Aza binuclear macrocyclic complex of large volume cation and anion and its preparation method and application

Abstract

The application provides a kind of azabicyclometalated macrocyclic complex of formula (I) and its preparation method and application. As a catalyst, it can effectively catalyze the polymerization of ethylene and other olefins, and is suitable for continuous or intermittent solution method to prepare olefin materials, and has better catalytic effect than mononuclear metal complexes.

Description

Technical Field

[0001] This invention belongs to the field of polyolefin catalysts, specifically relating to a class of nitrogen-based binuclear bulk anionic and cationic complexes, their preparation methods, and applications. Background Technology

[0002] Solar energy is currently recognized as a green energy source, and photovoltaic (PV) cells are devices that directly convert solar energy into electrical energy through the photoelectric effect, possessing broad development and application prospects. The most important component of a PV cell is the solar cell chip, and the quality and stability of the PV encapsulation film directly affect the conversion efficiency and stability of the PV cell. Therefore, the encapsulation film material needs to possess characteristics such as good light transmittance, high adhesion, excellent aging resistance, and high resistivity.

[0003] Currently, EVA (ethylene-vinyl acetate copolymer) films are the most widely used, and my country has achieved domestic production from imports. However, these films are prone to aging, yellowing, cracking, and delamination during continuous use, which affects their conversion efficiency and lifespan, hindering their further application. Polyolefin elastomers are elastomers obtained by random copolymerization of ethylene and α-olefins. Compared with EVA, polyolefin elastomers have better thermal stability, optical properties, and resistance to drying cracks. They also have good flexibility and molding properties, and are economical, gradually becoming a good alternative to encapsulation films.

[0004] CN103289582 reports a cross-linked polyolefin elastomer encapsulating film for solar photovoltaic modules. The method involves grafting a silane coupling agent onto a polyolefin elastomer to obtain a grafted modified material, which is then mixed with cross-linking agents, cross-linking aids, antioxidants, and other additives, and extruded to form a polyolefin elastomer film. CN114015364A reports a polyolefin photovoltaic encapsulating film and its preparation method. The resin matrix of the upper polyolefin film, the core polyolefin film, and the lower polyolefin film are all polyolefin elastomers (copolymers of ethylene and butene). The film layers exhibit good compatibility, preventing interlayer separation during photovoltaic module use, thereby significantly improving module lamination efficiency.

[0005] Dow Chemicals conducted a comparative study of EVA films, ordinary POE films, and ENGAGE films. TM Properties of PV POE encapsulant films and the anti-PID performance of bifacial photovoltaic modules using different encapsulant films. TM The volume resistivity of PV POE film is 1-2 orders of magnitude higher than that of ordinary POE film and EVA film. Ordinary POE film exhibits significantly higher stability than EVA film, and ENGAGE TM Bifacial photovoltaic modules with PV POE encapsulant film exhibit excellent anti-PID performance.

[0006] As is well known, catalysts represent the core of olefin coordination polymerization technology. Since the advent of ethylene propylene rubber elastomers (EPR, EPDM) in the 1960s, major petrochemical companies and research institutions have invested heavily in developing catalyst technologies for olefin copolymerization. Early ethylene propylene rubber elastomers were prepared using traditional Z-type catalysts, while currently, the types of catalysts used in the industrial production of ethylene / α-olefin copolymer elastomers have expanded to include single-active-center metallocene catalysts and novel post-metallocene catalysts.

[0007] Exxon Petroleum Corporation (now ExxonMobil) was the first to file a patent for metallocene catalysts (US4871705A). This patent application covered both non-bridged and bridged bis-metallocene catalysts, thereby enabling control over the activity of olefin polymerization, the molecular weight and distribution of products, and the stereoselectivity for α-olefins, thus producing polymer products with specific properties.

[0008] Dow Chemical Company has filed a patent application (US5064802A) for a bridged semi-metallocene catalyst. This bridged monometallocene catalyst exhibits good thermal stability and excellent copolymerization performance at high temperatures, making it particularly suitable for the high-temperature solution process production of ethylene / α-olefin random copolymer elastomer POE. The company refers to this type of catalyst as a Constrained Geometry Catalyst (CGC) and has registered its CGC catalyst technology as the trademark Insite. TM In 1993, they pioneered the development of POE products with a narrow molecular weight distribution using this technology, branded as Engage. TM (US5064802A). ExxonMobil has registered its metallocene catalyst technology as the trademark Exxpol. TM They also quickly developed a PoE product, branded as Exact. TM The POE products developed based on these two types of metallocene catalysts are all vinyl elastomers, covering three types of random copolymers: ethylene / 1-butene, ethylene / 1-hexene, and ethylene / 1-octene.

