Catalyst for preparing olefin polymer with high molecular weight and high branching degree as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for preparing a high-molecular-weight and high-branching-degree olefin polymer as well as a preparation method and application of the catalyst, and belongs to the technical field of olefin catalytic polymerization. The invention provides a catalyst for preparing a high-molecular-weight and high-branching-degree olefin polymer, and the catalyst can realize catalytic polymerization of the same olefin or catalytic copolymerization of different olefins to obtain the high-molecular-weight and high-branching-degree olefin polymer. The number-average molecular weight Mn of the olefin polymer prepared through catalysis of the catalyst is 10-500 kg / mol, the branching degree of every 1000 carbons is 30-150, the stress is 1-40 MPa, the elongation at break is 500-3500%, the 10-time tensile recovery rate at 300% strain is 40%-90%, and the olefin polymer can be applied to packaging materials, high-performance films and polymer processing aids.

Description

Technical Field

[0001] This invention relates to a catalyst for preparing high molecular weight, highly branched olefin polymers, its preparation method, and its application, belonging to the field of olefin catalytic polymerization technology. Background Technology

[0002] Polyolefin elastomers are a class of thermoplastic elastomers polymerized from ethylene, propylene, or other α-olefins (such as 1-butene and 1-hexene) through metallocene or other catalysts. They combine the processability of plastics with the elasticity of rubber, making them excellent alternatives to traditional rubbers (such as EPDM). As modifiers, they enhance the properties of polypropylene and polyethylene. For example, when added to PP materials such as car bumpers, dashboards, and interior parts, they significantly improve their impact toughness. They are also used in PE pipes and films to improve resistance to slow crack growth and impact resistance. Furthermore, they serve as main materials in films, wires and cables, and footwear materials.

[0003] In the 1990s, Dow Chemical developed a defined geometry catalyst (CGC) and combined it with a high-temperature solution polymerization process to launch the Insite technology, achieving the industrial production of POE and producing the Engage™ series of elastomers (EP416815A2, 1991). Around the same time, ExxonMobil also developed the Exact™ series of polyolefin elastomers (WO9516716A1, 1995) using a bridged metallocene catalyst combined with the Exxpol process. Subsequently, LG Chem, Mitsui Chemicals, and Borealis developed unique metallocene catalysts and high-temperature solution polymerization processes, successfully producing different grades of POE. Currently, industrial POE production uses high-temperature solution polymerization (above 120 °C). The specificity of the polymerization process and the high activity and copolymerization performance of the catalyst at high temperatures are key to the high-temperature solution polymerization process for POE production. The main catalysts used in industrial high-temperature solution polymerization processes are Dow Chemical's CGC catalysts (…). Coord. Chem. Rev. 2006, 250 , 2691-2720) and ExxonMobil's bridged metallocene catalysts ( Chem. Rev. 2000, 100 (1205-1222). In 2024, Sinopec Beijing Research Institute of Chemical Industry adopted its independently developed solution polymerization technology, utilizing the unique "chain walking" characteristics of nickel-based metal catalysts in the ethylene polymerization process. During the polymerization process, branches of different lengths are continuously generated, and POE is prepared using ethylene as the sole monomer. This avoids the use of α-olefin monomers such as 1-octene, significantly reducing production costs. The product has excellent performance and can be used in photovoltaic, automotive, aerospace, wire and cable, construction and other fields.

[0004] Given the limited variety of catalysts available for the preparation of highly branched olefin polymers, it is essential to develop an efficient method and corresponding catalytic system for the direct preparation of branched high molecular weight polymers from inexpensive olefins such as ethylene and propylene to prepare polyolefin elastomers. Summary of the Invention

[0005] To overcome the above-mentioned technical defects, the present invention provides a catalyst for preparing high molecular weight, highly branched olefin polymers, its preparation method and application, and through the regulation of catalyst structure, high molecular weight, highly branched polymers can be directly prepared from ethylene and the like.

[0006] The technical solution of the present invention: One objective of this invention is to provide a catalyst compound for preparing high molecular weight, highly branched olefin polymers, the structure of which is shown in Formula I:

[0007] In the formula, R1 and R2 are each independently selected from halogens, -NO2, -NH2, -CN, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C14 aryl; or R1 and R2 are connected to form substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 heteroatoms selected from N, O, S or P; R3 is independently selected from -H, halogen, -NO2, -NH2, -CN, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C14 aryl; or R3 is connected to R2 to form substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 heteroatoms selected from N, O, S or P; R4, R5, R6, R7, and R8 are each independently selected from H, halogens, -NO2, -NH2, -CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S, or P, substituted or unsubstituted C6-C29 aryl, substituted or unsubstituted carbonyl (COR) a ), carboxyl group (CO2H), substituted or unsubstituted ester group (CO2R) a ), substituted or unsubstituted amide groups (CONH2, CONHR) a Or CONR a R b ), nitroso (NO), substituted or unsubstituted phosphono groups (OPR) a R b ), substituted or unsubstituted phosphonates [OP(OR a (OR) b )], substituted or unsubstituted phosphonamides [OP(NR a R b (NR) c R d )], sulfone group (-SO2R a ), -SR a ; or two adjacent R4, R5, R6, R7 and R8 are connected to form a substituted or unsubstituted C3-C8 heterocyclic alkyl group containing 1-3 heteroatoms selected from N, O, S or P, a substituted or unsubstituted C6-C14 aryl group, or a substituted or unsubstituted 5-14 heteroaryl group containing 1-3 heteroatoms selected from N, O, S or P; The R a R b R c R d Independently selected from -H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, and C6-C14 aryl; The substitution is performed by one or more of the following substituents: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, C6-C14 aryl, C6-C14 aryl, -C1-C6 alkyl.

[0008] Further specified, R1 and R2 are each independently selected from H, halogen, -NO2, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C14 aryl; or R1 and R2 are connected to form substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted 5-14 heteroaryl containing 1-3 heteroatoms selected from N, O, S or P.

[0009] Furthermore, R1 and R2 are linked together to form an anthracene- or methoxy-substituted unsaturated seven-membered ring.

[0010] Further specified, R3 is independently selected from H, halogen, -NO2, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, and substituted or unsubstituted C3-C8 cycloalkyl.

[0011] To further specify, R3 is H.

[0012] Further specifying, R8 can be methoxy, ethoxy, isopropoxy, or carbonyl (COR). a ), carboxyl group (CO2H), ester group (CO2R) a ), amide group (CONH2, CONHR) a Or CONR a R b ), nitroso (NO), phosphoyl (OPR) a R b ), phosphonates [OP(OR a (OR) b )], Phosphamide [OP(NR a R b (NR) c R d )] or sulfone group (-SO2R) a ).

[0013] To further specify, R a R b R c R d Independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O, S or P, and substituted or unsubstituted phosphinyl.

