A heteroanthracene-bridged aryloxy tridentate ligand-metal complex and a method of preparation and a method of olefin polymerization

Abstract

The application discloses a heteroanthracene bridged aryloxy tridentate ligand-metal complex and a preparation method and an olefin polymerization method. In the olefin polymerization method, a heteroanthracene bridged aryloxy tridentate ligand-metal complex is used as a main catalyst, and one or more of a metal aluminum activator and an optional borate assistant is used as a cocatalyst to carry out homopolymerization or copolymerization to prepare a polymerized olefin. The catalyst provided by the application has excellent heat resistance and can be applied to catalyzing ethylene / alpha-olefin copolymerization and ethylene / cyclic olefin copolymerization at the same time, and has high high-temperature catalytic activity and a high comonomer insertion rate.

Description

Technical Field

[0001] This application relates to a heteroanthracene-bridged aryloxytridentate ligand-metal complex, its preparation method, and a method for olefin polymerization, belonging to the field of olefin polymerization catalyst technology. Background Technology

[0002] Polyolefin materials, due to their readily available raw materials, low price, and superior performance, have become the most popular resin materials, with an annual output exceeding 100 million tons. With continuous socio-economic development, the demand for the performance of polyolefin materials is increasing. The olefin industry is now shifting from general-purpose materials to functional materials, especially high-end polyolefin products, such as polyolefin elastomers (POE) used in photovoltaic materials and cyclic olefin copolymers (COC) used in high-end optical materials. The research and industrialization of olefin polymerization catalysts are central to polyolefin production. Different types of catalysts have their own advantages and disadvantages, and are used in combination with different polymerization processes to produce different grades of polyolefin products. High-end polyolefin products place higher demands on catalyst systems. For example, POE production requires high-temperature solution polymerization, while COC preparation requires a high insertion rate of the comonomer norbornene. Therefore, the development of novel polyolefin catalyst systems is crucial.

[0003] Many monotitanium-based metal catalysts, such as confined geometry catalysts (CGC), have been developed for catalyzing ethylene polymerization and copolymerization with α-olefins (US5064802, EP0416815A2, US5026798, US5057475), exhibiting high catalytic activity. However, these catalysts suffer from poor temperature resistance, and the copolymers have low molecular weights. Kol et al. developed a series of non-titanium-based tetradentate ONNO zirconium-based catalysts for olefin polymerization, but their activity was poor, only 1.8 × 10⁻⁶. 4 g mol -1 h -1 (J.Am.Chem.Soc.2000,122,10706-10707). Chinese patent CN 111747976 B proposes an O,O,O tripentate coordination catalyst based on an aryloxy ether skeleton. Its catalytic system exhibits excellent catalytic activity and thermal stability in olefin / α-olefin copolymerization, but its effect on ethylene / cycloolefin copolymerization is unknown. Summary of the Invention

[0004] To address the aforementioned problems in existing technologies, there is an urgent need to develop a catalyst for the copolymerization of ethylene / α-olefins and ethylene / cycloolefins that possesses good temperature resistance, high catalytic activity, and a high comonomer insertion rate.

[0005] According to one aspect of this application, a xanthracene-bridged aryloxytridentate ligand-metal complex is provided, the aryloxytridentate ligand-metal complex having the structure shown in Formula I:

[0006]

[0007] R1 to R8 are independently selected from one of -H, halogen I, C1 to C30 alkyl I, C1 to C30 substituted alkyl, C1 to C30 alkoxy, C1 to C30 substituted alkoxy, C1 to C30 amino, C1 to C30 substituted amino, C6 to C30 aryl I, C6 to C30 substituted aryl, C6 to C30 aromatic heterocyclic I, and C6 to C30 substituted aromatic heterocyclic.

[0008] The substituents in the C1-C30 substituted alkyl, C1-C30 substituted alkoxy, C1-C30 substituted amino, C6-C30 substituted aromatic, and C6-C30 substituted aromatic heterocyclic groups are independently selected from at least one of halogen, alkoxy, nitro, trifluoromethyl, vinyl, and silyl.

[0009] M is selected from one of titanium, zirconium, and hafnium;

[0010] X is independently selected from one of the following: halogen II, C1-C50 alkyl II, C6-C50 aromatic II, C6-C50 aromatic heterocyclic II, the group shown in -N(RN)2, and the group shown in -NCORC;

[0011] Wherein, the R in -N(RN)2 and -NCORC is independently selected from one of methyl, ethyl, isopropyl, diisopropyl, and tert-butyl;

[0012] The halogen I and halogen II are independently selected from at least one of F, Cl, Br, and I;

[0013] Y represents oxygen or sulfur.

[0014] Optionally, R1 to R8 are independently selected from one of hydrogen, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C6 to C30 aromatic, and substituted or unsubstituted C6 to C30 aromatic heterocyclic.

[0015] Optionally, M is a metal of titanium, zirconium, or hafnium, said metal having an oxidation state of +2, +3, or +4.

[0016] Optionally, X is selected from one of halogenated or unsaturated (C2-C50) hydrocarbons, unsaturated (C2-C50) heterohydrocarbons, (C1-C50) hydrocarbon groups, (C6-C50) aryl groups, (C6-C50) heteroaryl groups, cyclopentadienyl groups, substituted cyclopentadienyl groups, (C4-C12) dienes, -N(RN)2 and -NCORC monodentate ligands or bidentate ligands.

