Bimetallic metallocene compound and preparation method thereof, polycyclic bimetallic metallocene catalyst, catalyst system and application thereof

Abstract

The invention relates to the field of olefin coordination polymerization catalysts and polyolefin, and discloses a bimetallic metallocene compound and a preparation method thereof, a polycyclic bimetallic metallocene catalyst, and a catalyst system and application thereof. The general formula of the compound is a formula (A), wherein R and R1 are respectively H, a C1-C20 fatty group, a C6-C30 aryl group, a C3-C30 cycloalkyl group, a C1-C20 perfluoro or polyfluoro substituted fatty group, a C6-C30 perfluoro or polyfluoro substituted aryl group, a C3-C30 perfluoro or polyfluoro substituted cycloalkyl group, a C1-C20 alkoxy group, a C6-C30 aryloxy group or a C3-C30 cycloalkyloxy group; x is halogen, a C1-C10 fatty group or a C3-C10 cycloalkyl group; z and M are each selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd or Ru; # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the fields of olefin coordination polymerization catalysts and polyolefins, and particularly relates to a bimetallic metallocene compound, a preparation method thereof, a polycyclic bimetallic metallocene catalyst, a catalyst system and an application thereof. Background Art

[0002] Since the industrial production of metallocene polyethylene was realized in 1991, it has been applied in various fields. The demand for metallocene polyethylene products has been growing rapidly. The mPE products circulating in the Chinese market are those produced by ExxonMobil Corporation and Dow Chemical Company. Daelim Corporation of South Korea introduced the technology of Dow Chemical Company, and the mPE products produced were put on the market with the lowest price and became the main source of mPE in China. The mPE produced by Mitsui Chemicals, Inc. of Japan has a relatively small market share due to its high price.

[0003] Chinese researchers such as Huang Qigu made unremitting efforts at the beginning of the emergence of metallocene catalysts and published articles in "Polymer Bulletin, 2010, 6, 1 - 33". After years of development, some achievements have been made in the basic theoretical research of metallocene catalysts.

[0004] CN108752509A discloses a metallocene catalyst, a preparation method thereof and an application.

[0005] Bayer AG of Germany [DE 19 850 898, 2000] used a 1-(9-fluorenyl)-1,2,3,6-tetrahydro-1,3,3-trimethylindenyl zirconium dichloride / MAO catalytic system to prepare ethylene / propylene / 5-ethylidene-2-norbornene copolymer (EPDM). The polymerization temperature was 20 - 80°C, the polymerization pressure was 0.3 - 3 MPa, the ethylene mass fraction of the copolymer was 0.4 - 0.9, the propylene mass fraction was 0.095 - 0.59, and the non-conjugated diene mass fraction was 0.005 - 0.12.

[0006] Uniroyal Chemical Company of the United States [WO 2 000 022 005, 2000] used a metallocene catalyst to synthesize EPDM with high molecular weight, narrow molecular weight distribution and low Tg. The polymerization temperature was 30 - 80°C, the polymerization pressure was 0.07 - 21 MPa, and the ethylene mass fraction of EPDM was 0.35 - 0.8.

[0007] Mitsui Petrochemical Industries, Ltd. of Japan [US5 218 071, 1993] used an ethyl-bridged metallocene / MAO catalytic system to copolymerize ethylene and α-olefins at normal pressure to 5 MPa using toluene as a solvent to synthesize a polyolefin elastomer Tafmer. The molar content of α-olefins in the molecular chain of the compound was as high as 9%, and the density of the product was low, being 0.85 - 0.92 g / cm3 , with a molecular weight distribution in the range of 1.2 - 4.0. The feature of this patent is that an organosilicon compound is added to the metallocene compound before polymerization.

[0008] Luft[J Mol Catal A,Chem,1995,102,1] used Me 2 Si(H 4 Ind) 2 ZrCl 2 / MAO to study the copolymerization of ethylene and propylene at 0.1 - 150 MPa and 120 - 220 °C. The molar content of propylene in the copolymer is low, and the density of the copolymer is relatively high, 0.940 - 0.946 g / cm 3 ; Luft[J Mol Catal A,Chem,1996,105,87] used Me 2 Si(H 4 Ind) 2 ZrCl 2 / MAO to compare the copolymerization of ethylene with propylene, 1-butene, 1-hexene, and 1-decene at 0.1 - 150 MPa and 120 - 220 °C, and found that the higher the carbon number of the α-olefin, the more difficult it is to copolymerize with ethylene. When ethylene copolymerizes with 1-butene, the ratio of the reactivity ratios is r e / r b = 53.45 / 0.02. When ethylene copolymerizes with 1-hexene, the ratio of the reactivity ratios is r e / r h = 62.70 / 0.02. When ethylene copolymerizes with 1-decene, the ratio of the reactivity ratios is r e / r d = 80.02 / 0.01.

[0009] Jin E-lin[WO2016 / 076509,KO,2016] reported a novel constrained geometry metallocene catalyst and used it for olefin polymerization. Among them, R 9 is H, an alkyl group with 1 - 20 carbon atoms, an alkenyl group with 2 - 20 carbon atoms, an alkoxy group with 1 - 20 carbon atoms, an aryl group with 6 - 20 carbon atoms, an aryloxyalkyl group with 7 - 20 carbon atoms, an alkylaryl group with 7 - 20 carbon atoms, or an aralkyl group with 7 - 20 carbon atoms.

[0010] Soares[Macromolecular Chemistry and Physics,2000,201,2195] used a supported metallocene catalyst Et(Ind) 2 ZrCl 2Copolymerize ethylene with 1-hexene under a pressure of 10 MPa, with a catalytic activity as high as 4341.7 kg P / mol Zr·h, and the molar content of 1-hexene in the copolymer is about 3%.

[0011] Soares [Colin Li Pi Shan, et al. Macromol. Chem. Phys. 2000, 201(16), 2195 - 2202] used a supported metallocene catalyst Et(Ind) 2 ZrCl 2 Copolymerize ethylene with 1-hexene under a pressure of 10 MPa, with a catalytic activity as high as 4341.7 kg PE / mol·Zr·h, and the molar content of 1-hexene in the copolymer is about 3%.

[0012] The above research results show that, despite using metallocene catalysts (except for those with a constrained geometry) and a high feed ratio of α-olefins, the copolymerization ability of α-olefins (C4 and above) with ethylene is low.

[0013] When Huang Qigu studied the influence of the co-ligand structure of metallocene catalysts on their catalytic activity and performance, it was found that introducing a phenoxy group with strong electron-withdrawing ability [Huang Qigu et al., CN103159803A, 2013; CN104693327A, 2015], a benzidine group [Huang Qigu et al., CN106046208A, 2016] into the metallocene compound structure can improve the thermal stability of metallocene catalysts.

[0014] Jing Wang, Qigu Huang, et al. studied the influence of the ortho- and para-substituents R of the N atom directly connected to the early transition metal atoms Ti (Zr, etc.) on the catalytic performance of the catalyst: compared with R being H or Me, when R is F, the catalyst has the best catalytic performance, high catalyst activity, high molecular weight of the copolymerized olefin, and high incorporation amount of the comonomer. Compared with R being Me (an electron-donating group), F is a strong electron-withdrawing group. When R is F, due to the strong electron-withdrawing ability of F, the electron cloud density around the transition metal atom decreases, and the catalytic activity of the catalyst increases. This result is contrary to the regularity reported in the literature. When R is F, F belongs to a Lewis base, and the transition metal atom belongs to a Lewis acid. Therefore, F can weaken the Lewis acidity of the transition metal atom, make the catalytic active center more stable, and it is difficult to occur β-H elimination reaction during olefin polymerization. Even at a relatively high polymerization temperature of 160 °C, high molecular weight polyolefins can still be obtained. The research group of Huang Qigu discovered a new regularity and proposed a new theory for regulating the active sites of olefin coordination polymerization catalysts: by introducing strong electron-withdrawing groups (including groups containing halogen, N, O, etc. atoms) into the structure / composition of the catalyst system (including ligands, co-ligands, third components, electron donors, etc.), through regulating the electronic effect and coordination environment around the transition metal atom, the thermal stability of the catalytic active center can be enhanced, the catalytic activity of the catalyst at a relatively high polymerization temperature can be improved; the ability of the active center to coordinate with, insert into, and chain-grow with olefin monomers can be enhanced to obtain a highly active catalyst system; the activation energy of the β-H chain transfer reaction during olefin polymerization can be increased, making the β-H elimination reaction difficult to occur, and high molecular weight polyolefins can be obtained. At the same time, it can provide a guiding ideology for the design and preparation of high-end catalysts and high-end polyolefins.