[0014] Further specifying, compound I is compound a of formula a:

[0015] In the formula, Y is 0-3 substituents, each independently selected from the following: halogen, -OH, -NO2, -NH2, -CN, oxo, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, and C6-C14 aryl.

[0016] Further specifying, the compound of formula II is the compound of formula b:

[0017] In the formula, Y is 0-3 substituents, each independently selected from the following: halogen, -OH, -NO2, -NH2, -CN, oxo, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, and C6-C14 aryl.

[0018] Further specifying, the structure of the compound is as shown in L1-1 to L2-5:

[0019]

[0020] .

[0021] A second objective of this invention is to provide a method for preparing the above-mentioned compound, the method being as follows: Will and A coupling reaction was performed to obtain compound I; Or will and A condensation reaction is carried out to obtain compound I.

[0022] Further specifying, the preparation equation for compound I is as follows: .

[0023] To further specify, the equation for compound B is as follows:

[0024] The preparation method is as follows: the compound shown in Formula A is prepared by a Friedel-Crafts reaction with a methanol reagent containing R6 or R8 in an anhydrous and oxygen-free argon atmosphere and in the presence of acidic ZnCl2.

[0025] Furthermore, the reaction temperature is specified as 120-160 ℃, and the reaction time as 0.5-2.0 h.

[0026] Further specifying, the preparation equation for compound I is as follows:

[0027] A third objective of this invention is to provide a complex formed by the combination of the aforementioned compound and a divalent metal salt via coordinate bonds.

[0028] Further specifying, the structure of the coordination compound is shown in formula IA:

[0029] In the formula, R9 and R 10 Each of the following is independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O, S or P, or substituted or unsubstituted phosphinyl; M is Ni or Pd.

[0030] Further specifying, M is Ni.

[0031] Further specifying, the structure of the complex is as shown in Ni1-1~N12-5:

[0032]

[0033] .

[0034] The fourth objective of this invention is to provide a method for preparing the above-mentioned complex, wherein the method comprises reacting the compound of formula I with a divalent or trivalent metal salt in an inert solvent to obtain the complex.

[0035] Further specifying, the divalent or trivalent metal salt is one or more of NiCl2, NiBr2, (TMEDA)NiPhCl, (TMEDA)NiPh(o-CF3)Cl, (PPh3)2NiPhCl, (PEt3)2NiPhCl, (TMEDA)NiMe2, NiI2, and (TMEDA)NiPh(o-CH3)Cl.

[0036] Further specifying, the inert solvent is an alcohol, an alkane, an aromatic hydrocarbon, or a halogenated hydrocarbon.

[0037] Furthermore, the inert solvent is a C5-C12 saturated hydrocarbon, halohydrocarbon, or aromatic hydrocarbon.

[0038] Furthermore, the inert solvent is specified as hexane, heptane, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, toluene, and xylene.

[0039] The fifth objective of this invention is to provide an application of the above-mentioned complex, specifically as a catalyst for the preparation of high molecular weight, highly branched olefin polymers.

[0040] The sixth objective of this invention is to provide a method for preparing a high molecular weight, highly branched olefin polymer. The method involves using a complex of formula IA as a catalyst in an inert solvent, with or without the addition of a co-catalyst, to catalytically polymerize the same olefin or catalytically copolymerize different olefins to obtain a high molecular weight, highly branched olefin polymer.

[0041] Further specifying, the cocatalyst is an alkylaluminum compound, Ni(cod)2, or an organoboron reagent.

[0042] Further specifying, when the co-catalyst is an alkylaluminum compound, the molar ratio of aluminum in the co-catalyst to the metal in the complex is 10-5000:1.

[0043] Furthermore, when the co-catalyst is an alkylaluminum compound, the molar ratio of aluminum in the co-catalyst to the metal in the complex is 1-100:1.

[0044] Further specifying, when the cocatalyst is Ni(cod)2 or an organoboron reagent, the molar ratio of the cocatalyst to the metal in the complex is 1-2:1.

[0045] To further specify, alkylaluminum compounds are compounds containing carbon-aluminum bonds.

[0046] Furthermore, the alkylaluminum compounds are methylaluminoxane (MAO), MMAO, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.

[0047] Further specifying, the co-catalyst is AlCl3 and / or alkylaluminum compounds. AlCl3 alone or together with alkylaluminum compounds can play a co-catalytic role and can also achieve the desired co-catalytic effect.

[0048] Further specifying, the organoboron reagent is tris(pentafluorophenylboron) or triphenylmethyltetra(pentafluorophenylboron).

[0049] Further specifying, the inert solvent is an alkane, aromatic hydrocarbon, ether, or haloalkanes.

[0050] Furthermore, the inert solvent is a C5-C12 saturated hydrocarbon, halohydrocarbon, or aromatic hydrocarbon.

[0051] Furthermore, the inert solvent is one or more of tetrahydrofuran, hexane, heptane, methylcyclohexane, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, toluene, chlorobenzene, and xylene.

[0052] Furthermore, the inert solvent is one or more of toluene, n-hexane, cyclohexane, methylcyclohexane, dichloromethane, 1,2-dichloroethane, chlorobenzene, and tetrahydrofuran.

[0053] Further specified, the reaction temperature is 0-100 ℃, the reaction time is 0.5-72 h, and the pressure is 0.1-4 MPa.

[0054] Further specifying, the preparation method of high molecular weight, highly branched olefin polymer is as follows: in an inert solvent, using a mixture of the above-mentioned compound of formula I or formula II and a divalent or trivalent metal salt as a catalyst, the olefin is catalytically polymerized with or without the addition of a co-catalyst to obtain high molecular weight, highly branched polyolefin.

[0055] The seventh objective of this invention is to provide a high molecular weight, highly branched olefin polymer prepared by the above method, wherein the polymer has a number-average molecular weight. M n It ranges from 10 to 500 kg / mol, with a branching degree of 30 to 150 per 1000 carbon atoms.

[0056] Further specifying, the stress of the above-mentioned high molecular weight, highly branched olefin polymer is 1-40 MPa, the elongation at break is between 500-3500%, and the recovery rate after 10 tensile cycles at 300% strain is 40%-90%.

[0057] The eighth objective of this invention is to provide an application of the above-mentioned high molecular weight, highly branched olefin polymer, specifically as a solubilizer or elastomer.

[0058] Beneficial effects: (1) This invention provides a catalyst for preparing high molecular weight, highly branched olefin polymers. This catalyst can directly yield high molecular weight, highly branched polyethylene from simple olefins such as ethylene, and significantly reduce costs. Furthermore, the number-average molecular weight of the olefin polymers prepared using this catalyst is [not specified in the original text]. M nIt has a strength of 10-500 kg / mol, a branching degree of 30-150 (the number of methyl groups corresponding to 1000 methylene groups in the polymer chain), a stress of 1-40 MPa, an elongation at break of 500-3500, and a recovery rate of 40%-90% after 10 tensile cycles at 300% strain. It can be used in packaging materials, high-performance films and polymer processing aids.