[0017] Optionally, R1 to R8 are independently selected from one of -H, halogen I, C1 to C10 alkyl I, C1 to C10 substituted alkyl, C1 to C10 alkoxy, C1 to C10 substituted alkoxy, C1 to C10 amino, C1 to C10 substituted amino, C6 to C15 aryl I, C6 to C15 substituted aryl, C6 to C15 aromatic heterocyclic I, and C6 to C15 substituted aromatic heterocyclic.

[0018] The substituents in the C1-C10 substituted alkyl, C1-C10 substituted alkoxy, C1-C10 substituted amino, C6-C15 substituted aromatic, and C6-C15 substituted aromatic heterocyclic groups are independently selected from at least one of halogen, alkoxy, nitro, trifluoromethyl, vinyl, and silyl.

[0019] The X is independently selected from one of the following: halogen II, C1-C20 alkyl II, C6-C20 aromatic II, C6-C20 aromatic heterocyclic II, C1-C6 alkyl-substituted C6-C12 aromatic group, and the group shown in -CH2SiL3;

[0020] In -CH2SiL3, L is selected from C1 to C12 hydrocarbon groups.

[0021] Optionally, R1 to R8 may be the same as or different from each other, and are selected from hydrogen, halogen, C1 to C10 alkyl, phenyl-substituted alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C1 to C10 amino, C6 to C10 bridged cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraceneyl, and substituted or unsubstituted C6 to C20 aromatic heterocyclic groups.

[0022] Optionally, M is a metal of titanium, zirconium, or hafnium, the metal having an oxidation state of +4.

[0023] Optionally, X is independently selected from halogens, (C1C20)alkyl, (C7-C20)aralkyl, (C1-C6)alkyl-substituted (C6-C12)aryl, or (C1-C6)alkyl-substituted benzyl, CH2SiL3, wherein L is a (C1-C12) hydrocarbon.

[0024] According to another aspect of this application, a method for preparing the above-described aryloxytridentate ligand-metal complex is provided, the method comprising:

[0025] A mixture containing an aryloxytridentate ligand and a metal compound is reacted to obtain the aryloxytridentate ligand-metal complex.

[0026] Optionally, the molar ratio of the aryloxytridentate ligand to the metal compound is 1:(1-2).

[0027] Optionally, the metal compound is selected from at least one of TiCl4, ZrCl4, HfBn4, HfCl4, ZrBn4, and Ti(Nme2)4.

[0028] Optionally, the aryloxytridentate ligand is selected from at least one of the structures shown in L1, L2, L3, and L4;

[0029]

[0030] Optionally, the reaction temperature is -80 to 120°C, and the reaction time is 0.1 to 72 hours.

[0031] According to another aspect of this application, a method for olefin polymerization is provided, the method comprising:

[0032] In a closed reactor, olefin feedstock is polymerized with a mixture containing a main catalyst and a co-catalyst to obtain polymerized olefins.

[0033] The main catalyst is selected from the aryloxytridentate ligand-metal complex described above.

[0034] Optionally, the olefin feedstock is selected from ethylene feedstock or ethylene and α-olefin feedstock.

[0035] Optionally, the α-olefin is selected from at least one of propylene, 1-butene, 1-hexene, 1-octene, norbornene, and norbornene derivatives.

[0036] Optionally, the norbornene derivative is selected from at least one of alkyl-substituted norbornene, alkoxy-substituted norbornene, vinyl-substituted norbornene, ester-substituted norbornene, amino-substituted norbornene, phenyl-substituted norbornene, and phenoxy-substituted norbornene.

[0037] Optionally, when the olefin feedstock is ethylene and α-olefin, the concentration of the α-olefin is 0.01 to 50 mol / L.

[0038] Optionally, the co-catalyst is selected from aluminum activators and / or borate auxiliaries.

[0039] Optionally, the aluminum activator is selected from at least one of C1-C8 alkylaluminoxanes and modified aluminumoxanes.

[0040] Optionally, the modified aluminum oxane is selected from at least one of modified methyl aluminum oxane, modified ethyl aluminum oxane, and modified octyl aluminum oxane.

[0041] Optionally, the borate additive is selected from at least one of triphenylmethyltetra(pentafluorophenyl)borate, tetra(pentafluorophenyl)borate-methyl di-(octadecyl)ammonium salt, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0042] Optionally, when the co-catalyst is an aluminum activator, the molar ratio of the aluminum activator to the main catalyst is (3-5000):1.

[0043] Wherein, the molar amount of the aluminum activator is calculated as the molar amount of aluminum, and the molar amount of the main catalyst is calculated as the molar amount of the metal element in the main catalyst.

[0044] Optionally, when the co-catalyst is an aluminum activator, the molar ratio of the aluminum activator to the main catalyst is (50-5000):1.

[0045] Optionally, when the co-catalyst is a borate promoter, the molar ratio of the borate promoter to the main catalyst is (1-40):1.

[0046] Wherein, the molar amount of the borate additive is expressed as the molar amount of boron, and the molar amount of the main catalyst is expressed as the molar amount of the metal element in the main catalyst.

[0047] Optionally, when the co-catalyst is a borate promoter, the molar ratio of the borate promoter to the main catalyst is 1 to 15.