[0015] In summary, although there have been many reports on the copolymerization of α-olefins and ethylene using metallocene catalysts, it is still of great significance to further study and develop a metallocene catalyst based on how to improve the catalytic activity of the catalyst during olefin polymerization at high temperatures and improve the properties of polyolefins. Summary of the Invention

[0016] The object of the present invention is to overcome the problem of poor temperature resistance of the existing catalysts, and to provide a bimetallic metallocene compound, a preparation method thereof, a polycyclic bimetallic metallocene catalyst, a catalyst system and its application, and this catalyst system can efficiently catalyze olefin polymerization at high temperatures.

[0017] To achieve the above object, in the first aspect of the present invention, a bimetallic metallocene compound is provided, wherein the bimetallic metallocene compound has a general structural formula shown in formula (A):

[0018]

[0019] Among them, R and R 1 are the same or different and are each independently selected from H, C 1 -C 20 alkyl group, C 6 -C 30 aryl group, C 3 -C 30 cycloalkyl group, C 1 -C 20 perfluoro- or polyfluoro-substituted alkyl group, C 6 -C 30 perfluoro- or polyfluoro-substituted aryl group, C 3 -C 30 perfluoro- or polyfluoro-substituted cycloalkyl group, C 1 -C 20 alkoxy group, C 6 -C 30 aryloxy group and C 3 -C 30 cycloalkoxy group, one or more of them;

[0020] X is one or more of halogen, C 1 -C 10 alkyl group and C 3 -C 10 cycloalkyl group, one or more of them;

[0021] Z and M are each independently selected from one or more of Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd and Ru.

[0022] The second aspect of the present invention provides a method for preparing the aforementioned bimetallic metallocene compound, wherein the preparation method includes:

[0023] (1) In the presence of a first organic solvent, phthalaldehyde (ketone) is contacted with C 4 -C 15 amine to carry out a first reaction to obtain a compound represented by formula (D);

[0024]

[0025] (2) In the presence of a second organic solvent, the compound represented by formula (D) is contacted with indene to carry out a second reaction to obtain a compound represented by formula (E);

[0026]

[0027] (3) In the presence of a third organic solvent, the compound represented by formula (E) is contacted with a halogenated salt containing Z and M to carry out a third reaction to obtain a compound represented by formula (A);

[0028] wherein, R and R 1 are the same as those defined above.

[0029] The third aspect of the present invention provides a polycyclic bimetallocene catalyst, wherein the polycyclic bimetallocene catalyst is the bimetallocene compound as described above.

[0030] The fourth aspect of the present invention provides a catalyst system, wherein the catalyst system includes a main catalyst and a cocatalyst, and the main catalyst is the bimetallocene compound as described above.

[0031] The fifth aspect of the present invention provides an application of the catalyst system as described above in olefin polymerization.

[0032] Through the above technical solutions, by using the polycyclic bimetallocene catalyst containing the bimetallocene compound of the present invention as the main catalyst, the catalytic activity is high; in addition, the preparation method of the bimetallocene compound provided by the present invention has a simple process, low cost, low requirements for equipment, low energy consumption, and little environmental pollution. Detailed Embodiments

[0033] The endpoints and any values disclosed herein are not limited to the exact range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0034] As described above, the first aspect of the present invention provides a bimetallocene compound, wherein the bimetallocene compound has the general structural formula shown in formula (A):

[0035]

[0036] wherein, R and R 1 are the same or different and each independently selected from H, C 1 -C 20 aliphatic group, C 6 -C 30 aryl group, C 3 -C 30 cycloalkyl group, C 1 -C 20 perfluoro- or polyfluoro-substituted aliphatic group, C 6 -C 30 perfluoro- or polyfluoro-substituted aryl group, C 3 -C 30 perfluoro- or polyfluoro-substituted cycloalkyl group, C1 -C 20 alkoxy of, C 6 -C 30 aryloxy of and C 3 -C 30 one or more of cycloalkoxy of;

[0037] X is halogen, C 1 -C 10 aliphatic group of and C 3 -C 10 one or more of cycloalkyl group of;

[0038] Z and M are each independently selected from one or more of Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, and Ru.

[0039] Furthermore, the inventors of the present invention have found that: in the research and development of novel multifunctional polycyclic bimetallocene catalysts, the ligand is a multifunctional polycyclic organic compound containing a cyclopentadienyl group and an α-diimine group, which can bind to two identical or different transition metal atoms to form a novel multifunctional polycyclic bimetallocene catalyst. In the presence of a cocatalyst such as alkoxyaluminum or alkylaluminum, it can efficiently catalyze various copolymerizations such as ethylene homopolymerization, propylene homopolymerization, ethylene-α-olefin copolymerization, propylene-α-olefin copolymerization, ethylene-polar olefin monomer copolymerization, or propylene-polar olefin monomer copolymerization at a temperature of 0 - 150 °C to obtain high molecular weight polyolefins.

[0040] In the present invention, it should be noted that: for example, in the "perfluoro- or polyfluoro-substituted aliphatic group of C 1 -C 20 ", "perfluoro-substituted" means that all substituents are replaced by fluorine, and "polyfluoro-substituted" means that at least two substituents are replaced by fluorine.

[0041] According to the present invention, preferably, R and R 1 are each independently selected from one or more of H, phenyl, 2,6-difluorophenyl, 4-fluorophenyl, 2,4,6-trifluorophenyl, 2,6-dimethylphenyl, 4-methylphenyl, and 2,4,6-trimethylphenyl.

[0042] According to the present invention, preferably, X is Cl.

[0043] According to the present invention, preferably, Z and M are each independently selected from one or more of Ti, Zr, Hf, Fe, Ni, Pd, Co, and Ru.

[0044] According to the present invention, more preferably, the metallocene compound includes one or more of formulas (1) to (8);

[0045]

[0046]

[0047] The second aspect of the present invention provides a method for preparing the aforementioned bimetallic metallocene compound, wherein the preparation method includes:

[0048] (1) In the presence of a first organic solvent, phthalaldehyde (ketone) is contacted with an amine of C 4 -C 15 to carry out a first reaction to obtain a compound represented by formula (D);

[0049]

[0050] (2) In the presence of a second organic solvent, the compound represented by formula (D) is contacted with indene to carry out a second reaction to obtain a compound represented by formula (E);

[0051]

[0052] (3) In the presence of a third organic solvent, the compound represented by formula (E) is contacted with a halogenated salt containing Z and M to carry out a third reaction to obtain a compound represented by formula (A);

[0053] wherein, R and R 1 are the same as those defined above.

[0054] According to the present invention, the amine of C 4 -C 15 can preferably be one or more of aniline, 2,6-difluoroaniline, 2,4,6-trifluoroaniline, 4-fluoroaniline, 4-methylaniline, 2,4,6-trimethylaniline, and 2,6-dimethylaniline.

[0055] According to the present invention, in step (1), relative to 50-100 ml of the first organic solvent, the amount of phthalaldehyde (ketone) used is 0.01-3 mol, preferably 0.01-2 mol; the amount of the amine used is 0.01-4 mol, preferably 0.01-3 mol.

[0056] According to the present invention, in step (1), the conditions of the first reaction include: reacting at a temperature of -60°C to 120°C for 1-15 hours.

[0057] According to the present invention, in step (2), relative to 60-150 ml of the second organic solvent, the amount of the compound represented by formula (D) used is 0.5-20, preferably 0.5-10 g; the amount of indene used is 0.5-20 g, preferably 0.5-10 g.

[0058] According to the present invention, in step (2), the conditions for the second reaction include: reacting at -60°C to 50°C for 4 to 20 hours.

[0059] According to the present invention, in step (3), relative to 80 - 150 ml of the third organic solvent, the amount of the compound represented by formula (E) is 2 - 10 g, preferably 2 - 5 g; the amount of the halogenated salt containing Z and M is 1 - 8 times that of formula (E), preferably 1 - 5 times.