[0059] (2) In this invention, nickel or palladium complexes can undergo rapid β-H elimination during olefin polymerization to generate polyolefins containing double bonds and active species containing Ni(Pd)-H bonds. Further, the active species containing Ni(Pd)-H bonds recombine and insert with α-olefins to obtain Ni(Pd)-C bonds. The obtained Ni(Pd)-C bonds then start a polymerization reaction with ethylene in the system again. Finally, the catalytic cycle reaction is terminated by β-H elimination. Therefore, the generated polymer contains a large number of branches. Moreover, since the catalytic cycle is terminated by the metal β-H elimination, the polymer chain inevitably contains double bonds. Attached Figure Description

[0060] Figure 1 This is a schematic diagram of the single crystal structure of Ni1-2; Figure 2 This is a photograph of the polymer prepared in Example 2. Detailed Implementation

[0061] Unless otherwise specified, in all compounds described in this invention, the chiral centers without specified optical configurations can be of any configuration, such as R-type, S-type, racemic, etc.

[0062] In this invention, unless otherwise specified, the terms used have the general meanings known to those skilled in the art.

[0063] In this invention, "C1-C6 alkyl" refers to a straight-chain or branched alkyl group comprising 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, pterpentyl, or similar groups.

[0064] In this invention, the term "C3-C8 cycloalkyl" refers to a cyclic alkyl group having 3-8 carbon atoms on a ring, and non-limitingly includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. The term "C3-C6 cycloalkyl" has a similar meaning. The cycloalkyl ring may be fused to an aryl, heteroaryl, or heterocyclic ring, wherein the ring connected to the parent structure is a cycloalkyl group.

[0065] In this invention, the term "C1-C6 alkoxy" refers to a straight-chain or branched alkoxy group having 1-6 carbon atoms, and includes, without limitation, methoxy, ethoxy, propoxy, isopropoxy, and butoxy. Preferably, it is a C1-C4 alkoxy group.

[0066] In this invention, the term "heterocyclic group" refers to a 4-8 membered heterocyclic group containing 1, 2, or 3 heteroatoms selected from N, O, and S, including (but not limited to) the following groups: The heterocyclic ring may be fused to an aryl, heteroaryl, or cycloalkyl ring, wherein the ring connected to the parent structure is a heterocyclic group.

[0067] In this invention, the terms "aromatic ring" and "aryl" have the same meaning, and are preferably "C6-C10 aryl". The term "C6-C10 aryl" refers to an aromatic cyclic group with 6-10 carbon atoms that does not contain heteroatoms on the ring, such as phenyl or naphthyl. The aromatic ring may be fused to a heteroaryl, heterocyclic alkyl, or cycloalkyl ring, wherein the ring connected to the parent structure is an aromatic ring.

[0068] In this invention, the terms "aromatic heterocycle" or "heteroaryl" have the same meaning, referring to a heteroaromatic group containing one or more heteroatoms. For example, "C3-C10 heteroaryl" refers to an aromatic heterocycle containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen, and 3 to 10 carbon atoms. Non-limiting examples include: furanyl, thiophene, pyridinyl, pyrazolyl, pyrroleyl, N-alkylpyrroleyl, pyrimidinyl, pyrazinyl, imidazolyl, tetrazolyl, etc. The heteroaryl ring may be fused to an aryl, heterocyclic, or cycloalkyl ring, wherein the ring connected to the parent structure is the heteroaryl ring. The heteroaryl group may be optionally substituted or unsubstituted.

[0069] In this invention, the term "substitution" refers to the substitution of one or more hydrogen atoms on a specific group by a specific substituent. The specific substituent is the substituent described accordingly above, or the substituent appearing in the various embodiments. Unless otherwise specified, a substituted group may have a substituent selected from a specific group at any substituted site of that group, and the substituents may be the same or different at each position. Those skilled in the art will understand that the combinations of substituents contemplated in this invention are stable or chemically feasible combinations. Such substituents include, but are not limited to: halogens, hydroxyl groups, carboxyl groups (-COOH), C1-C6 alkyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, C3-C8 cycloalkyl groups, 3- to 12-membered heterocyclic groups, aryl groups, heteroaryl groups, C1-C8 aldehyde groups, C2-C10 acyl groups, C2-C10 ester groups, amino groups, C1-C6 alkoxy groups, C1-C10 sulfonyl groups, etc.

[0070] In this invention, the term "1-6" refers to 1, 2, 3, 4, 5, or 6. Other similar terms each have a similar meaning independently. The term "multiple" refers to 2-6, such as 2, 3, 4, 5, or 6.

[0071] It should be understood that when a group exists simultaneously at multiple different positions in a compound, its definition at each position is independent and can be the same or different. That is, the term "selected from the following group:" and the term "each independently selected from the following group:" have the same meaning.

[0072] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Unless otherwise stated, percentages and parts are weight percentages and parts by weight.

[0073] All ligands and nickel complexes in the following examples were analyzed by nuclear magnetic resonance spectroscopy (NMR spectroscopy). 1 Characterized by 1H NMR and elemental analysis.

[0074] Total polymer activity (10) 5 g·mol -1 ·h -1 The value is determined based on the quality of the polymer product.

[0075] The molecular weight distribution index (PDI) was determined using a polystyrene standard by gel permeation chromatography (GPC), and the unit is g·mol⁻¹. -1 .

[0076] The structure of highly branched polyethylene is composed of 13 The molecular weight was determined by comparing the molecular weight measured by C NMR and high-temperature GPC with the actual molecular weight measured by high-temperature laser light scattering.

[0077] Example 1: The synthesis of ligand L1-1 follows these steps:

[0078] (1) A mixture of 2-methoxyaniline (1.23 g, 10.0 mmol) and benzyl alcohol (3.69 g, 20.0 mmol) was added to a 100 mL Schlenk tube and heated to approximately 120 °C until melted. A zinc chloride solution (0.680 g, 5.00 mmol) and concentrated hydrochloric acid (10.0 mmol, 36.5%) were prepared in another 20.0 mL Schlenk tube and added to the above reaction mixture. After stirring at 160 °C for 30 minutes, water (approximately 20.0 mL) was added to quench the reaction, and Na₂CO₃ was added until bubbling of carbon dioxide ceased. The resulting mixture was extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate. After filtration, volatiles were removed by rotary evaporation under vacuum. Add ethanol (approximately 30.0 mL) to the crude product, filter to remove the solid, wash with additional ethanol (approximately 20.0 mL), collect and finally vacuum dry at 90 °C for 2 h to obtain a white solid Al[4.01 g, 88.2%; R] f = ~0.8 (ethyl acetate:hexane = 1:10)).