[0048] Optionally, the concentration of the main catalyst in the mixture is 0.1–20 μmol / L, based on the molar concentration of the metal element in the main catalyst.

[0049] Optionally, the concentration of the main catalyst is independently selected from any value among 0.1 μmol / L, 0.5 μmol / L, 1 μmol / L, 5 μmol / L, 10 μmol / L, 15 μmol / L, 20 μmol / L, or a range between any two of the above.

[0050] Optionally, the polymerization reaction temperature is 25–250°C, and the polymerization reaction time is 0.01–120 h.

[0051] Optionally, the temperature of the polymerization reaction is independently selected from any value of 25°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, or a range between any two of the above.

[0052] Optionally, the polymerization reaction time is independently selected from any value of 0.01h, 0.5h, 1h, 20h, 40h, 60h, 80h, 100h, 120h or a range between any two of the above.

[0053] Optionally, the pressure of the polymerization reaction is 0.1 to 40 MPa.

[0054] Optionally, the pressure of the polymerization reaction is independently selected from any value of 0.1 MPa, 0.5 MPa, 1 MPa, 5 MPa, 10 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa, 35 MPa, 40 MPa, or a range between any two of the above.

[0055] The catalyst provided by this invention has excellent heat resistance and can be used simultaneously for catalytic polymerization of ethylene / α-olefins and copolymerization of ethylene / cycloolefins. It has high high-temperature catalytic activity and comonomer insertion rate.

[0056] In this application, C1 to C30, C6 to C30, etc., all refer to the number of carbon atoms contained in the group.

[0057] In this application, the term "alkyl" refers to a group formed by the loss of any one hydrogen atom from an alkane molecule.

[0058] In this application, the term "aromatic group" refers to a group formed by the loss of a hydrogen atom from an aromatic ring in an aromatic compound molecule; for example, p-tolyl formed by the loss of a hydrogen atom at the para-position of the methyl group on the benzene ring of toluene.

[0059] In this application, the term "aromatic heterocyclic group" refers to a heterocycle with planar structure characteristics, in which the atoms in the ring form a closed conjugated system, the molecule is planar, and there are ring-shaped delocalized electron clouds on the upper and lower sides of this plane. The number of p electrons in the conjugated system all conforms to Hückel's rule. It is a group formed by losing a hydrogen atom from the molecule of a compound.

[0060] In this application, "substituted alkyl" and "substituted aromatic group" refer to alkyl groups substituted by any group and aromatic groups substituted by any group, respectively.

[0061] In this application, "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0062] The beneficial effects that this application can produce include:

[0063] 1) The anthracene structure provided in this application has a rigid structure. The metal complex catalyst obtained by using it as a framework structure has high thermal stability. At the same time, anthracene, as a bridging group, is easy to modify and can effectively adjust the electronegativity and coordination space of the metal center, so that it can still maintain high polymerization activity and high comonomer insertion rate at high temperature.

[0064] 2) The catalyst system provided in this application, when activated by preferred co-catalysts such as aluminum alkoxy or organoboron salts, can be used to catalyze the copolymerization of ethylene / α-olefins or ethylene / cycloolefins, and to catalyze the copolymerization of ethylene / α-olefins, such as 1-octene, with a catalytic activity reaching 10. 8 g poly / mol metal h, the molar insertion rate of 1-octene can reach over 30%. It catalyzes ethylene / cycloolefin copolymerization, such as norbornene and its derivatives, with catalytic activity reaching 10. 7 g poly / mol metal The norbornene insertion rate can reach 60 wt%; the catalyst exhibits good temperature resistance, maintaining high activity even at 140℃. It is suitable for the large-scale industrial production of high-end polyolefin materials such as POE and COC, and has significant industrial application prospects. Detailed Implementation

[0065] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0066] Unless otherwise specified, all raw materials and reagents used in the embodiments of this application were purchased commercially.

[0067] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0068] The polymerization activity of the polymers described in the following examples was calculated using the following formula:

[0069] Polymerization activity = polymer mass / (number of moles of metal in catalyst * polymerization time).

[0070] The weight-average molecular weight (Mw) of the polymer was obtained by GPC instrument at 150℃ using three PL gel 10μm MIXED-B separation columns in series, with 1,2,4-trichlorobenzene as solvent.

[0071] The calculation method for comonomer insertion rate is referenced in Macromolecules 1999, 32, 3817 and Journal of Polymer Science Part A: Polymer Chemistry, 1998, 36(10): 1633-8.

[0072] Example 1: Preparation of ligand L1

[0073] The anthracene-bridged aryloxytridentate ligand-metal complex ligand of the present invention has the structure shown in Formula II:

[0074]

[0075] Ligand L1 was prepared according to the following synthetic route:

[0076]

[0077] (1) In a 250 ml reaction flask, 9,9-dimethyloxanthracene (1 eq) and TMEDA (2 eq) were dissolved in anhydrous diethyl ether. The mixture was cooled to 0 °C, and n-BuLi (2.4 eq) was added dropwise. The mixture was then heated to room temperature and stirred for 2 h. The mixture was cooled to 0 °C again, and TMSCl (2.4 eq) was added dropwise. The reaction mixture was then heated to room temperature and reacted for 12 h. Deionized water was then added, and the organic phase was collected. The aqueous phase was extracted with n-hexane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, separated by column chromatography (petroleum ether), and further recrystallized from ethanol to obtain colorless crystals A1.