[0009] EP241560A1 reported a non-bridged semi-metallocene catalyst and applied it to the homopolymerization of propylene and the copolymerization of ethylene and propylene, yielding products with molecular weights above 200,000, but with very low catalytic activity. In 1998, Kotohiro Nomura et al. found that this type of catalyst, combined with dried MAO (dMAO), exhibited similar catalytic activity to [Me2Si(C5Me4)(N t Bu)]TiCl2 is almost the same or even higher.

[0010] CN1431232 reported the preparation of a metallocene catalyst with a phenoxy side chain and conducted a study on the copolymerization of ethylene and hexene, achieving an activity of 6.3 × 10⁻⁶. 6 The catalyst has a molecular weight of 66,000-69,000 g / mol and a polymer molecular weight of 66,000-69,000 g / mol.

[0011] EP0874005 synthesized a series of highly active pre-transition metal catalysts by appropriately designing the structure of phenoxyimine ligands. Since these catalysts all contain phenoxyimine ligands, they are collectively referred to as FI catalysis.

[0012] WO2012103057A1 reports the structure of a non-bridged semi-ceramic catalyst and studies the polymerization reaction of this type of catalyst on the preparation of polyethylene elastomers from ethylene and 1-hexene.

[0013] CN 1173186A discloses a nitrogen-based metallocene polymerization catalyst and uses it for ethylene polymerization, achieving a polymerization activity of up to 70 kg / g Zr. No reports have been found on the homopolymerization of ethylene and α-olefins.

[0014] CN 1329940A discloses a transition metal catalyst containing a nitrogen-containing or diaza-containing framework, which exhibits an activity of 4.3 × 10⁻⁶ for ethylene polymerization. 5 The activity for the copolymerization of ethylene and 1-hexene can reach 2.3 × 10⁻⁶ g / mol·M·h. 5 g / mol·M·h, molecular weight distribution is 2.56, weight-average molecular weight M w 3.12×10 5 .

[0015] CN 1331252A discloses a metal catalyst containing pyridine-2-acylimide, which exhibits an activity of 1.3 × 10⁻⁶ for ethylene polymerization. 5 g / mol·M·h, no reports of copolymerization with α-olefins have been found.

[0016] However, the production process of polyolefin elastomers has always been a gap in the domestic materials industry. Developing polyolefin elastomer production processes with independent intellectual property rights is key to meeting the domestic demand for polyolefin elastomers. The key catalyst technologies and solution polymerization processes for preparing ethylene / α-olefin copolymer elastomers using high-temperature solution polymerization are almost all protected by foreign patents. Even for the catalytic systems disclosed in some patents that have expired or are about to expire, my country lacks in-depth understanding of the characteristics of these catalysts, and there are no reports of engineering research on high-temperature solution copolymerization of olefins.

[0017] Therefore, it is of great significance to develop low-cost catalytic systems and more efficient metal complex catalysts for the polymerization of ethylene and α-olefins. Summary of the Invention

[0018] This paper presents a nitrogen-binuclear bulk anionic-cationic complex of formula (I):

[0019]

[0020] M is selected from titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0021] Z is selected from the following groups, either unsubstituted or substituted by one, two, or more R0 groups: C 1-20 Alkylene, C 6-20 arylene, 5-20 heteroarylene, q is an integer from 0 to 20; each R0 may be the same or different, and is independently selected from hydrogen, halogen, C 1-20 alkyl;

[0022] Each R1, R2 may be the same or different, and is independently selected from hydrogen, without substitution or optionally by one, two or more R... a The following groups are substituted: C 1-20 Alkyl, C 6-20 Aryl, 5-20 heteroaryl; m selected from 0, 1, 2 or 3; n selected from 0, 1, 2, 3 or 4;

[0023] Alternatively, two adjacent R1s can be connected by end groups to form a fused ring of 5-20 heteroaryl groups together with the pyrrole ring;