[0079]

[0080] 1 H NMR (400 MHz, Chloroform-d) δ 13.45 (s, 1H), 8.56 (s, 1H), 8.31 (s, 1H), 8.12 – 8.06 (m, 2H), 7.76 (dd, J = 8.6, 1.3 Hz, 2H), 7.50 – 7.37 (m,5H), 7.28 – 7.24 (m, 4H), 7.22 – 7.18 (m, 2H), 7.16 – 7.04 (m, 12H), 6.95 –6.90 (m, 4H), 6.68 (d, J = 1.8 Hz, 1H), 6.32 (d, J = 1.7 Hz, 1H), 5.68 (s, 1H), 5.42 (s, 1H), 3.70 (s, 3H). (2) Aniline A1 (4.00 g, 8.80 mmol), 2-methoxy-7-bromo-2,4,6-cycloheptatrien-1-one (1.72 g, 8.00 mmol) were added to a 100 mL Schlenk tube. Under anhydrous and oxygen-free conditions, Cs2CO3 (3.65 g, 11.2 mmol), rac-BINAP (0.99 g, 1.6 mmol), and Pd2(dba)3 (0.73, 0.8 mmol) were added and stirred at 110 °C for 24.0 h. The mixture was filtered, and volatiles were removed using a rotary evaporator. The crude product was further purified by column chromatography to obtain a yellow solid L1-1, which was dried under vacuum at 90 °C for 2 h (3.92 g, 83%; Rf = ~0.8 (ethyl acetate:hexane = 1:1)).

[0081] 1H NMR (400 MHz, Chloroform-d) δ 8.03 (s, 1H), 7.31 – 6.87 (m, 23H), 6.75 (t, J = 10.0 Hz, 1H), 6.69 – 6.61 (m, 2H), 6.51 (d, J = 1.9 Hz, 1H), 6.32 (d, J = 10.0 Hz, 1H), 5.54 (s, 1H), 5.46 (s, 1H), 3.96 (s, 3H), 3.56 (s, 3H). Example 2: Synthesis of ligand L1-2.

[0082]

[0083] The synthesis steps differ from those in Example 1 in that 2-(1-methylethoxy)aniline is used instead of 2-methoxyaniline in step (1), and dibenzothiazole is used instead of dibenzyl alcohol. The remaining process steps and parameter settings are the same as in Example 1. The structure of the aniline prepared in step (1) is shown in formula A2 below.

[0084]

[0085] Example 3: Synthesis of ligand L1-3.

[0086]

[0087] The synthesis steps differ from those in Example 1 in that 2-chloro-2,4,6-cycloheptatrien-1-one is used instead of 2-methoxy-7-bromo-2,4,6-cycloheptatrien-1-one in step (2), while the remaining process steps and parameter settings are the same as in Example 1.

[0088] Example 4: Synthesis of ligand L1-4.

[0089]

[0090] The synthesis steps differ from those in Example 1 in that 2-methoxy-6-methylaniline is used instead of 2-methoxyaniline in step (1). The remaining process steps and parameter settings are the same as in Example 1. The structure of the aniline prepared in step (1) is shown in formula A3 below.

[0091]

[0092] Example 5: Synthesis of ligand L1-5.

[0093]

[0094] The synthesis steps differ from those in Example 1 in that 2-isopropoxyaniline is used instead of 2-methoxyaniline in step (1). The remaining process steps and parameter settings are the same as in Example 1. The structure of the aniline prepared in step (1) is shown in formula A4 below.

[0095]

[0096] Example 6: Synthesis of ligand L1-6.

[0097]

[0098] The synthesis steps differ from those in Example 1 in that 2-chloro-2,4,6-cycloheptatrien-1-one is used instead of 2-methoxy-7-bromo-2,4,6-cycloheptatrien-1-one in step (2), and A4 is used instead of A1. The remaining process steps and parameter settings are the same as in Example 1.

[0099] Example 7: Synthesis of ligand L1-7.

[0100]

[0101] The synthesis steps differ from those in Example 1 in that p-methylaniline is used instead of 2-methoxyaniline in step (1). The remaining process steps and parameter settings are the same as in Example 1. The structure of the aniline prepared in step (1) is shown in formula A5 below.

[0102]

[0103] Example 8: Synthesis of ligand L1-8.

[0104]

[0105] The synthesis steps differ from those in Example 1 in that 2-chloro-2,4,6-cycloheptatrien-1-one is used instead of 2-methoxy-7-bromo-2,4,6-cycloheptatrien-1-one in step (2), and A5 is used instead of A1. The remaining process steps and parameter settings are the same as in Example 1.

[0106] Example 9: Synthesis of ligand L1-9.

[0107]

[0108] The synthesis steps differ from those in Example 1 in that 2-fluoro-4-methylaniline is used instead of 2-methoxyaniline in step (1). The remaining process steps and parameter settings are the same as in Example 1. The structure of the aniline prepared in step (1) is shown in the following formula A6.

[0109]

[0110] Example 10: Synthesis of ligand L2-1.

[0111]

[0112] The A1 (4.55 g, 10 mmol) and 2-hydroxy-1,4-naphthoquinone (1.74 g, 10 mmol, 1.0 equivalence) prepared in Example 1 were added to a 250 mL Schlenk tube, and 75 mL of toluene was added to dissolve the mixture. Then, trifluoroacetic acid (0.23 mL, 3.2 mmol) was added to the reactor as a reaction catalyst. The solution was stirred and heated at 110 °C for 24 h, cooled, and ligand crystals were crystallized. Finally, the crystals were filtered, washed with a small amount of water, and dried under vacuum at 70 °C for 12 h. The residual solution was purified by recrystallization from acetic acid to obtain a reddish-brown solid L2-1 [5.55 g, 90.7%; R f = ~0.8 (ethyl acetate:hexane = 1:5)).

[0113] 1H NMR (400 MHz, Benzene-d6) δ 7.97 (dd, J = 7.7, 1.3 Hz, 1H), 7.69 (dd, J = 7.7, 1.3 Hz, 1H), 6.94 (q, J = 1.2 Hz, 4H), 6.92 – 6.86 (m, 4H), 6.85 – 6.82 (m, 5H), 6.81 – 6.77 (m, 6H), 6.75 – 6.66 (m, 4H), 6.44 (d, J =1.8 Hz, 1H), 6.34 (d, J = 1.8 Hz, 1H), 5.67 (s, 1H), 5.37 (s, 1H), 5.13 (s, 1H), 2.77 (s, 3H). Example 11: Synthesis of ligand L2-2.