[0078] The NMR data for compound A1 are as follows:

[0079] 1 H NMR (400MHz, CDCl3)0.40(s,18H),1.61(s,6H),7.08(t,2H),7.36(dd,2H),7.46(dd,2H).

[0080] (2) Under nitrogen protection, compound A1 (1 eq) was dissolved in 60 ml of anhydrous dichloromethane in a 250 ml reaction flask, and then BBr3 (2.4 eq) was added. The mixture was stirred overnight at room temperature. After the reaction was completed, deionized water was added, and the mixture was filtered. The filter cake was washed with deionized water and dichloromethane and dried under vacuum to obtain white solid A2.

[0081] The NMR data for compound A2 are as follows:

[0082] 1 H NMR (400MHz, CDCl3)1.61(s,6H),4.2(s,4H),7.08(t,2H),7.36(dd,2H),7.46(dd,2H).

[0083] (3) Under nitrogen protection, compound A2 (1 eq), 1-bromo-2-methoxy-3-methylbenzene (2.2 eq), potassium carbonate (2.2 eq), and Pd(PPh3)4 (0.2 eq) were added to a 250 ml reaction flask. Toluene / deionized water was added as a solvent, and the mixture was refluxed and stirred at 110 °C for 24 h. The reaction was then stopped, concentrated, dissolved in dichloromethane, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain a light yellow crude product solid. The solid was separated by column chromatography to obtain a white solid. This white solid was then dissolved in anhydrous dichloromethane, BBr3 (1 eq) was added, and the reaction was carried out at room temperature for 24 h. The reaction was then stopped, quenched with saturated NH4Cl aqueous solution, extracted with dichloromethane, washed with brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain a white solid, L1.

[0084] The NMR data for ligand L1 are as follows:

[0085] 1 H NMR (400MHz, CDCl3)1.62(s,6H),2.16.(s,6H),7.05(t,4H),7.25-7.36(dd,4H),7.46(d,2H),7.65(d,2H).

[0086] Example 2 Preparation of ligand L2

[0087] Ligand L2 was prepared according to the following synthetic route:

[0088]

[0089] (1) Under nitrogen protection, 1-isopropyl-2-methoxybenzene (1 eq) and TMEDA (1.2 eq) were dissolved in 50 ml of anhydrous diethyl ether in a 250 ml reaction flask. The reaction flask was placed in a dry ice acetone bath and cooled to -78 °C. n-BuLi (1.2 eq) was added dropwise, and the mixture was slowly heated to room temperature and stirred for 2 h. The dry ice acetone bath was removed, and the mixture was heated to room temperature and reacted for 2 h. Then, the mixture was cooled to -78 °C again, and B(OMe)3 (1.5 eq) was added. After stirring for half an hour, the mixture was heated to room temperature and stirred overnight. The reaction was quenched with 1 M hydrochloric acid, and the organic phase was separated. The organic phase was washed with saturated brine and water, collected, dried over anhydrous sodium sulfate, filtered, evaporated to dryness, and separated by column chromatography to obtain a white solid B2.

[0090] The NMR data for compound B2 are as follows:

[0091] 1 H NMR (CDCl3, 400MHz): δ7.52(d,1H),7.35(d,1H),7.10(d,1H),4.80(s,2H),3.64(s,3H),3.04(m,1H),1.10(d,6H).

[0092] (2) Compound A3 was prepared according to the reference (CCS Chem. 2021, 3, 274-286). Under nitrogen protection, compound A3 (1 eq), B2 (2.2 eq), potassium carbonate (2.2 eq), and Pd(PPh3)4 (0.2 eq) were added to a 250 ml reaction flask. Toluene / deionized water was added, and the mixture was refluxed and stirred at 110 °C for 24 h. The reaction was stopped, concentrated, dissolved in dichloromethane, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain a light yellow crude product solid. The solid was separated by column chromatography to obtain a white solid. This white solid was then dissolved in anhydrous dichloromethane, BBr3 (1 eq) was added, and the reaction was carried out at room temperature for 24 h. The reaction was stopped, quenched with saturated NH4Cl aqueous solution, extracted with dichloromethane, washed with brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain a white solid, L2.

[0093] The NMR data for ligand L2 are as follows:

[0094] 1 H NMR(400MHz, CDCl3)7.49(d,2H),7.29.(d,2H),7.16(d,2H),7.06(dd,2H),6. 81(d,2H),5.25(d,2H),3.35(m,2H),1.59(s,6H),1.29(d,12H),1.20(s,18H).

[0095] Example 3 Preparation of ligand L3

[0096] Ligand L3 was prepared according to the following synthetic route:

[0097]

[0098] (1) The synthesis steps of ligand L3 are similar to those of L2, except that the starting materials 1-isopropyl-2-methoxybenzene are replaced with 1-tert-butyl-2-methoxybenzene and 9,9-dimethyloxanthracene is replaced with 9,9-dimethylthioxanthracene. Ligand L3 is a pale yellow solid.

[0099] The NMR data for ligand L3 are as follows:

[0100] 1 H NMR(400MHz,C6D6)7.69(d,2H),7.59.(d,2H),7.36(d,2H),7.08(dd,2H),6.71(d,2H),5.45(d,2H),1.59(s,6H),1.26(s,36H).