[0024] Each R3 may be identical or different, and is independently selected from without substitution or arbitrarily determined by one, two or more R3s. b Replacement C 1-20 alkyl;

[0025] Each R4 may be identical or different, and is independently selected from hydrogen, halogens, and is unsubstituted or optionally converted by one, two or more R4 groups. b The following groups are substituted: C 1-20 Alkyl, C 1-20 Alkoxy, C 6-20 Aryl, C 6-20 Aryl C 1-20 alkyl;

[0026] Each R a R b They are the same or different, and are independently selected from halogens and C. 1-20 Alkyl, C 6-20 Aryl, 5-20 heteroaryl.

[0027] According to some embodiments, Z can be selected from the following groups, either unsubstituted or substituted by one, two or more R0 groups: C 1-6 Alkylene, C 6-14arylene, 5-14 heteroarylene, q is an integer from 0 to 6; each R0 may be the same or different, and is independently selected from hydrogen, halogen, C 1-6 alkyl;

[0028] Each R1 and R2 may be the same or different, and is independently selected from hydrogen, without substitution or optionally by one, two or more Rs. a The following groups are substituted: C 1-6 Alkyl, C 6-8 Aryl, 5-8 quinone heteroaryl, C 6-20 Aryl, 5-20 heteroaryl; m is selected from 0, 1, 2 or 3; n is selected from 0, 1 or 2;

[0029] Alternatively, two adjacent R1s can be connected by end groups to form a fused ring 5-14 membered heteroaryl group together with the pyrrole ring;

[0030] Each R3 can be the same or different, and can be independently selected from C3s that are unsubstituted or arbitrarily substituted by one, two or more Rb. 1-6 alkyl;

[0031] Each R4 may be the same or different, and may be independently selected from hydrogen, halogens, unsubstituted or optionally surrounded by one, two or more R4 groups. b Replacement C 1-6 Alkyl, C 1-6 Alkoxy, C 6-8 Aryl, C 6-8 Aryl C 1-6 alkyl;

[0032] Each R a R b They are the same or different, and are independently selected from halogens and C. 1-6 Alkyl, C 6-8 Aryl, 5-8 heteroaryl.

[0033] According to some implementation schemes, Z can be selected from C. 1-3 Alkylene, C 6-10 aryl, where q is 0, 1, 2 or 3;

[0034] R1 and R2 can be selected from C. 1-6 Alkyl, C 6-8 Aryl; or, two adjacent R1s are connected by terminal groups to form a fused ring of 5-10 heteroaryl groups together with the pyrrole ring;

[0035] R3 can be selected from C. 1-6 alkyl;

[0036] R4 can be selected from unsubstituted or arbitrarily assigned to one, two or more R4s. b Replacement C 6-8 Aryl;

[0037] Each R b They are the same or different, and are independently selected from halogens and C. 1-6 alkyl.

[0038] According to some implementation schemes, Z can be selected from substituted methylene, isopropylene, or phenylene, q = 0 or 1; R1 and R2 can be selected from H, methyl, isopropyl, or tert-butyl; or, two adjacent R1s are connected by terminal groups to form an indole group together with the pyrrole ring; R3 can be selected from methyl; and R4 can be selected from pentafluorophenyl.

[0039] According to some implementation schemes, the azabinuclear bulk anionic-cationic complexes shown in formula (I) are selected from:

[0040]

[0041]

[0042] This paper also provides a method for preparing the aza-binuclear bulk anionic-cationic complex represented by formula (I), including the following steps:

[0043]

[0044] 1) Compound I-2 reacts with R3-MgX to give alkylated complex I-1;

[0045] 2) Compound I-1 reacts with B(R4)3 to give the aza-binuclear bulk anionic-cationic complex shown in formula (I);

[0046] Wherein, M, Z, R1, R2, R3, R4, m, n, and q have the definitions described above; X1 is selected from Cl, Br, and I; X is selected from Cl, Br, and I;

[0047] According to some implementation schemes, in step 1), the reaction can be carried out in an organic solvent, which can be selected from at least one of tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dioxane, and 2-methyltetrahydrofuran;

[0048] According to some implementation schemes, in step 2), the reaction can be carried out in an organic solvent, which may be selected from toluene;

[0049] According to some implementation schemes, step 2) further includes a purification step after the reaction is completed, in which the reaction solution is added to a poor solvent to precipitate the aza-binuclear large-volume anionic-cationic complex of formula (I); the poor solvent may be selected from at least one of diethyl ether, methyl tert-butyl ether, n-hexane, cyclohexane, and petroleum ether.