[0060] According to the present invention, in step (3), the conditions for the third reaction include: reacting at a temperature of -80°C to 80°C for 4 to 15 hours.

[0061] According to the present invention, the first organic solvent, the second organic solvent, and the third organic solvent are the same or different, and each is selected from one or more of saturated hydrocarbons of C 5 ~C 30 , alicyclic hydrocarbons of C 5 ~C 30 , aromatic hydrocarbons of C 6 ~C 30 , saturated heterocyclic hydrocarbons of C 3 ~C 20 , and paraffin oil; preferably, the first organic solvent, the second organic solvent, and the third organic solvent are the same or different, and each is selected from one or more of toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane, and hexadecane.

[0062] According to a preferred specific embodiment of the present invention, a method for preparing a bimetallic metallocene compound (metallocene catalyst), characterized by comprising the following steps:

[0063] (1) Add phthalaldehyde (ketone) to an organic solvent. Based on 1 mole of phthalaldehyde (ketone), add at least 2 moles of organic primary amine, and react at -60 to 120°C for 1 - 15 hours to obtain a compound conforming to general formula 2, wherein R or R 1 is selected from H, aliphatic groups of C 1 -C 20 , aryl groups of C 6 -C 30 , cycloalkyl groups of C 3 -C 30 , perfluoro or polyfluoro aliphatic groups of C 1 -C 20 , perfluoro or polyfluoro aryl groups of C 6 -C 30 , perfluoro or polyfluoro cycloalkyl groups of C 3 -C 30 , and perfluoro or polyfluoro cycloalkyl groups of C 1-C 20 alkoxy, C 6 -C 30 aryloxy or C 3 -C 30 cycloalkoxy;

[0064]

[0065] (2) Add 1 mole of indene at -60 °C to 10 °C and react for 4 - 20 hours to obtain a compound conforming to General Formula 3, wherein the R or R 1 is selected from H, C 1 -C 20 aliphatic group, C 6 -C 30 aryl group, C 3 -C 30 cycloalkyl group, C 1 -C 20 perfluoro or polyfluoro aliphatic group, C 6 -C 30 perfluoro or polyfluoro aryl group, C 3 -C 30 perfluoro or polyfluoro cycloalkyl group, C 1 -C 20 alkoxy, C 6 -C 30 aryloxy or C 3 -C 30 cycloalkoxy;

[0066]

[0067] (3) Add 2 moles of transition metal salt at -80 °C to 80 °C and react for 4 - 15 hours; filter, extract with organic solvent, concentrate, crystallize at -50 °C to 50 °C, filter, dry, with a yield greater than 50%, to obtain a multifunctional polycyclic metallocene catalyst conforming to General Formula 1;

[0068]

[0069] The third aspect of the present invention provides a polycyclic bimetallic metallocene catalyst, wherein the polycyclic bimetallic metallocene catalyst is the aforementioned bimetallic metallocene compound.

[0070] The fourth aspect of the present invention provides a catalyst system, wherein the catalyst system includes a main catalyst and a cocatalyst, and the main catalyst is the aforementioned bimetallic metallocene compound.

[0071] According to the present invention, the molar ratio of the content of the main catalyst to the cocatalyst is 1:(5 - 2000).

[0072] According to the present invention, the cocatalyst is an alkyl aluminum and / or an alkoxy aluminum; preferably, the cocatalyst is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-tert-butyl aluminum, trioctylaluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, sesquiethyl aluminum chloride, modified or unmodified MAO.

[0073] The fifth aspect of the present invention provides an application of the aforementioned catalyst system in olefin polymerization.

[0074] According to the present invention, the application includes: one or more catalysts selected from ethylene polymerization, propylene polymerization, and copolymerization of ethylene (or propylene) and α-olefin, wherein the α-olefin is selected from C 3 ~C 20 Olefins, preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, norbornene, ethylidene norbornene or their derivatives, halogenated olefins, hydroxy olefins, carboxyl olefins, ester olefins or blends thereof.

[0075] According to the present invention, the olefin polymerization conditions include: the olefin polymerization conditions are: the polymerization temperature is 0-150°C, the hydrogen partial pressure is 0-0.2MPa, the ethylene partial pressure is 0.1-10MPa, the propylene partial pressure is 0.5-10MPa, the reaction time is 0.1-4h, and the molar ratio of the multifunctional polycyclic metallocene catalyst to the co-catalyst is 1:(5-2000).

[0076] The present invention will be described in detail below through examples.

[0077] Example 1

[0078] Multifunctional polycyclic bimetallic metallocene catalyst (1) and preparation method and application:

[0079]

[0080] (1) Take 50 ml of toluene and weigh 10.0 g (0.075 mol) of o-phthalaldehyde in a 300 ml schlenk bottle, then add 13.9 g (0.15 mol) of aniline, stir at -10°C, react for 8 hours, remove the solvent in vacuo, add 100 ml of n-hexane to the remaining solid, dissolve and filter, recrystallize the filtrate, and obtain 19.3 g of o-phthalaldehyde phenylene imide solid, with a yield of 91.9%.

[0081] 1 H NMR (400MHz, CDCl 3: 7.26 ppm): δ = 8.75 (d, 2H, CH); 7.73 (d, 2H, Ph), 7.53 (d, 2H, Ph); 7.49 - 7.41 (m, 8H, Ph); 7.09 (d, 2H, Ph). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 165.25, 149.32, 135.41, 129.42, 129.09, 128.74, 126.49, 121.26. Anal. Calcd. (%) for C 20 H 16 N 2 (284): C, 84.48; H, 5.67; N, 9.85; found (experimental test): C, 84.50; H, 5.66; N, 9.84; ESI-MS m / z calculated for (theoretical calculation) [M + H] + . C 20 H 16 N 2 : 284.1, found, 285.1。

[0082] (2) Measure 60 ml of toluene, weigh 19.3 g (0.068 mol) of phthalaldehyde phenylenediamine in a 300 ml schlenk flask, add an equimolar amount of indene, 7.88 g, at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash with 300 ml of n-hexane three times, and dry under vacuum to obtain 24.6 g of phthalaldehyde phenylenediamine indene, with a yield of 90.4%.

[0083] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.35 (d, 2H, CH), 7.36 - 7.29 (m, 4H, Ph), 7.18 - 7.09 (m, 6H, Ph), 6.11 - 5.98 (m, 4H, Ph), 5.92 - 5.87 (m, 1H, Cp), 5.68 (d, 1H, Cp), 3.06 - 2.95 (m, 2H, Cp), 2.77 (d, 1H, Ph), 2.72 (t, 1H, Ph), 2.37 (d, 1H, Ph), 2.24 - 2.10 (m, 2H, Ph), 1.93 (d, 1H, Ph); 13 C NMR (125 MHz, CDCl 3: 77.2 ppm): δ = 158.11, 158.05, 145.36, 145.35, 143.53, 143.39, 132.61, 131.91, 129.83, 127.68, 127.59, 127.38, 126.98, 126.54, 126.51, 122.27, 122.25, 122.23, 47.47, 41.20, 40.88, 39.61, 38.39, 37.45, 34.38; Anal.Calcd.(%) for C 29 H 26 N 2 (402): C, 86.53; H, 6.51; N, 6.96; found: C, 86.55; H, 6.50; N, 6.95; ESI-MS m / z calculated for [M+H] + .C 29 H 26 N 2 : 402.2, found, 403.2。

[0084] (3) Catalyst synthesis

[0085] Measure 80 ml of toluene, weigh 5 g of phthalaldehyde phenylenediamine indene ligand into a 300 ml schlenk flask, and add 3 times the amount of ligand of TiCl 4 at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 7.23 g of multifunctional polycyclic bimetallic metallocene catalyst (1) with a yield of 91.5%.

[0086] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.70 (d, 2H), 7.37 - 7.28 (m, 4H), 7.10 (t, 2H), 6.96 - 6.89 (m, 4H), 6.22 (d, 2H), 6.13 (d, 1H), 5.86 - 5.75 (m, 3H), 5.29 (d, 1H), 3.04 - 2.93 (m, 3H), 2.71 - 2.57 (m, 2H), 2.08 (m, 1H). Anal.Calcd.(%) for C 29 H 25 N 2 Cl 5 Ti 2(671.9): C, 51.64; H, 3.74; Cl, 26.28; N, 4.15; Ti, 14.19; found: C, 51.57; H, 3.87; Cl, 26.25; N, 4.14; Ti, 14.17.