[0114]

[0115] The synthesis steps differ from those in Example 10 in that A2 prepared in Example 2 is used instead of A1 prepared in Example 1, while the remaining process steps and parameter settings are the same as in Example 10.

[0116] Example 12: Synthesis of ligand L2-3.

[0117]

[0118] The synthesis steps differ from those in Example 10 in that 2-methoxyaniline is used instead of A1 prepared in Example 1, while the remaining process steps and parameter settings are the same as in Example 10.

[0119] Example 13: Synthesis of ligand L2-4.

[0120]

[0121] The synthesis steps differ from those in Example 10 in that A6 prepared in Example 9 is used instead of A1 prepared in Example 1, while the remaining process steps and parameter settings are the same as in Example 10.

[0122] Example 14: Synthesis of ligand L2-5.

[0123]

[0124] The synthesis steps differ from those in Example 10 in that A5 prepared in Example 7 is used instead of A1 prepared in Example 1, while the remaining process steps and parameter settings are the same as in Example 10.

[0125] Example 15: Synthesis of complex Ni1-1.

[0126]

[0127] In a glove box, L1-1 (230 mg, 0.390 mmol) and KHMDS (77.8 mg, 0.390 mmol) were dissolved in toluene (10.0 mL) and stirred at room temperature for 2.0 h. After adding (PEt3)2NiPhCl (158.9 mg, 3.90 mmol), the reaction mixture was stirred at room temperature for 24.0 h. The mixture was concentrated to approximately 0.5 mL under vacuum and recrystallized from n-hexane (2.0 mL) at -30 °C. The precipitated yellow solid was collected and dried under vacuum at room temperature for approximately 2 h to give the orange product Ni1-1 (269.5 mg, 82.0%).

[0128] 1H NMR (400 MHz, Benzene-d6) δ 7.74 (d, J = 7.6 Hz, 1H), 7.33 (s, J =6.2 Hz, 3H), 7.25 – 6.57 (m, 24H), 6.38 (s, 1H), 6.09 – 5.83 (m, 3H), 5.31(s, 1H), 3.61 (s, 3H), 3.27 (s, 3H), 1.46 – 1.19 (m, 6H), 1.16-0.98 (m, 9H). Example 16: The synthesis of complex Ni1-2, and its single-crystal structure diagram are attached. Figure 1 As shown.

[0129]

[0130] The synthesis steps differ from those in Example 15 in that L1-2 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0131] Example 17: Synthesis of complex Ni1-3.

[0132]

[0133] The synthesis steps differ from those in Example 15 in that (PPh3)2NiPhCl is used instead of (PEt3)2NiPhCl, while the remaining process steps and parameter settings are the same as in Example 15.

[0134] Example 18: Synthesis of complex Ni1-4.

[0135]

[0136] The synthesis steps differ from those in Example 15 in that (PPh3)2NiPhCl is used instead of (PEt3)2NiPhCl, while the remaining process steps and parameter settings are the same as in Example 15.

[0137] Example 19: Synthesis of complex Ni1-5.

[0138]

[0139] The synthesis steps differ from those in Example 15 in that L1-5 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0140] Example 20: Synthesis of complex Ni1-6.

[0141]

[0142] The synthesis steps differ from those in Example 15 in that L1-6 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0143] Example 21: Synthesis of complex Ni1-7.

[0144]

[0145] The synthesis steps differ from those in Example 15 in that L1-7 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0146] Example 22: Synthesis of complex Ni1-8.

[0147]

[0148] The synthesis steps differ from those in Example 15 in that L1-8 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0149] Example 23: Synthesis of complex Ni1-9.

[0150]

[0151] The synthesis steps differ from those in Example 15 in that L1-9 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0152] Example 24: Synthesis of complex Ni2-1.

[0153]

[0154] The synthesis steps differ from those in Example 15 in that L2-1 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0155] Example 25: Synthesis of complex Ni2-2.

[0156]

[0157] The synthesis steps differ from those in Example 15 in that L2-2 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0158] Example 26: Synthesis of the complex Ni2-3.

[0159]

[0160] The synthesis steps differ from those in Example 15 in that L2-3 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0161] Example 27: Synthesis of the complex Ni2-4.

[0162]

[0163] The synthesis steps differ from those in Example 15 in that L2-4 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0164] Example 28: Synthesis of complex Ni2-5.

[0165]

[0166] The synthesis steps differ from those in Example 15 in that L2-5 is used instead of L1-1, while the remaining process steps and parameter settings are the same as in Example 15.

[0167] Examples of olefin polymerization are as follows: Example 1-1: Under an argon atmosphere, a toluene solution of the main catalyst Ni1-1 (1 μmol) and a heptane solution of the co-catalyst MMAO (500 μmol, 500 eq.) were added to a 50 mL autoclave. The mixture was stirred at 3 MPa and 60 °C for 0.50 h. After the reaction was completed, a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) was added to quench the reaction. The polymer was then washed three times with ethanol. The resulting polymer was vacuum dried at 60 °C to constant weight to obtain polyethylene.

[0168] Results: Yield: 0.71 g; Activity: 1.42 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 4.3 × 10 4 Molecular weight distribution (PDI): 2.4, branching degree: 56.

[0169] Examples 1-2: Under an argon atmosphere, a toluene solution of the main catalyst Ni1-1 (1 μmol) and a hexane solution of the co-catalyst triethylaluminum (5 μmol, 50 eq.) were added to a 50 mL autoclave. The mixture was stirred at 3 MPa and 60 °C for 0.50 h. After the reaction was completed, a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) was added to quench the reaction. The mixture was then washed three times with ethanol. The resulting polymer was dried under vacuum at 60 °C to constant weight to obtain polyethylene.

[0170] Results: Yield: 0.63 g; Activity: 1.23 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 4.1 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 54.

[0171] Examples 1-3: Under an argon atmosphere, a toluene solution of the main catalyst Ni1-1 (1 μmol) and a toluene solution of the co-catalyst Ni(cod)2 (2 μmol, 2.0 eq.) were added to a 50 mL autoclave. The mixture was stirred and polymerized at 3 MPa and 60 °C for 0.50 h. After the reaction was completed, ethanol was added and the mixture was washed three times. The resulting polymer was then vacuum dried at 60 °C to constant weight to obtain polyethylene.

[0172] Results: Yield: 0.80 g; Activity: 1.6 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h)M n ): 4.3 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 53.

[0173] Examples 1-4: The difference between this embodiment and embodiments 1-3 is that the temperature is 70℃ and the pressure is 1MPa. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0174] Results: Yield: 0.39 g; Activity: 7.8 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.6 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 87.

[0175] Examples 1-5: The difference between this embodiment and embodiments 1-4 is that the main catalyst is Ni1-2. The remaining process steps and parameter settings are the same as in embodiments 1-4.