[0050] This paper also provides the application of the aza-binuclear bulk anionic-cationic complex of formula (I) as a catalyst for catalytic polymerization of olefins, such as for the polymerization of ethylene and α-olefins.

[0051] Preferably, the aza-binuclear bulk anionic-cationic complex shown in formula (I) is used to catalyze the solution copolymerization of ethylene and α-olefins to prepare polyethylene elastomers.

[0052] According to some embodiments, the α-olefin may be 1-propylene, 1-butene, 1-pentene, and / or 1-hexene.

[0053] According to some implementation schemes, when the aza-binuclear bulk anionic-cationic complex shown in formula (I) is used as a catalyst to catalyze the polymerization of olefins, such as the polymerization of ethylene and α-olefins, the polymerization temperature can be 100℃-200℃, for example 120℃-180℃, and exemplary values ​​are 130℃, 140℃, 150℃, 160℃, and 170℃.

[0054] According to some implementation schemes, when the aza-binuclear bulk anionic-cationic complex shown in formula (I) is used to catalyze the polymerization of olefins, such as the polymerization of ethylene and α-olefins, the polymerization pressure can be 1-8 MPa, for example 2-6 MPa, exemplarily 3 MPa, 4 MPa, 5 MPa.

[0055] Beneficial effects

[0056] This invention provides a type of azabinuclear bulky anionic-cationic complex of formula (I), its preparation method, and its applications. The pairing of a bulky cationic compound with a bulky anion can stabilize the cationic complex; the larger the anionic group, the stronger the stability to the cationic group. As a catalyst, this type of ionic complex does not require large amounts of expensive methylaluminoxane (MAO) as a co-catalyst; only a small amount of alkylaluminum is needed to remove impurities (such as water) from the solvent to catalyze olefin polymerization.

[0057] When used as a catalyst, the complex prepared according to this invention can effectively catalyze the polymerization of ethylene and other olefins (such as α-olefins), and is suitable for the preparation of olefin materials by continuous or batch solution methods. Compared with mononuclear metal complex catalysts, the distance and interaction between metals directly affect the properties of the complex. The introduction of different substituents affects the electron cloud density and steric hindrance of the metal center, improving the catalyst activity while also significantly influencing the catalytic activity of olefin polymerization, the molecular weight, molecular weight distribution, and insertion rate of the polymer.

[0058] Terminology Definitions and Explanations

[0059] Unless otherwise stated, the numerical ranges described in this specification and claims are equivalent to describing at least each specific integer value therein. For example, the numerical range "1-20" is equivalent to describing each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-20", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0060] It should be understood that in this article, when describing one, two or more, "more" should refer to integers greater than 2, such as 3 or greater than or equal to 3, such as 3, 4, 5, 6, 7, 8, 9 or 10.

[0061] The term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0062] Term "C" 1-20 "Alkyl" should be understood as referring to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, "C 1-10 "Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. 1-8 "Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0063] Term "C" 6-20 "Aryl" should preferably be understood to represent a monocyclic, bicyclic (such as fused ring, bridged ring, spiro ring), or tricyclic hydrocarbon ring having 6 to 20 carbon atoms and possessing monovalent aromaticity or partial aromaticity. It can be a monoaromatic ring or a polyaromatic ring fused together, preferably "C". 6-14 "Aromatic". The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0064] The term "5-20-membered heteroaryl" should be understood to include monocyclic, bicyclic (e.g., fused, bridged, spirocyclic), or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzo[a]fused. "Hyperaryl" also refers to a group in which the heteroaryl ring is fused with one or more aryl, alicyclic, or heterocyclic rings, wherein the root or point of the connection is on the heteroaryl ring. Non-limiting examples include quinolinyl, isoquinolinyl, indolyl, benzo[b]thiophenyl, benzimidazolyl, and benzothiazolyl.

[0065] The term "spirocycle" refers to a ring system in which two rings share a single ring atom.

[0066] The term "fused ring" refers to a ring system in which two rings share two cyclic atoms.