[0087] (4) Ethylene polymerization:

[0088] Under anhydrous and anaerobic conditions, after the 2-L stainless steel autoclave was fully replaced with nitrogen, 1 L of toluene was added to the reaction kettle, 8 mg of the multifunctional polycyclic bimetallic metallocene catalyst (1), 2.5 mL of MAO solution (10 wt%), 0.1 L of hydrogen was charged, ethylene was charged to a pressure of 0.7 MPa, stirred, heated to 65 °C and reacted for 30 min, and 167 g of the polymerization product was collected.

[0089] (5) Ethylene copolymerization:

[0090] Under anhydrous and anaerobic conditions, after the 2-L stainless steel autoclave was fully replaced with nitrogen, 1 L of toluene was added to the reaction kettle, 5 mg of the multifunctional polycyclic bimetallic metallocene catalyst (1), 2 mL of MAO solution (10 wt%), 90 mL of 1-hexene, 0.05 L of hydrogen was charged, ethylene was charged to a pressure of 0.8 MPa, stirred, heated to 70 °C and reacted for 20 min, and 158 g of the polymerization product was collected.

[0091] Example 2

[0092] Multifunctional polycyclic bimetallic metallocene catalyst (2) and its preparation method and application:

[0093]

[0094] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde in a 300-ml schlenk flask, then add 19.4 g (0.15 mol) of 2,6-difluoroaniline, stir at -10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 24.4 g of phthalaldehyde-2,6-difluorobenzene diimine solid, yield: 91.5%.

[0095] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.78 (d, 2H, CH), 7.72 - 7.67 (m, 2H, Ph), 7.55 (d, 2H, Ph), 7.45 (t, 2H, Ph), 7.21 (t, 4H, Ph). 13 C NMR (125 MHz, CDCl 3: 77.2 ppm): δ = 162.68, 156.33, 137.56, 130.94, 129.05, 125.37, 113.61. Anal. Calcd. (%) for C 20 H 12 F 4 N 2 (356): C, 67.42; H, 3.39; F, 21.33; N, 7.86; found: C, 67.40; H, 3.42; F, 21.31; N, 7.87; ESI-MS m / z calculated for [M+H] + . C 20 H 12 F 4 N 2 : 356.1, found, 357.1。

[0096] (2) Measure 60 ml of toluene, weigh 24.4 g (0.068 mol) of o-phthalaldehyde-2,6-difluorobenzene diimine into a 300 ml Schlenk flask, add an equimolar amount of indene (7.88 g) at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 24.6 g of o-phthalaldehyde-2,6-difluorobenzene diimine indene, with a yield of 90.4%.

[0097] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.45 (d, 1H, CH), 8.32 (d, 1H, CH), 7.48 (t, 2H, Ph), 7.27 - 7.18 (m, 4H, Ph), 6.30 - 6.26 (m, 1H, Ph), 6.17 - 6.11 (m, 1H, Ph), 6.12 - 5.97 (m, 2H, Ph), 5.89 (d, 1H, Cp), 5.71 (d, 1H, Cp), 3.06 - 2.97 (m, 2H, Ph), 2.81 (d, 1H, Cp), 2.70 (t, 1H), 2.35 (d, 1H, Ph), 2.24 - 2.11 (m, 2H, Ph), 1.95 - 1.85 (m, 1H, Cp). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 159.28, 143.02, 132.14, 131.77, 130.55, 129.24, 126.96, 125.42, 113.67, 47.54, 41.26, 40.99, 39.63, 38.47, 37.45, 34.41. Anal. Calcd. (%) for C29 H 22 F 4 N 2 (474): C, 73.41; H, 4.67; F, 16.02; N, 5.90; found: C, 73.43; H, 4.66; F, 16.01; N, 5.90; ESI-MS m / z calculated for [M+H] + .C 29 H 22 F 4 N 2 : 474.1, found, 475.1。

[0098] (3) Catalyst synthesis

[0099] Measure 80 ml of toluene, weigh 5 g of o-phthalaldehyde-2,6-difluorobenzene diimine indene ligand into a 300 ml schlenk flask, and add 3 times the ligand amount of TiCl at -30 °C 4 , stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 7.19 multifunctional polycyclic bimetallic metallocene catalyst (2) with a yield of 91.5%.

[0100] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.73 (d, 2H), 7.63 - 7.55 (m, 4H), 7.52 - 7.43 (m, 2H), 6.22 (d, 2H), 6.15 (d, 1H), 5.88 - 5.81 (m, 3H), 5.29 (d, 1H), 3.04 - 2.95 (m, 3H), 2.71 - 2.57 (m, 2H), 2.09 (m, 1H). Anal. Calcd. (%) for C 29 H 21 Cl 5 F 4 N 2 Ti 2 (743.9): C, 46.66; H, 2.84; Cl, 23.74; F, 10.18; N, 3.75; Ti, 12.82; found: C, 46.68; H, 2.82; Cl, 23.72; F, 10.19; N, 3.76; Ti, 12.82。

[0101] (4) Ethylene polymerization:

[0102] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-L stainless steel autoclave with nitrogen, 1 L of toluene was added to the autoclave, 8 mg of a multifunctional polycyclic bimetallic metallocene catalyst (2), 3.5 mL of an MAO solution (10 wt%), 0.1 L of hydrogen was charged, ethylene was charged to a pressure of 0.9 MPa, stirred, heated to 65 °C and reacted for 30 min, and 239 g of the polymerization product was collected.

[0103] (5) Ethylene copolymerization:

[0104] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-L stainless steel autoclave with nitrogen, 1 L of toluene was added to the autoclave, 5 mg of a multifunctional polycyclic bimetallic metallocene catalyst (2), 3 mL of an MAO solution (10 wt%), 30 mL of 1-decene, 0.05 L of hydrogen was charged, ethylene was charged to a pressure of 0.85 MPa, stirred, heated to 70 °C and reacted for 25 min, and 231 g of the polymerization product was collected.

[0105] Example 3

[0106] Multifunctional polycyclic bimetallic metallocene catalyst (3) and its preparation method and application:

[0107]

[0108] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde in a 300-ml schlenk flask, then add 22.1 g (0.15 mol) of 2,4,6-trifluoroaniline, stir at -10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 26.7 g of phthalaldehyde-2,4,6-trifluorobenzene diimine solid, yield: 90.8%.

[0109] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.79 (d, 2H, CH), 7.71 (d, 2H, Ph), 7.50 (d, 2H, Ph), 6.87 (d, 4H, Ph); 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 164.08, 158.71, 153.47, 137.51, 128.92, 128.97, 127.69, 102.74. Anal. Calcd. (%) for C 20 H 10 F 6 N 2(392): C, 61.23; H, 2.57; found: C, 61.21; H, 2.55; ESI-MS m / z calculated for [M+H] + .C 20 H 10 F 6 N 2 : 392.1, found, 393.1。

[0110] (2) Measure 60 ml of toluene, weigh 26.7 g (0.068 mol) of phthalaldehyde-2,4,6-trifluorobenzene diimine into a 300 ml Schlenk flask, add an equimolar amount of indene, 7.89 g, at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 31.2 g of phthalaldehyde-2,4,6-trifluorobenzene diimine indene, with a yield of 90.4%.

[0111] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.46 (d, 1H, CH), 8.29 (d, 1H, CH), 6.85 (d, 4H), 6.26 - 6.17 (m, 1H, Cp), 6.15 - 6.07 (m, 1H, Ph), 6.11 - 6.01 (m, 2H, Ph), 5.88 (d, 1H, Cp), 5.67 (d, 1H, Cp), 3.07 - 2.97 (m, 2H, Ph), 2.81 (d, 1H, Ph), 2.73 (t, 1H, Ph), 2.39 (d, 1H, Ph), 2.23 - 2.10 (m, 2H, Ph), 1.96 - 1.87 (m, 1H, Cp). 13 C NMR (125 MHz, CDCl 3 : 7.26 ppm): δ = 163.38, 158.6, 153.71, 143.02, 132.14, 129.24, 127.5, 126.8, 125.29, 102.91, 47.54, 41.26, 40.99, 39.63, 38.47, 37.45, 34.41; Anal. Calcd. (%) for C 29 H 20 F 6 N 2 (510): C, 68.23; H, 3.95; F, 22.33; N, 5.49; found: C, 68.25; H, 3.93; F, 22.34; N, 5.48; ESI-MS m / z calculated for [M+H] + .C29 H 20 F 6 N 2 : 510.1, found, 511.1。

[0112] (3) Catalyst synthesis

[0113] Measure 80 ml of toluene, weigh 5 g of o-phthalaldehyde-2,4,6-trifluorobenzene diimine indene ligand into a 300 ml schlenk flask, and add 3 times the amount of TiCl as the ligand at -30 °C 4 , stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 7.07 multifunctional polycyclic bimetallic metallocene catalyst (3) with a yield of 91.2%.