[0176] Results: Yield: 0.44 g; Activity: 8.8 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 14.1 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 92.

[0177] Examples 1-6: The difference between this embodiment and Embodiments 1-5 is that the co-catalyst is diethylaluminum chloride. The remaining process steps and parameter settings are the same as in Embodiments 1-5.

[0178] Results: Yield: 0.23 g; Activity: 4.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 13.6 × 10 4 Molecular weight distribution (PDI): 2.3, branching degree: 86.

[0179] Examples 1-7: The difference between this embodiment and embodiments 1-5 is that the polymerization time is 1.0 h. The remaining process steps and parameter settings are the same as in embodiments 1-5.

[0180] Results: Yield: 0.91 g; Activity: 1.82 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n): 14.3 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 90.

[0181] Examples 1-8: The difference between this embodiment and embodiments 1-5 is that the polymerization temperature is 80℃. The remaining process steps and parameter settings are the same as in embodiments 1-5.

[0182] Results: Yield: 0.45 g; Activity: 9.0 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 11.5 × 10 4 Molecular weight distribution (PDI): 2.2, branching degree: 98.

[0183] Examples 1-9: The difference between this embodiment and Embodiments 1-3 is that the main catalyst is Ni1-3. The remaining process steps and parameter settings are the same as in Embodiments 1-3.

[0184] Results: Yield: 0.81 g; Activity: 1.62 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 4.5 × 10 4 Molecular weight distribution (PDI): 2.4, branching degree: 57.

[0185] Examples 1-10: The difference between this embodiment and Embodiments 1-9 is that the co-catalyst is triisobutylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-9.

[0186] Results: Yield: 0.73 g; Activity: 1.46 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 4.8 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 60.

[0187] Examples 1-11: The difference between this embodiment and embodiments 1-9 is that the polymerization temperature is 70℃ and the pressure is 1MPa. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0188] Results: Yield: 0.42 g; Activity: 8.4 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.3 × 10 4Molecular weight distribution (PDI): 2.1, Branching degree: 74.

[0189] Examples 1-12: The difference between this embodiment and Embodiments 1-3 is that the main catalyst is Ni1-4. The remaining process steps and parameter settings are the same as in Embodiments 1-3.

[0190] Results: Yield: 0.82 g; Activity: 1.64 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.1 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 62.

[0191] Examples 1-13: The difference between this embodiment and Embodiments 1-12 is that the co-catalyst is MAO. The remaining process steps and parameter settings are the same as in Embodiments 1-12.

[0192] Results: Yield: 0.79 g; Activity: 1.58 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 1.8 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 59.

[0193] Examples 1-14: The difference between this embodiment and embodiments 1-12 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-12.

[0194] Results: Yield: 0.32 g; Activity: 6.4 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 0.85 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 65.

[0195] Examples 1-15: The difference between this embodiment and embodiments 1-3 is that the main catalyst is Ni1-5. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0196] Results: Yield: 0.64 g; Activity: 1.28 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.5 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 61.

[0197] Examples 1-16: The difference between this embodiment and Embodiments 1-15 is that no co-catalyst is added during the polymerization process. The remaining process steps and parameter settings are the same as in Embodiments 1-15.

[0198] Results: Yield: 0.31 g; Activity: 6.2 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.4 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 57.

[0199] Examples 1-17: The difference between this embodiment and Embodiments 1-15 is that the co-catalyst is triethylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-15.

[0200] Results: Yield: 0.52 g; Activity: 1.02 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.1 × 10 4 Molecular weight distribution (PDI): 1.9, branching degree: 63.

[0201] Examples 1-18: The difference between this example and Examples 1-15 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in Examples 1-15.

[0202] Results: Yield: 0.25 g; Activity: 5.0 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.03 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 71.

[0203] Examples 1-19: The difference between this embodiment and embodiments 1-3 is that the main catalyst is Ni1-6. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0204] Results: Yield: 0.66 g; Activity: 1.32 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 4.1 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 46.

[0205] Examples 1-20: The difference between this embodiment and Embodiments 1-16 is that the main catalyst is Ni1-6. The remaining process steps and parameter settings are the same as in Embodiments 1-16.

[0206] Results: Yield: 0.30 g; Activity: 6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.8 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 50.

[0207] Examples 1-21: The difference between this embodiment and Embodiments 1-17 is that the main catalyst is Ni1-6. The remaining process steps and parameter settings are the same as in Embodiments 1-17.

[0208] Results: Yield: 0.54 g; Activity: 1.08 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.5 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 59.

[0209] Examples 1-22: The difference between this embodiment and Embodiments 1-18 is that the main catalyst is Ni1-6. The remaining process steps and parameter settings are the same as in Embodiments 1-18.

[0210] Results: Yield: 0.28 g; Activity: 5.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.3 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 62.

[0211] Examples 1-23: The difference between this embodiment and embodiments 1-3 is that the main catalyst is Ni1-7. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0212] Results: Yield: 0.76 g; Activity: 1.58 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 8.4 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 61.

[0213] Examples 1-24: The difference between this embodiment and Embodiments 1-23 is that the co-catalyst is triisobutylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-23.

[0214] Results: Yield: 0.73 g; Activity: 1.46 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 8.8 × 10 4 Molecular weight distribution (PDI): 2.0, branching degree: 64.

[0215] Examples 1-25: The difference between this embodiment and embodiments 1-23 is that the polymerization temperature is 70℃ and the pressure is 1MPa. The remaining process steps and parameter settings are the same as in embodiments 1-23.

[0216] Results: Yield: 0.43 g; Activity: 8.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 7.6 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 86.

[0217] Examples 1-26: The difference between this embodiment and Embodiments 1-25 is that the polymerization temperature is 80℃. The remaining process steps and parameter settings are the same as in Embodiments 1-25.

[0218] Results: Yield: 0.52 g; Activity: 1.04 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 7.1 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 93.

[0219] Examples 1-27: The difference between this embodiment and embodiments 1-3 is that the main catalyst is Ni1-8. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0220] Results: Yield: 0.76 g; Activity: 1.52 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 15.6 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 62.

[0221] Examples 1-28: The difference between this embodiment and Embodiments 1-24 is that the main catalyst is Ni1-8. The remaining process steps and parameter settings are the same as in Embodiments 1-24.

[0222] Results: Yield: 0.64 g; Activity: 1.28 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 16.5 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 60 Examples 1-29: The difference between this embodiment and Embodiments 1-25 is that the main catalyst is Ni1-8. The remaining process steps and parameter settings are the same as in Embodiments 1-25.

[0223] Results: Yield: 0.52 g; Activity: 1.02 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 8.6 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 81 Examples 1-30: The difference between this embodiment and Embodiments 1-26 is that the main catalyst is Ni1-8. The remaining process steps and parameter settings are the same as in Embodiments 1-26.