[0101] Example 4: Preparation of ligand L4

[0102] Ligand L4 was prepared according to the following synthetic route:

[0103]

[0104] (1) Compound A5 was prepared according to the reference (CCS Chem. 2021, 3, 274-286). The only difference was replacing the starting material 9H-oxanthracene with 2,3,6,7,9,9-hexamethyl-9H-oxanthracene. Under nitrogen protection, A5 (1 eq) and TMEDA (1.2 eq) were dissolved in anhydrous diethyl ether. The reaction flask was placed in a dry ice-acetone bath and cooled to -78°C. n-BuLi (1.2 eq) was added dropwise, and the mixture was slowly heated to room temperature and stirred for 2 hours. The dry ice-acetone bath was removed, and the mixture was heated to room temperature for 2 hours. Then, the mixture was cooled to -78°C again, and B(OMe)3 (1.5 eq) was added. After stirring for half an hour, the mixture was heated to room temperature and stirred overnight. The reaction was quenched with 1M hydrochloric acid. The organic phase was separated, washed with saturated brine, washed with water, and collected. The organic phase was dried over anhydrous sodium sulfate, filtered, evaporated to dryness, and separated by column chromatography to obtain A6.

[0105] The NMR data for compound A6 are as follows:

[0106] 1 H NMR (CDCl3, 400MHz): δ7.10 (s, 2H), 4.31 (s, 4H), 2.21-2.32 (s, 12H), 1.66 (s, 6H).

[0107] (2) 2-bromo-4-tert-butylphenol (1 eq), 3,6-dichlorocarbazole (3 eq), and Pd(PPh3)4 (0.1 eq) were added to 100 ml of ethylene glycol dimethyl ether. After thorough mixing, an aqueous solution of Na2CO3 (1 eq) was added, and the mixture was heated to 70 °C and reacted for 24 h. The starting material was completely eliminated by TLC. The reaction solution was concentrated, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1 (v / v)) to obtain compound B4.

[0108] (3) Compound B4 (1 eq) was added to 100 mL of dichloromethane and stirred thoroughly. The mixture was then placed in an ice bath at 0 °C, and liquid bromine (1.6 eq) was slowly added dropwise. After the addition was complete, the reaction continued for 12 h, and TLC monitoring showed complete disappearance of the starting material. Residual liquid bromine was quenched with 1 mol / L Na2S2O4 aqueous solution. The reaction solution was concentrated, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 15:1 (v / v)) to obtain compound B5.

[0109] The NMR data for compound B5 are as follows:

[0110] 1H NMR (CDCl3, 400MHz): δ7.68 (s, 2H), 7.57 (m, 2H), 7.46 (m, 4H), 5.61 (s, 1H), 1.36 (s, 9H).

[0111] (4) Under nitrogen protection, compounds A6 (1 eq), B5 (2.2 eq), potassium carbonate (2.2 eq) and Pd(PPh3)4 (0.2 eq) were added to a 250 ml reaction flask. Toluene / deionized water solvent was added, and the mixture was refluxed and stirred at 110 °C for 24 h. The reaction was stopped, concentrated, dissolved in dichloromethane, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain the crude product. The crude product was separated by column chromatography to obtain a pale yellow solid L4.

[0112] The NMR data for ligand L4 are as follows:

[0113] 1 H NMR (400MHz, CDCl3) δ7.58(s,4H),7.43(m,4H),7.26(m,8H),6.97(s,2H),5.43(s,2H),2.18(s,12H),1.62(s,6H),1.26(s,18H).

[0114] Example 5 Preparation of complexes M1 and M2

[0115]

[0116] The synthesis steps are as follows:

[0117] Inside the glove box, ligand L1 (1 eq) was dissolved in anhydrous toluene and added dropwise to a toluene solution of TiCl4 (1 eq). The reaction was carried out at 70 °C for 10 h. The toluene was dried under vacuum, and the mixture was washed with anhydrous n-hexane, filtered, dissolved again in toluene, filtered, and the filtrate was dried under vacuum to constant weight to obtain complex M1.

[0118] 1 H NMR(400MHz,C6D6)1.32(s,6H),2.06.(s,6H),6.75(t,4H),7.05-7.16(dd,4H),7.26(d,2H),7.35(d,2H).

[0119] ICP and elemental analysis: Measured (calculated) C: 65.1 (64.7); H: 4.1 (4.5); Ti: 9.6 (8.9).

[0120] Under anhydrous and oxygen-free conditions, M1 (1 eq) was dissolved in anhydrous toluene, cooled to -40°C, and MeMgBr (1 eq) was added dropwise. The mixture was then heated to room temperature and reacted overnight. The mixture was filtered, the filtrate was dried under vacuum, washed with anhydrous n-hexane, dissolved in toluene again, filtered, and the filtrate was dried under vacuum. The mixture was then recrystallized from toluene / n-hexane to obtain complex M2.

[0121] 1 H NMR (400MHz, C6D6)0.82(s,6H),1.35(s,6H),2.12.(s,6H),6.85(t,4H),7.08-7.16(dd,4H),7.32(d,2H),7.45(d,2H).

[0122] ICP and elemental analysis: Measured (calculated) C: 73.5 (74.7); H: 6.5 (5.7); Ti: 10.2 (9.6).