[0114] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.73 (d, 2H), 6.81 (t, 4H), 6.21 (d, 2H), 6.14 (d, 1H), 5.84 - 5.76 (m, 3H), 4.17 (d, 1H), 3.06 - 2.94 (m, 3H), 2.73 - 2.59 (m, 2H), 2.57 - 2.45 (m, 1H). Anal. Calcd. (%) for C 29 H 19 Cl 5 F 6 N 2 TiNi(789.8): C, 43.91; H, 2.41; Cl, 22.34; F, 14.37; N, 3.53; Ni, 7.40; Ti, 6.03; found: C, 43.93; H, 2.40; Cl, 22.33; F, 14.38; N, 3.52; Ni, 7.40; Ti, 6.03.

[0115] (4) Ethylene polymerization:

[0116] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-liter stainless steel autoclave with nitrogen, add 1 L of toluene to the reaction kettle, add 9 mg of multifunctional polycyclic bimetallic metallocene catalyst (3), 3.5 mL of MAO solution (10 wt%), charge 0.05 L of hydrogen, charge ethylene to a pressure of 0.8 MPa, stir, heat up to 65 °C and react for 20 min, and collect 233 g of the polymerization product.

[0117] (5) Ethylene copolymerization:

[0118] Under anhydrous and anaerobic conditions, after the 2-L stainless steel autoclave was fully replaced with nitrogen, 1 L of toluene, 5 mg of the multifunctional polycyclic bimetallic metallocene catalyst (3), 2.5 mL (10 wt%) of the MAO solution, and 90 mL of 1-octene were added to the autoclave. 0.05 L of hydrogen was charged, and ethylene was charged until the pressure reached 0.8 MPa. The mixture was stirred and heated to 70 °C for reaction for 20 min, and 246 g of the polymerization product was collected.

[0119] Example 4

[0120] Multifunctional polycyclic bimetallic metallocene catalyst (4) and its preparation method and application:

[0121]

[0122] (1) Measure 50 mL of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde into a 300-mL schlenk flask, then add 16.6 g (0.15 mol) of 4-fluoroaniline. Stir at -10 °C for 8 h, remove the solvent under vacuum. Add 100 mL of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 21.6 g of phthalaldehyde-4-fluorophenyl diimine solid, with a yield of 90.1%.

[0123] 1 H NMR (400 MHz, CDCl 3 :7.26 ppm): δ = 8.75 (d, 2H, CH), 7.73 (d, 2H, Ph), 7.50 (d, 2H, Ph), 7.27 - 7.20 (m, 4H, Ph), 7.16 - 7.08 (m, 4H, Ph). 13 C NMR (125 MHz, CDCl 3 :77.2 ppm): δ = 166.61, 159.16, 145.36, 135.40, 129.16, 128.73, 123.53, 116.37. Anal. Calcd. (%) for C 20 H 14 F 2 N 2 (320): C, 74.99; H, 4.41; found: C, 74.97; H, 4.39; ESI-MS m / z calculated for [M + H] + .C 20 H 14 F 2 N 2 : 320.1, found, 321.1.

[0124] (2) Measure 60 mL of toluene, weigh 21.6 g (0.068 mol) of phthalaldehyde 4-fluorobenzenediimine into a 300 mL Schlenk flask, add 7.88 g of indene in equimolar amount at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash with 300 mL of n-hexane three times, and dry under vacuum to obtain 24.6 of phthalaldehyde-4-fluorobenzenediimine indene, with a yield of 90.7%.

[0125] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.39 (d, 1H, CH), 8.31 (d, 1H, CH), 7.29 - 7.19 (m, 4H, Ph), 7.16 - 7.06 (m, 4H, Ph), 6.11 - 5.98 (m, 3H, Ph), 6.00 - 5.92 (m, 1H, Ph), 5.88 (d, 1H, Cp), 5.69 (d, 1H, Cp), 3.06 - 2.96 (m, 2H, Ph), 2.77 (d, 1H, Cp), 2.70 (t, 1H), 2.38 (d, 1H), 2.24 - 2.11 (m, 2H), 1.92 (d, 1H, Cp). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 164.47, 156.06, 143.61, 143.45, 143.61, 140.31, 132.15, 131.77, 127.60, 127.38, 127.04, 124.57, 123.75, 118.29, 114.85, 47.65, 41.29, 40.99, 39.64, 38.46, 37.45, 34.36. Anal. Calcd. (%) for C 29 H 24 F 2 N 2 (438): C, 79.43; H, 5.52; F, 8.66; N, 6.39; found: C, 79.45; H, 5.50; F, 8.67; N, 6.38; ESI-MS m / z calculated for [M + H] + .C 29 H 24 F 2 N 2 : 438.1, found, 439.1.

[0126] (3) Catalyst synthesis

[0127] Measure 80 mL of toluene, weigh 5 g of o-phthalaldehyde-4-fluorobenzene diimide indene ligand into a 300 mL Schlenk flask, and add 3 times the amount of ligand of TiCl at -30 °C. 4 , stir, react for 6 hours, remove the solvent under vacuum, wash with 300 mL of n-hexane 3 times, and dry under vacuum to obtain 8.37 g of multifunctional polycyclic bimetallic metallocene catalyst (4) with a yield of 90.6%.

[0128] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.73 (d, 2H), 7.26 - 7.15 (m, 8H), 6.24 (d, 2H), 6.15 (d, 1H), 5.87 - 5.75 (m, 3H), 4.15 (d, 1H), 3.05 - 2.94 (m, 3H), 2.71 - 2.56 (m, 2H), 2.06 (m, 1H). Anal. Calcd. (%) for C 29 H 23 F 2 N 2 Cl 5 ZrPd(807.8): C, 42.87; H, 2.85; Cl, 21.82; F, 4.68; N, 3.45; Pd, 13.10; Zr, 11.23; found: C, 42.89; H, 2.84; Cl, 21.81; F, 4.69; N, 3.44; Pd, 13.10; Zr, 11.23.

[0129] (4) Ethylene polymerization:

[0130] Under anhydrous and anaerobic conditions, after the 2 L stainless steel autoclave is fully replaced with nitrogen, add 1 L of toluene to the reaction kettle, add 8 mg of multifunctional polycyclic bimetallic metallocene catalyst (4), 2.5 mL of MAO solution (10 wt%), charge 0.1 L of hydrogen, charge ethylene to a pressure of 0.7 MPa, stir, heat up to 75 °C and react for 15 min, and collect 217 g of the polymerization product.

[0131] (5) Ethylene copolymerization:

[0132] Under anhydrous and anaerobic conditions, after the 2 L stainless steel autoclave is fully replaced with nitrogen, add 1 L of toluene to the reaction kettle, add 5 mg of multifunctional polycyclic bimetallic metallocene catalyst (4), 2 mL of MAO solution (10 wt%), 80 mL of 1-butene, charge 0.05 L of hydrogen, charge ethylene to a pressure of 0.8 MPa, stir, heat up to 60 °C and react for 20 min, and collect 203 g of the polymerization product.

[0133] Example 5

[0134] Multifunctional polycyclic bimetallic metallocene catalyst (5) and preparation method and application thereof:

[0135]

[0136] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde into a 300 ml schlenk flask, then add 16.1 g (0.15 mol) of 4-methylaniline, stir at -10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 21.2 g of phthalaldehyde-4-methylphenyl diimine solid, yield: 90.8%.