[0224] Results: Yield: 0.50 g; Activity: 1.0 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 8.0 × 10 4 Molecular weight distribution (PDI): 2.0, branching degree: 89.

[0225] Examples 1-31: The difference between this embodiment and embodiments 1-3 is that the main catalyst is Ni1-9. The remaining process steps and parameter settings are the same as in embodiments 1-3.

[0226] Results: Yield: 0.86 g; Activity: 1.72 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 6.8 × 10 4 Molecular weight distribution (PDI): 1.9, branching degree: 57.

[0227] Examples 1-32: The difference between this embodiment and Embodiments 1-31 is that the co-catalyst is MAO. The remaining process steps and parameter settings are the same as in Embodiments 1-31.

[0228] Results: Yield: 0.91 g; Activity: 1.82 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 6.2 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 60.

[0229] Examples 1-33: The difference between this embodiment and embodiments 1-31 is that the temperature is 70℃. The remaining process steps and parameter settings are the same as in embodiments 1-31.

[0230] Results: Yield: 0.86 g; Activity: 1.72 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 5.9 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 69.

[0231] Examples 1-34: The difference between this embodiment and embodiments 1-31 is that the temperature is 80℃. The remaining process steps and parameter settings are the same as in embodiments 1-31.

[0232] Results: Yield: 0.86 g; Activity: 1.72 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 5.2 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 73.

[0233] Examples 1-35: The difference between this embodiment and embodiments 1-34 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-34.

[0234] Results: Yield: 0.64 g; Activity: 1.28 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.9 × 10 4 Molecular weight distribution (PDI): 2.0, branching degree: 89.

[0235] Examples 1-36: The difference between this embodiment and Embodiments 1-3 is that the main catalyst is Ni2-1. The remaining process steps and parameter settings are the same as in Embodiments 1-3.

[0236] Results: Yield: 0.32 g; Activity: 6.4 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 16 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 30.

[0237] Examples 1-37: The difference between this embodiment and embodiments 1-36 is that the temperature is 90℃. The remaining process steps and parameter settings are the same as in embodiments 1-36.

[0238] Results: Yield: 0.85 g; Activity: 1.7 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 13.1 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 42.

[0239] Examples 1-38: The difference between this embodiment and embodiments 1-36 is that the temperature is 100℃. The remaining process steps and parameter settings are the same as in embodiments 1-36.

[0240] Results: Yield: 0.88 g; Activity: 1.76 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 10.1 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 56.

[0241] Examples 1-39: The difference between this embodiment and embodiments 1-38 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-38.

[0242] Results: Yield: 0.21 g; Activity: 4.2 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 7.8 × 10 4 Molecular weight distribution (PDI): 2.0, branching degree: 64.

[0243] Examples 1-40: The difference between this embodiment and Embodiments 1-36 is that the co-catalyst is triethylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-36.

[0244] Results: Yield: 0.41 g; Activity: 8.2 × 10⁻⁶ 5g / mol·h, number-average molecular weight (g / mol·h) M n ): 15.6 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 34.

[0245] Examples 1-41: The difference between this embodiment and Embodiments 1-36 is that the main catalyst is Ni2-2. The remaining process steps and parameter settings are the same as in Embodiments 1-36.

[0246] Results: Yield: 0.33 g; Activity: 6.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 44.2 × 10 4 Molecular weight distribution (PDI): 2.3, branching degree: 41.

[0247] Examples 1-42: The difference between this embodiment and Embodiments 1-41 is that the co-catalyst is triethylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-41.

[0248] Results: Yield: 0.31 g; Activity: 6.2 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 41.2 × 10 4 Molecular weight distribution (PDI): 2.3, branching degree: 43.

[0249] Examples 1-43: The difference between this embodiment and embodiments 1-41 is that the temperature is 100℃. The remaining process steps and parameter settings are the same as in embodiments 1-41.

[0250] Results: Yield: 0.86 g; Activity: 1.72 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 38.4 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 53.

[0251] Examples 1-44: The difference between this embodiment and embodiments 1-43 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-43.

[0252] Results: Yield: 0.53 g; Activity: 1.06 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) Mn ): 19.6 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 59.

[0253] Examples 1-45: The difference between this embodiment and Embodiments 1-36 is that the main catalyst is Ni2-3. The remaining process steps and parameter settings are the same as in Embodiments 1-36.

[0254] Results: Yield: 0.46 g; Activity: 9.2 × 10⁻⁶ g. 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 7.6 × 10 4 Molecular weight distribution (PDI): 2.0, Branching degree: 56.

[0255] Examples 1-46: The difference between this embodiment and embodiments 1-41 is that the temperature is 80℃. The remaining process steps and parameter settings are the same as in embodiments 1-41.

[0256] Results: Yield: 0.62 g; Activity: 1.24 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 5.6 × 10 4 Molecular weight distribution (PDI): 2.0, branching degree: 60.

[0257] Examples 1-47: The difference between this embodiment and embodiments 1-46 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-46.

[0258] Results: Yield: 0.43 g; Activity: 8.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.5 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 64.

[0259] Examples 1-48: The difference between this embodiment and Embodiments 1-36 is that the main catalyst is Ni2-4. The remaining process steps and parameter settings are the same as in Embodiments 1-36.

[0260] Results: Yield: 0.33 g; Activity: 6.6 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 3.2 × 10 4Molecular weight distribution (PDI): 2.0, branching degree: 30.

[0261] Examples 1-49: The difference between this embodiment and Embodiments 1-48 is that the polymerization temperature is 90℃. The remaining process steps and parameter settings are the same as in Embodiments 1-48.

[0262] Results: Yield: 0.71 g; Activity: 1.42 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 2.5 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 46.

[0263] Examples 1-50: The difference between this embodiment and embodiments 1-49 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-49.

[0264] Results: Yield: 0.49 g; Activity: 9.8 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 1.7 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 51.

[0265] Examples 1-51: The difference between this embodiment and Embodiments 1-36 is that the main catalyst is Ni2-5. The remaining process steps and parameter settings are the same as in Embodiments 1-36.

[0266] Results: Yield: 0.34 g; Activity: 6.8 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 18 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 36.

[0267] Examples 1-52: The difference between this embodiment and Embodiments 1-51 is that the co-catalyst is triisobutylaluminum. The remaining process steps and parameter settings are the same as in Embodiments 1-51.

[0268] Results: Yield: 0.31 g; Activity: 6.2 × 10⁻⁶ 5 g / mol·h, number-average molecular weight (g / mol·h) M n ): 19.3 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 38 Examples 1-53: The difference between this embodiment and Embodiments 1-51 is that the polymerization temperature is 100℃. The remaining process steps and parameter settings are the same as in Embodiments 1-51.

[0269] Results: Yield: 0.82 g; Activity: 1.64 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 16.8 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 47.