[0123] Example 6 Preparation of complexes M3 and M4

[0124]

[0125] The synthesis steps of complex M3 are similar to those of M1, and the synthesis steps of M4 are similar to those of M2, except that L1 is replaced by L2 ligand.

[0126] Characterization of complex M3: 1 H NMR(400MHz,C6D6)7.25(d,2H),7.1.(d,2H),6.96(d,2H),6.86(dd,2H),6.61(d,2H),2.85(m,2H),1.35(s,6H),1.19(d,12H),0.95(s,18H).

[0127] ICP and elemental analysis: Measured (calculated) C: 68.8 (69.6); H: 6.1 (6.8); Ti: 7.9 (6.8).

[0128] Characterization of complex M4: 1 H NMR(400MHz,C6D6)7.25(d,2H),7.1.(d,2H),6.96(d,2H),6.86(dd,2H),6.6 1(d,2H),2.85(m,2H),1.35(s,6H),1.19(d,12H),0.95(s,18H),0.52(s,6H).

[0129] ICP and elemental analysis: Measured (calculated) C: 78.3 (77.5); H: 7.4 (8.2); Ti: 7.6 (7.2).

[0130] Example 7 Preparation of complex M5

[0131]

[0132] The synthesis steps are as follows:

[0133] Under anhydrous and oxygen-free conditions, ZrCl4 (1 eq) was dispersed in anhydrous toluene and cooled to -40°C. A solution of magnesium methyl bromide in diethyl ether (1.1 eq) was added dropwise, and the mixture was stirred for 1 h. Then, 10 mL of a toluene solution containing ligand L3 (1 eq) was added to the solution, and the reaction was allowed to proceed for 10 h at room temperature. Insoluble matter was removed by filtration, and volatile components in the filtrate were removed under vacuum. The crude product was recrystallized from dichloromethane / n-hexane (volume ratio 1:3) to obtain complex M5.

[0134] 1 H NMR(400MHz,C6D6)7.39(d,2H),7.24.(d,2H),7.08(d,2H),6.73(dd,2H),6.52(d,2H),1.29(s,6H),0.96(s,36H),-0.56(s,6H).

[0135] ICP and elemental analysis: Measured (calculated) C: 72.3 (71.7); H: 6.9 (7.8); Zr: 13.2 (12.1).

[0136] Example 8 Preparation of complex M6

[0137]

[0138] Under anhydrous and oxygen-free conditions, HfBn4 (1 eq) was dissolved in anhydrous toluene, and a toluene solution containing ligand L3 (1 eq) was added to the solution. The reaction was carried out at room temperature for 12 h. Volatile components in the filtrate were removed under vacuum, and the crude product was recrystallized from dichloromethane / n-hexane to obtain complex M6.

[0139] 1 H NMR(400MHz,C6D6)7.88(d,2H),7.66(d,2H),7.54-7.20.(d,8H),6.85-7.1 (d,4H),6.63(dd,2H),6.51(d,2H),3.21(m,4H),1.29(s,6H),0.96(s,36H).

[0140] ICP and elemental analysis: Measured (calculated) C: 69.7 (68.9); H: 5.8 (6.7); Hf: 17.5 (18.0).

[0141] Example 9 Preparation of complex M7

[0142]

[0143] The synthesis steps of complex M7 are similar to those of M6, except that L4 is used as the ligand and HfBn4 is replaced with ZrBn4. The final complex obtained is M7.

[0144] 1 H NMR (400MHz, C6D6) δ7.68(d,2H),7.56-7.35(s,12H),7.05-7.21(m,12H),6.84(s,2H),3.43(s,4H),2.05(s,12H),1.55(s,6H),1.14(s,18H).

[0145] ICP and elemental analysis: Measured (calculated) C: 70.2 (71.0); H: 4.8 (5.3); Zr: 8.2 (7.0).

[0146] Example 10 Preparation of complex M8

[0147]

[0148] The synthesis steps of complex M8 are similar to those of M5, except that L4 is used as the ligand and ZrCl4 is replaced with HfCl4. The final complex obtained is M8.

[0149] 1 H NMR (400MHz, C6D6) δ7.48(s,4H),7.36(m,4H),7.19(m,8H),6.89(s,2H),2.10(s,12H),1.57(s,6H),1.16(s,18H),-0.8(s,6H).

[0150] ICP and elemental analysis: Measured (calculated) C: 62.4 (63.1); H: 5.7 (4.9); Hf: 15.1 (14.4).

[0151] Example 11 Study on catalytic homopolymerization of ethylene

[0152] The homopolymerization of ethylene was carried out in a 500 ml stainless steel high-pressure reactor. The reactor, equipped with a mechanical stirrer, was heated to 140 °C, evacuated under vacuum for 1 h, and ethylene gas was introduced to 1 bar. Then, a toluene solution containing methylaluminoxane (MAO), the main catalyst, was added to the polymerization reactor. The ethylene gas pressure was then increased to 1.0 MPa, and the mixture was stirred for a certain period. After the polymerization reaction was completed, the ethylene gas was rapidly released, the reactor was cooled to 30 °C, and the reactor was opened. The solid-liquid mixture inside the reactor was poured into a 1:3 volume ratio solution of 3M hydrochloric acid and ethanol. After stirring for a period of time, the mixture was filtered and dried in a vacuum oven at 60 °C for 12 h to obtain the polymer sample. The polymer analysis results are shown in Table 1.