[0137] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.73 (d, 2H, CH), 7.78 - 7.70 (m, 2H, Ph), 7.52 (d, 2H, Ph), 7.22 - 7.13 (m, 9H, Ph), 2.35 (s, 5H, CH 3 ); 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 164.97, 146.47, 136.88, 135.36, 130.00, 129.18, 128.88, 121.66, 21.17. Anal. Calcd. (%) for C 22 H 20 N 2 (312): C, 84.58; H, 6.45; N, 8.97; found: C, 84.59; H, 6.44; N, 8.97; ESI-MS m / z calculated for [M + H] + .C 22 H 20 N 2 : 312.1, found, 313.1.

[0138] (2) Measure 60 ml of toluene, weigh 21.2 g (0.068 mol) of phthalaldehyde-4-methylphenyl diimine into a 300 ml schlenk flask, add an equimolar amount of indene 7.88 g at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 26.3 g of phthalaldehyde-4-methylphenyl diimine indene, yield 90.4%.

[0139] 1 H NMR (400 MHz, CDCl3 : 7.26 ppm): δ = 8.43 (d, 1H, CH), 8.32 (d, 1H, CH), 7.24 - 7.19 (m, 4H, Ph), 7.13 - 7.04 (m, 4H, Ph), 6.12 - 5.98 (m, 3H, Ph), 5.98 - 5.83 (m, 2H, Cp), 5.68 (d, 1H, Cp), 3.06 - 2.96 (m, 2H, Ph), 2.74 (d, 1H, Ph), 2.74 - 2.65 (m, 1H, Ph), 2.38 (d, 1H, Ph), 2.34 (s, 6H, CH 3 ), 2.25 - 2.10 (m, 2H, Ph), 1.93 (d, 1H, Cp). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 157.75, 157.70, 143.61, 143.45, 142.95, 142.94, 136.93, 136.90, 132.15, 131.77, 130.50, 127.65, 127.55, 127.38, 127.04, 122.82, 47.65, 41.29, 40.99, 39.64, 38.46, 37.45, 34.37, 21.19. Anal. Calcd. (%) for C 31 H 30 N 2 (430): C, 86.47; H, 7.02; N, 6.51; found: C, 86.49; H, 7.01; N, 6.50; ESI - MS m / z calculated for [M + H] + . C 31 H 30 N 2 : 430.2, found, 431.2。

[0140] (3) Catalyst synthesis

[0141] Measure 80 ml of toluene, weigh 5 g of o - phthalaldehyde - 4 - methylphenylenediamine indene ligand into a 300 ml schlenk flask, add 3 times the amount of ligand of TiCl 4 at - 30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n - hexane, and dry under vacuum to obtain 9.48 multi - functional polycyclic bimetallic metallocene catalyst (5) with a yield of 91.4%.

[0142] 1 H NMR (400 MHz, CDCl 3: 7.26 ppm): δ = 8.29 (d, 2H), 7.25 (d, 5H), 7.10 - 7.03 (m, 4H), 6.70 - 6.61 (m, 2H), 6.17 - 6.07 (m, 2H), 5.90 - 5.80 (m, 2H), 4.20 (d, 1H), 3.00 (d, 1H), 2.97 - 2.87 (m, 3H), 2.74 (d, 1H), 2.48 (q, 1H), 2.39 - 2.34 (m, 5H). Anal. Calcd. (%) for C 31 H 29 N 2 Cl 5 HfPd(889.9): C, 41.77; H, 3.27; Cl, 19.87; Hf, 20.02; N, 3.14; Pd, 11.93.

[0143] (4) Ethylene polymerization:

[0144] Under anhydrous and anaerobic conditions, after a 2 - liter stainless - steel autoclave was fully replaced with nitrogen, 1 L of toluene was added to the autoclave, 8 mg of the multifunctional polycyclic bimetallic metallocene catalyst (5), 2.5 mL of MAO solution (10 wt%), 0.15 L of hydrogen was charged, ethylene was charged to a pressure of 0.9 MPa, stirred, heated to 70 °C and reacted for 30 min, and 217 g of the polymerization product was collected.

[0145] (5) Ethylene copolymerization:

[0146] Under anhydrous and anaerobic conditions, after a 2 - liter stainless - steel autoclave was fully replaced with nitrogen, 1 L of toluene was added to the autoclave, 5 mg of the multifunctional polycyclic bimetallic metallocene catalyst (5), 2 mL of MAO solution (10 wt%), 60 g of liquid propylene, 0.05 L of hydrogen was charged, ethylene was charged to a pressure of 0.8 MPa, stirred, heated to 70 °C and reacted for 20 min, and 228 g of the polymerization product was collected.

[0147] Example 6

[0148] Multifunctional polycyclic bimetallic metallocene catalyst (6) and its preparation method and application:

[0149]

[0150] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde into a 300 - ml schlenk flask, then add 16.6 g (0.15 mol) of 4 - fluoroaniline, stir at - 10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n - hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 21.6 g of phthalaldehyde - 4 - fluorophenyl diimine solid, yield: 90.1%.

[0151] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.75 (d, 2H, CH), 7.73 (d, 2H, Ph), 7.50 (d, 2H, Ph), 7.27 - 7.20 (m, 4H, Ph), 7.16 - 7.08 (m, 4H, Ph). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 166.61, 159.16, 145.36, 135.40, 129.16, 128.73, 123.53, 116.37. Anal. Calcd. (%) for C 20 H 14 F 2 N 2 (320): C, 74.99; H, 4.41; found: C, 74.97; H, 4.39; ESI-MS m / z calculated for [M + H] + .C 20 H 14 F 2 N 2 : 320.1, found, 321.1。

[0152] (2) Measure 60 ml of toluene, weigh 21.6 g (0.068 mol) of phthalaldehyde - 4 - fluorobenzene diimine into a 300 - ml Schlenk flask, add an equimolar amount of indene, 7.88 g, at - 30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n - hexane, and dry under vacuum to obtain 24.6 g of phthalaldehyde - 4 - fluorobenzene diimine indene, with a yield of 90.7%.

[0153] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.39 (d, 1H, CH), 8.31 (d, 1H, CH), 7.29 - 7.19 (m, 4H, Ph), 7.16 - 7.06 (m, 4H, Ph), 6.11 - 5.98 (m, 3H, Ph), 6.00 - 5.92 (m, 1H, Ph), 5.88 (d, 1H, Cp), 5.69 (d, 1H, Cp), 3.06 - 2.96 (m, 2H, Ph), 2.77 (d, 1H, Cp), 2.70 (t, 1H), 2.38 (d, 1H), 2.24 - 2.11 (m, 2H), 1.92 (d, 1H, Cp). 13 C NMR (125 MHz, CDCl3 : 77.2 ppm): δ = 164.47, 156.06, 143.61, 143.45, 143.61, 140.31, 132.15, 131.77, 127.60, 127.38, 127.04, 124.57, 123.75, 118.29, 114.85, 47.65, 41.29, 40.99, 39.64, 38.46, 37.45, 34.36. Anal. Calcd. (%) for C 29 H 24 F 2 N 2 (438): C, 79.43; H, 5.52; F, 8.66; N, 6.39; found: C, 79.45; H, 5.50; F, 8.67; N, 6.38; ESI-MS m / z calculated for [M+H] + . C 29 H 24 F 2 N 2 : 438.1, found, 439.1。

[0154] (3) Catalyst synthesis

[0155] Measure 80 ml of toluene, weigh 5 g of phthalaldehyde-4-fluorobenzene diimine indene ligand into a 300 ml schlenk flask, and add 3 times the amount of ligand of TiCl at -30 °C 4 , stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 7.23 multifunctional polycyclic bimetallic metallocene catalyst (6) with a yield of 91.5%. 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.70 (d, 2H, CH), 7.24 - 7.14 (m, 8H, Ph), 6.22 (d, 2H, Ph), 6.13 (d, 1H, Cp), 5.86 - 5.75 (m, 3H), 5.29 (d, 1H), 3.04 - 2.93 (m, 3H), 2.71 - 2.57 (m, 2H), 2.08 (m, 1H, Ph). Anal. Calcd. (%) for C 29 H 23 N 2 F 2 Cl 5TiFe(715.9): C, 48.48; H, 3.23; Cl, 24.67; F, 5.29; Fe, 7.77; N, 3.90; Ti, 6.66; found: C, 48.50; H, 3.21; Cl, 24.66; F, 5.30; Fe, 7.77; N, 3.90; Ti, 6.66.