[0270] Examples 1-54: The difference between this embodiment and embodiments 1-53 is that the pressure is 1 MPa. The remaining process steps and parameter settings are the same as in embodiments 1-53.

[0271] Results: Yield: 0.62 g; Activity: 1.24 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 10.2 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 56.

[0272] Examples 1-55: The difference between this embodiment and embodiments 1-4 is that 1-hexene monomer (2 mL) was added. The remaining process steps and parameter settings are the same as in embodiments 1-4.

[0273] Results: Yield: 0.70 g; Activity: 1.4 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 15 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 90.

[0274] Examples 1-56: The difference between this embodiment and Embodiments 1-4 is that 1-octene monomer (2 mL) was added. The remaining process steps and parameter settings are the same as in Embodiments 1-4.

[0275] Results: Yield: 0.64 g; Activity: 1.3 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 14 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 88.

[0276] Examples 1-57: The difference between this example and Examples 1-44 is that 1-hexene monomer (5 mL) was added. The remaining process steps and parameter settings are the same as in Examples 1-44.

[0277] Results: Yield: 1.3 g; Activity: 2.6 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 45 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 50.

[0278] Examples 1-58: The difference between this embodiment and Embodiments 1-44 is that 1-octene monomer (5 mL) was added. The remaining process steps and parameter settings are the same as in Embodiments 1-44.

[0279] Results: Yield: 1.2 g; Activity: 2.4 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 43 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 49.

[0280] Examples 1-59: The difference between this embodiment and embodiments 1-4 is that propylene monomer (5.0 g) is added simultaneously. The remaining process steps and parameter settings are the same as in embodiments 1-4.

[0281] Results: Yield: 0.50 g; Activity: 1.0 × 10⁻⁶ 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 10 × 10 4 Molecular weight distribution (PDI): 2.1, Branching degree: 130.

[0282] Examples 1-60: The difference between this embodiment and Embodiments 1-44 is that propylene monomer (5.0 g) was added. The remaining process steps and parameter settings are the same as in Embodiments 1-44.

[0283] Results: Yield: 0.76 g; Activity: 1.5 × 10⁻⁶ g. 6 g / mol·h, number-average molecular weight (g / mol·h) M n ): 27 × 10 4 Molecular weight distribution (PDI): 2.2, Branching degree: 91.

[0284] The mechanical properties of the high molecular weight, highly branched polyethylene prepared in the above examples were characterized, and some results are shown in the table below:

[0285] The above description is only a preferred embodiment of the present invention. Given that those skilled in the art can make appropriate changes and modifications to the above embodiments, the present invention is not limited to the specific embodiments described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention.

Claims

1. A catalyst compound for preparing high molecular weight, highly branched olefin polymers, characterized in that, The structure is shown in Equation I: In the formula, R1 and R2 are each independently selected from halogens, -NO2, -NH2, -CN, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C14 aryl; or R1 and R2 are connected to form substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 heteroatoms selected from N, O, S or P; R3 is independently selected from -H, halogen, -NO2, -NH2, -CN, oxo (C=O), substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C14 aryl; or R3 is connected to R2 to form substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 heteroatoms selected from N, O, S or P; R4, R5, R6, R7, and R8 are each independently selected from H, halogens, -NO2, -NH2, -CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S, or P, substituted or unsubstituted C6-C29 aryl, substituted or unsubstituted carbonyl (COR) a ), carboxyl group (CO2H), substituted or unsubstituted ester group (CO2R) a ), substituted or unsubstituted amide groups (CONH2, CONHR) a Or CONR a R b ), nitroso (NO), substituted or unsubstituted phosphono groups (OPR) a R b ), substituted or unsubstituted phosphonates [OP(OR a (OR) b )], substituted or unsubstituted phosphonamides [OP(NR a R b (NR) c R d )], sulfone group (-SO2R a ), -SR a ; or two adjacent R4, R5, R6, R7 and R8 are connected to form a substituted or unsubstituted C3-C8 heterocyclic alkyl group containing 1-3 heteroatoms selected from N, O, S or P, a substituted or unsubstituted C6-C14 aryl group, or a substituted or unsubstituted 5-14 heteroaryl group containing 1-3 heteroatoms selected from N, O, S or P; The R a R b R c R d Independently selected from -H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, and C6-C14 aryl; The substitution is performed by one or more of the following substituents: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O, S or P, C6-C14 aryl, C6-C14 aryl, -C1-C6 alkyl.

2. The compound according to claim 1, characterized in that, The structures of the compounds are shown in L1-1 to L2-5: 。 3. A method for preparing the compound according to claim 1 or 2, characterized in that, The method is as follows: Will and A coupling reaction was performed to obtain compound I; Or will and A condensation reaction is carried out to obtain compound I.

4. A complex, characterized in that, It is formed by combining the compound of claim 1 or 2 with a divalent metal salt through coordination bonds; The structure of the complex is shown in Formula IA: In the formula, R9 and R 10 Each of the following is independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O, S or P, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O, S or P, or substituted or unsubstituted phosphinyl; M is Ni or Pd.

5. The complex according to claim 4, characterized in that, The structure of the complex is shown in Ni1-1~N12-5: 。 6. A method for preparing the complex according to claim 4 or 5, characterized in that, In an inert solvent, the compound of claim 1 is reacted with a divalent or trivalent metal salt to obtain a complex. The divalent or trivalent metal salt is one or more of NiCl2, NiBr2, (TMEDA)NiPhCl, (TMEDA)NiPh(o-CF3)Cl, (PPh3)2NiPhCl, (PEt3)2NiPhCl, (TMEDA)NiMe2, NiI2, and (TMEDA)NiPh(o-CH3)Cl.

7. An application of the complex according to claim 4 or 5, characterized in that, It can be used as a catalyst in the preparation of high molecular weight, highly branched olefin polymers.

8. A method for preparing a high molecular weight, highly branched olefin polymer, characterized in that, In an inert solvent, using the complex described in claim 4 or 5 as a catalyst, or a mixture of the compound described in claim 1 or 2 and a divalent or trivalent metal salt as a catalyst, the same olefin is catalytically polymerized or different olefins are catalytically copolymerized with or without the addition of a co-catalyst to obtain a high molecular weight, highly branched olefin polymer.

9. A high molecular weight, highly branched olefin polymer prepared by the method of claim 8, characterized in that, Number average molecular weight M n The strength is 10-500 kg / mol, the degree of branching per 1000 carbons is 30-150; the stress is 1-40 MPa, the elongation at break is between 500-3500%, and the recovery rate after 10 tensile cycles at 300% strain is 40%-90%.

10. The application of the high molecular weight, highly branched olefin polymer of claim 9, characterized in that, Used as a solubilizer or elastomer.

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