[0153] Table 1. Results of ethylene homopolymerization catalyzed by complexes M1-M8 as the main catalysts. a

[0154]

[0155]

[0156] a Polymerization conditions: The amount of main catalyst M1 to M8 is 0.5 μmol, the co-catalyst is MAO, Al / M = 1500, the polymerization temperature is 140℃, the polymerization pressure is 1.0 MPa, and the polymerization time is 10 min. b Molecular weight and molecular weight distribution (PDI) were determined by high-temperature GPC.

[0157] Example 12: Catalytic copolymerization of ethylene and 1-octene

[0158] The copolymerization of ethylene and 1-octene was carried out in a 500 ml stainless steel high-pressure reactor. The reactor, equipped with a mechanical stirrer, was heated to 140 °C and evacuated under vacuum for 1 h. The system was then cooled to 140 °C, and ethylene gas was introduced to 1 bar. The main catalyst, a mixed isoalkane solution containing methylaluminoxane (MAO) and a certain concentration of 1-octene (Isopar E) were then added to the polymerization reactor. The ethylene gas pressure was then increased to 1.0 MPa, and the mixture was stirred for a certain period. After the polymerization reaction was completed, the ethylene gas was rapidly released, the reactor was cooled to 30 °C, and the reactor was opened. The solid-liquid mixture inside the reactor was poured into a 1:3 volume ratio solution of 3M hydrochloric acid and ethanol. After stirring for a period of time, the mixture was filtered and dried in a vacuum oven at 60 °C for 12 h to obtain the polymer sample. The polymer analysis results are shown in Table 2.

[0159] Table 2. Results of the copolymerization of ethylene and 1-octene catalyzed by complexes M1-M8 as the main catalysts. a

[0160]

[0161]

[0162] a Polymerization conditions: The amount of main catalyst M1 to M8 is 0.2 μmol, the co-catalyst is MAO, Al / M = 1000, the polymerization temperature is 140℃, the concentration of 1-octene is 0.5 mol / L, the polymerization pressure is 1.0 MPa, and the polymerization time is 10 min. b Molecular weight and molecular weight distribution (PDI) were determined by high-temperature GPC. c The 1-octene insertion rate was determined by high-temperature 1H NMR and 1C NMR.

[0163] Example 13: Catalytic copolymerization study of ethylene and norbornene

[0164] The copolymerization reaction of ethylene and norbornene was carried out in a 500 ml stainless steel high-pressure reactor. The reactor, equipped with a mechanical stirrer, was heated to 120 °C and evacuated under vacuum for 1 h. The system was then cooled to 90 °C, and ethylene gas was introduced to 1 bar. The main catalyst, a toluene solution containing methylaluminoxane (MAO) and a certain concentration of norbornene were then added to the polymerization reactor. The ethylene gas pressure was then increased to 0.5 MPa, and the mixture was stirred for a certain period. After the polymerization reaction was completed, the ethylene gas was rapidly released, the reactor was cooled to 30 °C, and the reactor was opened. The solid-liquid mixture inside the reactor was poured into a 1:3 volume ratio mixture of 3M hydrochloric acid and ethanol. After stirring for a period of time, the mixture was filtered and dried in a vacuum oven at 60 °C for 12 h to obtain the polymer sample. The polymer analysis results are shown in Table 3.

[0165] Table 3. Results of the copolymerization reaction of ethylene and norbornene catalyzed by complexes M1-M8 as the main catalysts. a

[0166]

[0167]

[0168] a Polymerization conditions: The amount of main catalyst M1 to M8 is 0.5 μmol, the co-catalyst is MAO, Al / M = 1000, the polymerization temperature is 90℃, the concentration of norbornene is 1.5 mol / L, the polymerization pressure is 0.5 MPa, and the polymerization time is 10 min. b Molecular weight and molecular weight distribution (PDI) were determined by high-temperature GPC. c The norbornene insertion rate was determined by high-temperature 1H NMR and 1C NMR spectroscopy.

[0169] As can be seen from the above embodiments, the present invention provides anthracene-bridged aryloxytridentate ligand-metal complex that can efficiently catalyze the homopolymerization of ethylene, and can simultaneously catalyze the copolymerization of ethylene / α-olefins, such as 1-octene, and ethylene / cycloolefins, such as norbornene, and has high polymerization activity, comonomer insertion rate and thermal stability.

[0170] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A xanthracene-bridged aryloxytridentate ligand-metal complex, characterized in that, The aryloxytridentate ligand-metal complex has the structure shown in Formula I: Formula I; R1 to R8 are independently selected from one of -H, halogen, C1 to C30 alkyl, C1 to C30 substituted alkyl, C1 to C30 alkoxy, C1 to C30 substituted alkoxy, C1 to C30 amino, C1 to C30 substituted amino, C6 to C30 aryl, C6 to C30 substituted aryl, C6 to C30 aromatic heterocyclic, and C6 to C30 substituted aromatic heterocyclic. The substituents in the substituted alkyl group of C1 to C30, the substituted alkoxy group of C1 to C30, the substituted amino group of C1 to C30, the substituted aromatic group of C6 to C30, and the substituted aromatic heterocyclic group of C6 to C30 are independently selected from at least one of halogen, alkoxy, nitro, trifluoromethyl, vinyl, and silyl. M is selected from one of titanium, zirconium, and hafnium; X is independently selected from one of the following groups: halogen, C1-C50 alkyl, C6-C50 aromatic group, and C6-C50 aromatic heterocyclic group; The halogen is independently selected from at least one of F, Cl, Br, and I; Y represents oxygen or sulfur.

