-C9 silyl; X is selected from halogen, C1-C20 alkyl, C7-C20 substituted or unsubstituted benzyl, and C2-C20 alkylamino.

2. The anthracene-bridged metallocene complex catalyst according to claim 1, characterized in that Cp is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, 1-tert-butyl-2-trimethylsilylcyclopentadienyl, 1,3-bis(trimethylsilyl)cyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2-diethylcyclopentadienyl indenyl, 1,2-diphenylcyclopentadienyl, cyclohexylcyclopentadienyl, 2,2′-biphenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 1,3-dimethylindenyl, 4,7-dimethylindenyl, benzoindenyl, 2-methylbenzoindenyl, 3-methylindenyl, 3-benzylindenyl, 3-phenylindenyl, 2-methyl-4-phenylindenyl, fluorenyl, octahydrofluorenyl, 2,7-di-tert-butylfluorenyl.

3. A method for preparing anthracene-bridged metallocene complex catalyst according to claim 1 or 2, characterized in that: The following steps are involved: In anhydrous, oxygen-free and inert atmosphere, the compound of formula II is dissolved in an ultra-dry organic solvent to obtain a solution or suspension thereof; an alkyl metal reagent is added at low temperature, and then a metal salt MX4 or an ether complex thereof is added to obtain a compound of formula III; The compound of formula IV is mixed with an alkyl metal reagent, and then added to the reaction solution of the compound of formula III, and the anthracene-bridged metallocene complex catalyst is obtained after the reaction; Wherein, the definitions of R1, R2, R3, R4, R5, Cp, M, X, and Y are the same as those in claim 1 or 2.

4. The method for preparing anthracene-bridged metallocene complex catalyst according to claim 3, characterized in that: The alkyl metal reagent is one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, and lithium diisopropylamide.

5. A catalyst composition, characterized in that Comprising the anthracene-bridged metallocene complex catalyst and a co-catalyst as claimed in claim 1 or 2; The co-catalyst is selected from at least one of alkyl aluminum, aluminoxane, modified aluminoxane, or a mixture of at least one of them and a boron salt; Preferably, the alkylaluminum is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum; Preferably, the aluminoxane is one or more of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; Preferably, the boron salt is one or more of triphenylcarbon tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and tetrakis(pentafluorophenyl)borate-methyldi-(octadecyl)ammonium salt.

6. The catalyst composition according to claim 5, characterized in that The amount ratio of the co-catalyst to the anthracene-bridged metallocene complex catalyst is (10-6000):1, preferably (200-2000):1, based on the molar ratio of metal Al to metal M; Preferably, the amount of the boron salt used is 0-4 times the molar amount of the element B as much as the metal M in the anthracene-bridged metallocene complex catalyst.

7. An olefin polymerization method, characterized in that: In the presence of the catalyst composition according to claim 5 or 6, ethylene and α-olefin are polymerized; Preferably, the α-olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene, norbornene, alkyl-substituted norbornene, alkoxy-substituted norbornene, vinyl-substituted norbornene, ester-substituted norbornene, phenyl-substituted norbornene, phenoxy-substituted norbornene, and amino-substituted norbornene.

8. The olefin polymerization method according to claim 7, characterized in that The polymerization reaction temperature is 70-200°C, the pressure is 0.3-8MPa, and the reaction time is 0.5-200min.

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