[0067] The term "bridged ring" refers to a ring system in which two rings share three or more ring atoms. Detailed Implementation

[0068] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0069] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0070] The following embodiments involve testing the obtained product, and the testing process includes:

[0071] Density: The density of solids was tested according to GB / T 1033.1-2008 standard.

[0072] Melt flow index: Tested according to GB / T 3682-2000 standard, the test temperature is 190℃, and the weights of the weights are 2.16kg, 5kg and 21.6kg respectively. MFR(190 / 2.16) represents the melt flow index of the resin when the weight of the weight is 2.16kg.

[0073] Molecular weight (Mw): Tested according to GB / T 36214.4-2018 standard.

[0074] PDI (Polymer Dispersion Index): Tested according to GB / T 36214.4-2018 standard.

[0075] Elemental analysis: Tested using a German vario EL cube elemental analyzer. Inductively coupled plasma atomic emission spectrometry (ICP-AES): Tested using an Agilent 5800. Mass content of α-olefins: determined by nuclear magnetic resonance (NMR). 1 The H NMR spectrum was used to determine the identity.

[0076] Catalyst activity: Calculated based on the quality of the product obtained and the quality of the catalyst used after the reaction process involving the catalyst is completed.

[0077] [Example 1]

[0078] Preparation of complex a and its polymerization reaction

[0079]

[0080] Preparation of intermediate 1

[0081]

[0082] Intermediate 1

[0083] 3 mmol of 4,4'-biphenyldiamine and 6 mmol of 2-pyrrolecarboxaldehyde were added to a 500 mL three-necked flask, followed by 150 mL of toluene and 5 drops of acetic acid. A water separator and reflux condenser were then added, and the mixture was heated to reflux overnight. The reaction mixture was cooled to room temperature with stirring, and a grayish-white solid precipitated. The solid was filtered and washed three times with 30 mL of n-hexane, yielding 88%. Elemental analysis results were: C%: 78.03 (theoretical value 78.08); H%: 5.37 (theoretical value 5.36); N%: 16.60 (theoretical value 16.56).

[0084] Preparation of intermediate 2

[0085]

[0086] Intermediate 2

[0087] Take 5 mmol of intermediate 1, add 150 mL of dry toluene and stir to dissolve. Add 10.2 mmol of triethylamine dropwise and stir for 1 h. Add 10 mmol of TiCl4 in toluene solution dropwise through a constant pressure dropping funnel at room temperature and stir for 72 h at room temperature. Filter under nitrogen protection, concentrate the filtrate to about 10 mL under vacuum at 40 °C. Add 30 mL of n-hexane, filter under nitrogen protection, wash the solid twice with 20 mL of hexane to obtain a deep yellow complex, which is intermediate 2, with a yield (ω) of 56%. Elemental analysis results are as follows: C%: measured value 40.97 (theoretical value 40.98); H%: 2.55 (theoretical value 2.50); ​​N%: 8.66 (theoretical value 8.69); Ti%: 14.82 (theoretical value 14.85). 1 1H NMR (δ, CDCl3): 6.30 (2H, multi-peak); 6.78 (2H, dd peak); 7.26-7.33 (6H, multi-peak); 7.53 (4H, double peak); 8.51 (2H, single peak).

[0088] Preparation of intermediate 3

[0089]

[0090] 3 mmol of the intermediate was added to 100 mL of diethyl ether, and 9.2 mL of methylmagnesium chloride (2M) reagent was added dropwise. The mixture was stirred at room temperature for 5 h. Under nitrogen protection, the diethyl ether was removed under reduced pressure at room temperature to a final volume of 10 mL. 20 mL of n-hexane was added, and the mixture was filtered under nitrogen protection. The solution was washed twice with 10 mL of anhydrous n-hexane. Intermediate 3 was obtained, with a yield of 70%. Elemental analysis results were as follows: C%: 64.39 (theoretical value 64.38); H%: 6.58 (theoretical value 6.56); N%: 10.70 (theoretical value 10.73); Ti%: 18.33 (theoretical value 18.33).