2. The aryloxytridentate ligand-metal complex according to claim 1, characterized in that, R1 to R8 are independently selected from one of -H, halogen, C1 to C10 alkyl, C1 to C10 substituted alkyl, C1 to C10 alkoxy, C1 to C10 substituted alkoxy, C1 to C10 amino, C1 to C10 substituted amino, C6 to C15 aryl, C6 to C15 substituted aryl, C6 to C15 aromatic heterocyclic, and C6 to C15 substituted aromatic heterocyclic. The substituents in the C1-C10 substituted alkyl, C1-C10 substituted alkoxy, C1-C10 substituted amino, C6-C15 substituted aromatic, and C6-C15 substituted aromatic heterocyclic groups are independently selected from at least one of halogen, alkoxy, nitro, trifluoromethyl, vinyl, and silyl. X is independently selected from halogens, C1-C20 alkyl groups, C6-C20 aromatic groups, and C6-C20 heterocyclic aromatic groups.

3. The method for preparing the aryloxytridentate ligand-metal complex according to any one of claims 1 to 2, characterized in that, The preparation method includes: A mixture containing aryloxytridentate ligands and metal compounds is reacted to obtain the aryloxytridentate ligand-metal complex.

4. The preparation method according to claim 3, characterized in that, The molar ratio of the aryloxytridentate ligand to the metal compound is 1:(1~2).

5. The preparation method according to claim 3, characterized in that, The metal compound is selected from at least one of TiCl4, ZrCl4, and HfCl4.

6. The preparation method according to claim 3, characterized in that, The aryloxytridentate ligand is selected from at least one of the structures shown in L1, L2, L3, and L4; 。 7. The preparation method according to claim 3, characterized in that, The reaction temperature is -80~120 ℃, and the reaction time is 0.1~72 h.

8. A method for olefin polymerization, characterized in that, The method includes: In a closed reactor, olefin feedstock is polymerized with a mixture containing a main catalyst and a co-catalyst to obtain polymerized olefins. The main catalyst is selected from the aryloxytridentate ligand-metal complex according to any one of claims 1 to 2.

9. The method according to claim 8, characterized in that, The olefin feedstock is selected from ethylene feedstock or ethylene and α-olefin feedstock; The α-olefin is selected from at least one of propylene, 1-butene, 1-hexene, 1-octene, norbornene, and norbornene derivatives; The norbornene derivative is selected from at least one of alkyl-substituted norbornene, alkoxy-substituted norbornene, vinyl-substituted norbornene, ester-substituted norbornene, amino-substituted norbornene, phenyl-substituted norbornene, and phenoxy-substituted norbornene.

10. The method according to claim 8, characterized in that, When the olefin feedstock is ethylene and α-olefin, the concentration of the α-olefin is 0.01~50 mol / L.

11. The method according to claim 8, characterized in that, The co-catalyst is selected from aluminum activators and / or borate auxiliaries.

12. The method according to claim 11, characterized in that, The aluminum activator is selected from at least one of C1-C8 alkylaluminoxanes and modified aluminoxanes.

13. The method according to claim 12, characterized in that, The modified aluminum oxane is selected from at least one of modified methyl aluminum oxane, modified ethyl aluminum oxane, and modified octyl aluminum oxane.

14. The method according to claim 11, characterized in that, The borate additive is selected from at least one of triphenylmethyltetra(pentafluorophenyl)borate, tetra(pentafluorophenyl)borate-methyl di-(octadecyl)ammonium salt, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

15. The method according to claim 8, characterized in that, When the co-catalyst is an aluminum activator, the molar ratio of the aluminum activator to the main catalyst is (3~5000):

1. Wherein, the molar amount of the aluminum activator is calculated as the molar amount of aluminum, and the molar amount of the main catalyst is calculated as the molar amount of the metal element in the main catalyst.

16. The method according to claim 8, characterized in that, When the co-catalyst is an aluminum activator, the molar ratio of the aluminum activator to the main catalyst is (50~5000):

1.

17. The method according to claim 8, characterized in that, When the cocatalyst is a borate promoter, the molar ratio of the borate promoter to the main catalyst is (1~40):

1. Wherein, the molar amount of the borate additive is expressed as the molar amount of boron, and the molar amount of the main catalyst is expressed as the molar amount of the metal element in the main catalyst.

18. The method according to claim 8, characterized in that, When the cocatalyst is a borate cocatalyst, the molar ratio of the borate cocatalyst to the main catalyst is (1~15):

1.

19. The method according to claim 8, characterized in that, In the mixture, the concentration of the main catalyst is 0.1~20 μmol / L, based on the molar concentration of the metal element in the main catalyst.

20. The method according to claim 8, characterized in that, The polymerization reaction is carried out at a temperature of 25~250 ℃ and for a time of 0.01~120 h.

21. The method according to claim 8, characterized in that, The polymerization reaction is carried out at a pressure of 0.1~40 MPa.

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