[0156] (4) Ethylene polymerization:

[0157] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-liter stainless steel autoclave with nitrogen, 1 L of heptane was added to the autoclave, 8 mg of the multifunctional polycyclic bimetallic metallocene catalyst (6), 2.5 mL (10 wt%) of the MAO solution, 0.1 L of hydrogen was charged, ethylene was charged to a pressure of 0.7 MPa, stirred, heated to 65 °C and reacted for 35 min, and 217 g of the polymerization product was collected.

[0158] (5) Ethylene copolymerization:

[0159] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-liter stainless steel autoclave with nitrogen, 1 L of toluene was added to the autoclave, 5 mg of the multifunctional polycyclic bimetallic metallocene catalyst (6), 2 mL (10 wt%) of the MAO solution, 15 g of 4-methyl-1-pentene, 0.05 L of hydrogen was charged, ethylene was charged to a pressure of 0.8 MPa, stirred, heated to 60 °C and reacted for 40 min, and 143 g of the polymerization product was collected.

[0160] Example 7

[0161] Multifunctional polycyclic bimetallic metallocene catalyst (7) and its preparation method and application:

[0162]

[0163] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde into a 300 ml schlenk flask, then add 20.3 g (0.15 mol) of 2,4,6-trimethylaniline, stir at -10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 24.9 g of phthalaldehyde-2,4,6-trimethylphenyl diimine solid, yield: 90.2%. 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.63 (d, 2H, CH), 7.74 (d, 2H, Ph), 7.52 (d, 2H, Ph), 7.15 (s, 4H, Ph), 2.43 (s, 12H, CH 3 ), 2.27 (s, 6H, CH 3 ).13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 163.59, 150.74, 136.51, 133.86, 129.19, 128.93, 128.77, 20.77, 18.44. Anal. Calcd. (%) for C 26 H 28 N 2 (368): C, 84.74; H, 7.66; N, 7.60; found: C, 84.76; H, 7.64; N, 7.60; ESI-MS m / z calculated for [M+H] + .C 26 H 28 N 2 : 368.2, found, 369.2。

[0164] (2) Measure 60 ml of toluene, weigh 25.0 g (0.068 mol) of phthalaldehyde-2,4,6-trimethylbenzenediamine into a 300 ml Schlenk flask, add an equimolar amount of indene, 7.88 g, at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 29.9 g of phthalaldehyde-2,4,6-trimethylbenzenediamine indene, with a yield of 90.4%.

[0165] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.27 (d, 1H, CH), 8.22 (d, 1H, CH), 7.17 (s, 3H, Ph), 6.11 - 6.00 (m, 3H, Ph), 5.95 - 5.86 (m, 2H, Cp), 5.69 (d, 1H, Cp), 3.06 - 2.96 (m, 2H, Ph), 2.82 (d, 1H, Ph), 2.71 (t, 1H, Ph), 2.44 (s, 6H, CH 3 ), 2.38 (s, 6H, CH 3 ), 2.26 (s, 6H, CH 3 ), 2.23 - 2.10 (m, 2H, Cp), 1.91 (d, 1H, Cp). 13 C NMR (125 MHz, CDCl 3: 77.2 ppm): δ = 157.97, 150.36, 143.10, 133.86, 132.14, 130.06, 127.56, 47.54, 41.26, 39.63, 38.47, 37.45, 34.41, 20.77, 18.48. Anal. Calcd. (%) for C 35 H 38 N 2 (486): C, 86.37; H, 7.87; N, 5.76; found: C, 86.39; H, 7.85; N, 5.76; ESI-MS m / z calculated for [M+H] + . C 35 H 38 N 2 : 486.3, found, 487.3。

[0166] (3) Catalyst synthesis

[0167] Measure 80 ml of toluene, weigh 5 g of o-phthalaldehyde-2,4,6-trimethylbenzenediimine indene ligand into a 300 ml schlenk flask, and add 3 times the amount of ligand of TiCl 4 at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 7.21 g of a multifunctional polycyclic bimetallic metallocene catalyst (7) with a yield of 91.5%. 1 HNMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.66 (d, 2H, CH), 7.50 (s, 4H, Ph), 6.22 (d, 2H), 6.12 (d, 1H, Cp), 5.86 - 5.75 (m, 3H, Cp), 5.29 (d, 1H, Cp), 3.06 - 2.93 (m, 3H), 2.72 - 2.58 (m, 2H), 2.53 (m, 1H, Ph), 2.47 (s, 12H, CH 3 ), 2.28 (s, 6H, CH 3 ). Anal. Calcd. (%) for C 35 H 37 Cl 5 N 2 NiTi (766.1): C, 54.63; H, 4.85; Cl, 23.03; N, 3.64; Ni, 7.63; Ti, 6.22; found: C, 54.65; H, 4.83; Cl, 23.02; N, 3.65; Ni, 7.63; Ti, 6.22。

[0168] (4) Ethylene polymerization:

[0169] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-L stainless steel autoclave with nitrogen, 1 L of toluene was added to the autoclave, 10 mg of the multifunctional polycyclic bimetallic metallocene catalyst (7), 5.5 mL of MAO solution (10 wt%), 0.1 L of hydrogen was charged, ethylene was charged to a pressure of 0.8 MPa, stirred, heated to 65 °C and reacted for 30 min, and 215 g of the polymerization product was collected.

[0170] (5) Ethylene copolymerization:

[0171] Under anhydrous and anaerobic conditions, after thoroughly displacing a 2-L stainless steel autoclave with nitrogen, 1 L of toluene was added to the autoclave, 5 mg of the multifunctional polycyclic bimetallic metallocene catalyst (7), 2 mL of MAO solution (10 wt%), 20 mL of styrene, 0.05 L of hydrogen was charged, ethylene was charged to a pressure of 0.8 MPa, stirred, heated to 70 °C and reacted for 20 min, and 126 g of the polymerization product was collected.

[0172] Example 8

[0173] Multifunctional polycyclic bimetallic metallocene catalyst (8) and its preparation method and application:

[0174]

[0175] (1) Measure 50 ml of toluene, weigh 10.0 g (0.075 mol) of phthalaldehyde in a 300-ml schlenk flask, then add 25.5 g (0.15 mol) of 2,6-dimethylaniline, stir at -10 °C for 8 hours, remove the solvent under vacuum, add 100 ml of n-hexane to the remaining solid, dissolve and filter, and recrystallize the filtrate to obtain 23.2 g of phthalaldehyde-2,6-dimethylbenzenediimine solid, yield: 91.1%.

[0176] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.65 (d, 2H, CH), 7.72 (d, 2H), 7.50 (d, 2H), 7.24 - 7.17 (m, 2H), 6.99 (d, 4H), 2.24 (s, 12H, CH 3 ). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 163.82, 152.82, 136.51, 130.38, 129.15, 128.77, 128.42, 126.29, 17.97. Anal. Calcd. (%) for C 24 H24 N 2 (340): C, 81.58; H, 6.04; found: C, 81.56; H, 6.07; ESI-MS m / z calculated for [M+H] + .C 24 H 24 N 2 : 340.1, found, 341.1。

[0177] (2) Measure 60 ml of toluene, weigh 19.3 g (0.068 mol) of phthalaldehyde-2,6-dimethylbenzenediimine into a 300 ml schlenk flask, add an equimolar amount of indene, 7.88 g, at -30 °C, stir, react for 6 hours, remove the solvent under vacuum, wash 3 times with 300 ml of n-hexane, and dry under vacuum to obtain 24.6 phthalaldehyde-2,6-dimethylbenzenediimine indene, with a yield of 90.4%.