[0091] Preparation of complex a

[0092] Intermediate 3 (0.5 mmol) was added to a sample vial, followed by 3 mL of toluene and stirring to dissolve. Tris(pentafluorophenyl)borane (1.2 mmol) was then added, and the mixture was stirred for 2 hours. 15 mL of diethyl ether was added, and the mixture was stirred and placed in a refrigerator. A solid precipitated, was filtered, and washed three times with diethyl ether to obtain complex a, with a yield of 75%. Elemental analysis results were as follows: C%: 49.70 (theoretical value 49.71); H%: 2.25 (theoretical value 2.22); N%: 3.58 (theoretical value 3.62); Ti%: 6.18 (theoretical value 6.19).

[0093] A 0.5 μmol / mL toluene solution of complex a was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of triisobutylaluminum (TIBA) / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0094] [Example 2]

[0095] Preparation of complex b and its polymerization reaction

[0096]

[0097] Referring to Example 1, complex b was synthesized using 3,3',5,5'-tetramethyl-4,4'-biphenyldiamine, 2-aldehyde pyrrole, and titanium tetrachloride as starting materials, with an overall yield of 67%. Elemental analysis results were as follows: C%: measured value 50.98 (theoretical value 50.97); H%: 2.60 (theoretical value 2.64); N%: 3.53 (theoretical value 3.50); ​​Ti%: 5.96 (theoretical value 5.97).

[0098] A 0.5 μmol / mL toluene solution of complex b was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0099] [Example 3]

[0100] Preparation of complex C and its polymerization reaction

[0101]

[0102] Referring to Example 1, complex c was synthesized using 3,3',5,5'-tetraisopropyl-4,4'-biphenyldiamine, 2-aldehyde pyrrole, and titanium tetrachloride as starting materials, with an overall yield of 64%. Elemental analysis results were as follows: C%: measured value 53.25 (theoretical value 53.24); H%: 3.38 (theoretical value 3.41); N%: 3.32 (theoretical value 3.27); Ti%: 5.57 (theoretical value 5.58).

[0103] A 0.5 μmol / mL toluene solution of complex c was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0104] [Example 4]

[0105] Preparation of complex d and its polymerization reaction

[0106]

[0107] Referring to Example 1, complex d was synthesized using 3,3',5,5'-tetratert-butyl-4,4'-biphenyldiamine, 2-aldehyde pyrrole, and titanium tetrachloride as starting materials, with an overall yield of 67%. Elemental analysis results were as follows: C%: measured value 54.28 (theoretical value 54.26); H%: 3.74 (theoretical value 3.76); N%: 3.15 (theoretical value 3.16); Ti%: 5.42 (theoretical value 5.41).

[0108] A 0.5 μmol / mL toluene solution of complex d was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0109] [Example 5]

[0110] Preparation of complex e and its polymerization reaction

[0111]

[0112] Referring to Example 1, complex e was synthesized using 3 mmol of 4,4'-biphenyldiamine, 6 mmol of 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 64%. Elemental analysis results were as follows: C%: measured value 52.56 (theoretical value 52.53); H%: 2.30 (theoretical value 2.33); N%: 3.39 (theoretical value 3.40); Ti%: 5.79 (theoretical value 5.81).

[0113] A 0.5 μmol / mL toluene solution of complex e was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0114] [Example 6]

[0115] Preparation of complex f and its polymerization reaction

[0116]

[0117] Referring to Example 1, complex f was synthesized using 3,3',5,5'-tetramethyl-4,4'-biphenyldiamine, 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 73%. Elemental analysis results were as follows: C%: measured value 53.65 (theoretical value 53.62); H%: 2.70 (theoretical value 2.72); N%: 3.32 (theoretical value 3.29); Ti%: 5.64 (theoretical value 5.62).

[0118] A 0.5 μmol / mL toluene solution of complex f was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and then vacuum dried. The polymerization results are shown in Table 1.

[0119] [Example 7]

[0120] Preparation of complex g and its polymerization reaction

[0121]

[0122] Referring to Example 1, using 3,3',5,5'-tetraisopropyl-4,4'-biphenyldiamine, 2-aldehyde indole, and titanium tetrachloride as starting materials, a complex g was synthesized with an overall yield of 71%. Elemental analysis results were as follows: C%: measured value 55.59 (theoretical value 55.60); H%: 3.42 (theoretical value 3.44); N%: 3.11 (theoretical value 3.09); Ti%: 5.27 (theoretical value 5.28).