[0178] 1 H NMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.31 (d, 2H, CH), 7.26 (d, 2H, Ph), 7.03 - 6.98 (m, 4H, Ph), 6.12 - 5.96 (m, 4H, Ph), 5.88 (d, 1H, Cp), 5.69 (d, 1H, Cp), 3.06 - 2.98 (m, 2H, Ph), 2.78 (d, 1H, Cp), 2.71 (t, 1H, Ph), 2.37 (d, 1H, Ph), 2.26 (d, 12H, CH 3 ), 2.25 - 2.10 (m, 2H, Cp), 1.93 (d, 1H, Cp). 13 C NMR (125 MHz, CDCl 3 : 77.2 ppm): δ = 158.31, 152.84, 143.10, 132.14, 131.77, 130.50, 130.40, 128.65, 128.63, 127.57, 126.96, 47.60, 41.26, 38.44, 18.05. Anal. Calcd. (%) for C 33 H 34 N 2 (458): C, 86.42; H, 7.47; N, 6.11; found: C, 86.45; H, 7.45; N, 6.10; ESI-MS m / z calculated for [M+H] + .C 29 H 24 N 2: 458.2, found, 459.2。

[0179] (3) Catalyst synthesis

[0180] Measure 80 ml of toluene, weigh 5 g of phthalaldehyde-2,6-dimethylbenzenediimine indene ligand into a 300 ml schlenk flask, and add 3 times the amount of TiCl as the ligand at -30 °C 4 , stir, react for 6 hours, remove the solvent under vacuum, wash with 300 ml of n-hexane 3 times, and dry under vacuum to obtain 7.31 multifunctional polycyclic bimetallic metallocene catalyst (8) with a yield of 90.8%. 1 HNMR (400 MHz, CDCl 3 : 7.26 ppm): δ = 8.66 (d, 2H, CH), 7.25 (t, 2H, Ph), 6.99 (d, 4H, Ph), 6.22 (d, 2H, Ph), 6.13 (d, 1H, Cp), 5.86 - 5.75 (m, 3H, Ph), 5.29 (d, 1H, Cp), 3.04 - 2.93 (m, 3H, Ph), 2.71 - 2.57 (m, 2H, Ph), 2.27 (s, 12H, CH3). Anal. Calcd. (%) for C 33 H 33 N 2 Cl 5 NiTi(737.9): C, 53.46; H, 4.49; Cl, 23.91; N, 3.78; Ni, 7.92; Ti, 6.46; found: C, 53.48; H, 4.47; Cl, 23.92; N, 3.77; Ni, 7.92; Ti, 6.46.

[0181] (4) Ethylene polymerization:

[0182] Under anhydrous and anaerobic conditions, after the 2-liter stainless steel autoclave is fully replaced with nitrogen, add 1 L of hexane to the reaction kettle, add 8 mg of multifunctional polycyclic bimetallic metallocene catalyst (8), 4.5 mL of MAO solution (10 wt%), charge 0.1 L of hydrogen, charge ethylene to a pressure of 0.7 MPa, stir, heat to 65 °C and react for 30 min, and collect 179 g of the polymerization product.

[0183] (5) Ethylene copolymerization:

[0184] Under anhydrous and anaerobic conditions, after a 2-L stainless steel autoclave was fully replaced with nitrogen, 1 L of toluene, 5 mg of a multifunctional polycyclic bimetallic metallocene catalyst (8), 2 mL (10 wt%) of an MAO solution, 30 g of liquid propylene, and 45 mL of 1-hexene were added to the autoclave. Then, 0.05 L of hydrogen was charged, and ethylene was charged until the pressure reached 0.8 MPa. The mixture was stirred and heated to 65 °C for reaction for 45 min, and 221 g of the polymerization product was collected.

[0185] In summary, as can be seen from the above results, the polycyclic bimetallic metallocene catalyst containing a bimetallic metallocene compound of the present invention has high catalytic activity; in addition, the polycyclic bimetallic metallocene catalyst of the present invention can efficiently catalyze olefin polymerization at a relatively high temperature and has high catalytic activity.

[0186] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A bimetallic metallocene compound, characterized in that: The bimetallic metallocene compound has a general structural formula shown in formula (A): Wherein, R and R1 are the same or different and are each selected from H, C1-C 20 Fatty acid group, C6-C 30 Aryl, C3-C 30 Cycloalkyl, C1-C 20 Perfluorinated or polyfluorinated aliphatic groups, C6-C 30 Perfluorinated or polyfluorinated aryl, C3-C 30 Perfluorinated or polyfluorinated cycloalkyl, C1-C 20 Alkoxy, C6-C 30 Aryloxy and C3-C 30 One or more of the cycloalkoxy groups; X is halogen, C1-C 10 The fatty groups and C3-C 10 One or more of the cycloalkyl groups; Z and M are each selected from one or more of Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd and Ru.

2. The bimetallic metallocene compound according to claim 1, wherein R and R1 are each selected from one or more of H, phenyl, 2,6-difluorophenyl, 4-fluorophenyl, 2,4,6-trifluorophenyl, 2,6-dimethylphenyl, 4-methylphenyl and 2,4,6-trifluorophenyl; X is Cl; Z and M are each selected from one or more of Ti, Zr, Hf, Fe, Ni, Pd, Co and Ru.

3. The bimetallic metallocene compound according to claim 1 or 2, wherein The metallocene compound includes one or more of formula (1) to formula (8); 4. A method for preparing a bimetallic metallocene compound according to any one of claims 1 to 3, characterized in that: The preparation method comprises: (1) In the presence of a first organic solvent, o-phthalaldehyde (ketone) and C4-C 15 A first reaction is carried out by contacting with an amine to obtain a compound represented by formula (D); (2) contacting the compound represented by formula (D) with indene in the presence of a second organic solvent to carry out a second reaction to obtain a compound represented by formula (E); (3) contacting the compound represented by formula (E) with a halide salt containing Z and M in the presence of a third organic solvent to carry out a third reaction to obtain a compound represented by formula (A); Wherein, R and R1 are the same as defined in any one of claims 1-3.

5. The preparation method according to claim 4, wherein In step (1), relative to 50-100 ml of the first organic solvent, the amount of the o-phthalaldehyde (ketone) is 0.01-3 mol, preferably 0.01-2 mol; the amount of the amine is 0.01-4 mol, preferably 0.01-3 mol; And / or, the conditions of the first reaction include: reacting at a temperature of -60°C to 120°C for 1-15 hours.

6. The preparation method according to claim 4, wherein In step (2), relative to 60-150 ml of the second organic solvent, the amount of the compound represented by formula (D) is 0.5-20 g, preferably 0.5-10 g; the amount of indene is 0.5-20 g, preferably 0.5-10 g; And / or, the conditions of the second reaction include: reacting at a temperature of -60°C to 50°C for 4-20 hours.

7. The preparation method according to claim 4, wherein In step (3), the amount of the compound represented by formula (E) is 2-10 g, preferably 2-5 g, relative to 80-150 ml of the third organic solvent; the amount of the halide salt containing Z and M is 1-8 times, preferably 1-5 times, that of formula (E); And / or, the conditions of the third reaction include: reacting at a temperature of -80°C to 80°C for 4-15 hours.

8. The preparation method according to claim 4, wherein C4-C 15 The amine is selected from one or more of aniline, 2,6-difluoroaniline, 2,4,6-trifluoroaniline, 4-fluoroaniline, 4-methylaniline, 2,4,6-trimethylaniline and 2,6-dimethylaniline; And / or, the first organic solvent, the second organic solvent and the third organic solvent are the same or different, and each is selected from C5 to C 30 Saturated hydrocarbons, C5~C 30 Alicyclic hydrocarbons, C6~C 30 Aromatic hydrocarbons, C3~C 20 One or more of saturated heterocyclic hydrocarbons and paraffin oil; Preferably, the first organic solvent, the second organic solvent and the third organic solvent are the same or different, and each is selected from one or more of toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane and hexadecane.

9. A polycyclic bimetallic metallocene catalyst, characterized in that: The polycyclic bimetallic metallocene catalyst is a bimetallic metallocene compound as claimed in any one of claims 1 to 3.

10. A catalyst system, characterized in that The catalyst system comprises a main catalyst and a co-catalyst, wherein the main catalyst is the bimetallic metallocene compound according to any one of claims 1 to 3.

11. The catalyst system according to claim 10, wherein The molar ratio of the main catalyst to the co-catalyst is 1:(5-2000); And / or, the co-catalyst is an alkyl aluminum and / or an alkoxy aluminum; preferably, the co-catalyst is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-tert-butyl aluminum, trioctylaluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, sesquiethyl aluminum chloride, modified or unmodified MAO.

12. Use of the catalyst system according to claim 10 or 11 in olefin polymerization.

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