[0123] A 0.5 μmol / mL toluene solution of complex g was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed on the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0124] [Example 8]

[0125] Preparation of complex h and its polymerization reaction

[0126]

[0127] Referring to Example 1, complex h was synthesized using 3,3',5,5'-tetratert-butyl-4,4'-biphenyldiamine, 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 75%. Elemental analysis results were as follows: C%: measured value 56.52 (theoretical value 56.50); ​​H%: 3.78 (theoretical value 3.77); N%: 3.00 (theoretical value 2.99); Ti%: 5.14 (theoretical value 5.12).

[0128] A 0.5 μmol / mL toluene solution of complex h was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and then vacuum dried. The polymerization results are shown in Table 1.

[0129] [Example 9]

[0130] Preparation of Complex i and its Polymerization Reaction

[0131]

[0132] Referring to Example 1, complex i was synthesized using 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline, 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 73%. Elemental analysis results were as follows: C%: 53.87 (theoretical value 53.88); H%: 2.80 (theoretical value 2.82); N%: 3.24 (theoretical value 3.26); Ti%: 5.60 (theoretical value 5.58).

[0133] A 0.5 μmol / mL toluene solution of complex i was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0134] [Example 10]

[0135] Preparation of complex j and its polymerization reaction

[0136]

[0137] Referring to Example 1, complex j was synthesized using 2,2-bis(3,5-dimethyl-4-aminophenyl)propane, 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 78%. Elemental analysis results were as follows: C%: measured value 54.37 (theoretical value 54.39); H%: 2.98 (theoretical value 3.00); N%: 3.20 (theoretical value 3.21); Ti%: 5.47 (theoretical value 5.49).

[0138] A 0.5 μmol / mL toluene solution of complex j was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0139] [Example 11]

[0140] Preparation and polymerization reaction of complex k

[0141]

[0142] Referring to Example 1, complex j was synthesized using 1,4-bis(3,5-dimethyl-4-aminophenyl)benzene, 2-aldehyde indole, and titanium tetrachloride as starting materials, with an overall yield of 75%. Elemental analysis results were as follows: C%: measured value 55.37 (theoretical value 55.37); H%: 2.85 (theoretical value 2.83); N%: 3.12 (theoretical value 3.15); Ti%: 5.40 (theoretical value 5.38).

[0143] A 0.5 μmol / mL toluene solution of complex K was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0144] [Example 12]

[0145] Preparation of complex 1 and its polymerization reaction

[0146]

[0147] Referring to Example 1, complex f was synthesized using 3,3',5,5'-tetramethyl-4,4'-biphenyldiamine, 2-aldehyde indole, and zirconium tetrachloride as starting materials, with an overall yield of 76%. Elemental analysis results were as follows: C%: measured value 51.00 (theoretical value 51.02); H%: 2.60 (theoretical value 2.59); N%: 3.12 (theoretical value 3.13); Zr%: 10.19 (theoretical value 10.20).

[0148] A 0.5 μmol / mL toluene solution of complex 1 was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed onto the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0149] [Example 13]

[0150] Preparation and polymerization reaction of complex m

[0151]

[0152] Referring to Example 1, complex f was synthesized using 3,3',5,5'-tetramethyl-4,4'-biphenyldiamine, 2-aldehyde indole, and hafnium tetrachloride as starting materials, with an overall yield of 74%. Elemental analysis results were as follows: C%: 53.65 (theoretical value 46.48); H%: 2.70 (theoretical value 2.36); N%: 3.32 (theoretical value 2.85); Ti%: 5.64 (theoretical value 18.18).

[0153] A 0.5 μmol / mL toluene solution of complex m was prepared in a glove box as the catalyst solution. 0.5 mL of the catalyst solution was added to the catalyst container from the glove box. A 500 mL jacketed stainless steel high-pressure reactor was purged with nitrogen three times, and the catalyst container was transferred out of the glove box and installed on the reactor. 300 mL of n-hexane, 30 mL of 1-hexene, and 10 mL of TIBA / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 90 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced until the pressure reached 4 MPa. After the reaction temperature reached 100 °C, the catalyst solution in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 5 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was quenched with ethanol acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed three times with ethanol and dried under vacuum. The polymerization results are shown in Table 1.

[0154] [Example 14] Same as Example 2, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0155] [Example 15] Same as Example 3, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0156] [Example 16] Same as Example 4, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0157] [Example 17] Same as Example 5, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0158] [Example 18] Same as Example 6, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0159] [Example 19] Same as Example 7, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0160] [Example 20] Same as Example 8, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0161] [Example 21] Same as Example 9, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0162] [Example 22] Same as Example 10, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0163] [Example 23] Same as Example 11, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0164] [Example 24] Same as Example 12, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0165] [Example 25] Same as Example 13, except that 13.7g of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0166] [Example 26] Same as Example 6, except that the amount of 1-hexene added was 20 mL. The polymerization results are shown in Table 1.

[0167] [Example 27] Same as Example 6, except that 40 mL of 1-hexene was added. The polymerization results are shown in Table 1.

[0168] [Example 28] Same as Example 6, except that the polymerization temperature was controlled at 130°C. The polymerization results are shown in Table 1.

[0169] [Example 29] Same as Example 6, except that the polymerization temperature was controlled at 100°C. The polymerization results are shown in Table 1.

[0170] [Example 30] Same as Example 6, except that the polymerization pressure was controlled at 6 MPa. The polymerization results are shown in Table 1.

[0171] [Example 31] Same as Example 6, except that the polymerization pressure was controlled at 2 MPa. The polymerization results are shown in Table 1.

[0172] Table 1. Aggregation Results

[0173]

[0174]

[0175] The embodiments of the technical solution of the present invention have been described above by way of example. It should be understood that the protection scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the protection scope of the claims of this application.

Claims

1. A large-volume anionic-cationic complex of formula (I): （I） in, M is selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); Z is selected from C 1-3 Alkylene, C 6-10 aryl, q is 0 or 1; R1 is hydrogen; m is selected from 0, 1, 2 or 3; Alternatively, two adjacent R1s are connected by end groups and together with the pyrrole ring form an indole group; Each R2 may be the same or different, and each is independently selected from hydrogen or C. 1-6 Alkyl group; n is selected from 0, 1, 2, 3 or 4; R3 is a methyl group; R4 is pentafluorophenyl.

2. The complex according to claim 1, characterized in that, Z is selected from methylene, isopropylene, and phenylene, q=0 or 1; R1 is H; or, two adjacent R1s are connected by terminal groups to form an indole group together with the pyrrole ring; R2 is selected from H, methyl, isopropyl, and tert-butyl; R3 is methyl; R4 is pentafluorophenyl.

3. The complex according to claim 1, characterized in that, The structure is selected from: 、 、 ab 、 、 cd 、 、 ef 、 、 gh 、 、 ij 、 、 k l m。 4. A method for preparing the complex according to any one of claims 1-3, comprising the following steps: 1) Compound I-2 reacts with R3-MgX to give alkylated complex I-1; 2) Compound I-1 reacts with B(R4)3 to obtain the complex described above; Wherein, M, Z, R1, R2, R3, R4, m, n, and q have the definitions described in any one of claims 1-3; X1 is selected from Cl, Br, and I; X is selected from Cl, Br, and I.

5. The preparation method according to claim 4, characterized in that, In step 1), the reaction is carried out in an organic solvent selected from at least one of tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dioxane, and 2-methyltetrahydrofuran.

6. The preparation method according to claim 4, characterized in that, In step 2), the reaction is carried out in an organic solvent, which is selected from toluene.

7. The preparation method according to claim 4, characterized in that, In step 2), after the reaction is completed, a purification step is also included, in which the reaction solution is added to a poor solvent to precipitate the complex; the poor solvent is selected from at least one of diethyl ether, methyl tert-butyl ether, n-hexane, cyclohexane, and petroleum ether.

8. The use of the complex according to any one of claims 1-3 as a catalyst for catalyzing the polymerization of ethylene and α-olefins.

9. The application according to claim 8, characterized in that, The complex is used to catalyze the solution copolymerization of ethylene and α-olefins to prepare polyethylene elastomers.

10. The application according to claim 8, characterized in that, The α-olefin is selected from 1-propylene, 1-butene, 1-pentene, and / or 1-hexene.

11. The application according to claim 8, characterized in that, The polymerization temperature is 100℃-200℃; The polymerization pressure is 1-8 MPa.

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