Bulk cation-anion complex and preparation method and application thereof

Abstract

This invention provides a type of diketone-semi-celocene metal bulk anionic and cationic complex of formula (I), its preparation method, and its applications. When used as a catalyst, it can effectively catalyze the polymerization of ethylene and other olefins (such as α-olefins), and is suitable for continuous or batch solution methods to prepare olefin materials. It provides a novel and better catalytic system for the polymerization of ethylene and other olefins (such as α-olefins).

Description

Technical Field

[0001] This invention belongs to the field of polyolefin catalysts, specifically relating to a class of large-volume anion-cation pairing compounds, 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 materials used for the encapsulation film need to be selected for their 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] Patent CN103289582 reports a cross-linked polyolefin elastomer encapsulating film for solar photovoltaic modules. The process 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 film to obtain the polyolefin elastomer encapsulating film.

[0005] Patent CN114015364A reports a polyolefin photovoltaic encapsulation 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 (polymers of ethylene and butene). The film layers have good compatibility and will not cause interlayer separation during the use of photovoltaic modules, thereby significantly improving the lamination efficiency of the modules.

[0006] 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.

[0007] 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.

[0008] 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.

[0009] Dow Chemical Company has applied for a patent for a bridged semi-metallocene catalyst, US5064802A. 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 to produce ethylene / α-olefin random copolymer elastomer POE.

[0010] Steven et al. of Dow Chemical Company also refer to this type of catalyst as a Constrained Geometry Catalyst (CGC). Dow has registered its CGC catalyst technology as a 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.

[0011] EP241560A1 reported a non-bridging 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. discovered that this type of catalyst, combined with dried MAO (dMAO), could catalyze the copolymerization of ethylene with 1-butene or 1-hexene to obtain [Me2Si(C5Me4)(N tBu)]TiCl2 has almost the same or even higher catalytic activity.

[0012] 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.

[0013] Patent CN1132855 reported the synthesis of [O,O]CpMX and studied its catalytic performance for the polymerization of styrene and ethylene, but no study on the catalytic performance of this catalyst for the copolymerization of ethylene and α-olefins has been reported.

[0014] 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.

[0015] 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.

[0016] CN111187291A reports a class of amine bisphenol tetradentate ligand metal catalysts and their applications, which can catalyze the copolymerization reaction of ethylene and hexene when alkylaluminoxanes or mixtures of alkylaluminum and organoboron additives are used as cocatalysts.

[0017] 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.

[0018] Therefore, it is of great significance to develop effective and more efficient metal complex catalysts for the polymerization of ethylene and α-olefins. Summary of the Invention

[0019] To address the aforementioned technical problems, this paper provides a large-volume anion-cation complex of formula (I):

[0020]

[0021] M is selected from titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0022] Cy is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Ra: cyclopentadienyl, indenyl, fluorenyl;

[0023] Each R1 and R2 may be the same or different, and is independently selected from hydrogen, and consists of the following groups that are unsubstituted or optionally substituted by one, two or more Rb groups: C 1-20 Alkyl, C 6-20 Aryl, 5-20 heteroaryl; m selected from 0, 1, 2, 3 or 4; n selected from 0, 1, 2, 3 or 4;

[0024] Alternatively, two adjacent R1s can be connected by end groups to form a fused ring C with the benzene ring. 6-20 The aryl group, and / or two adjacent R2 groups, can be connected by end groups to form a fused ring C with the benzene ring. 6-20 Aryl;

[0025] R3 is selected from C3 that is unsubstituted or optionally substituted by one, two or more Rc. 1-20 alkyl;

[0026] Each R4 may be identical or different, and is independently selected from hydrogen, halogen, unsubstituted or optionally substituted by one, two or more Rc groups of the following groups: C 1-20 Alkyl, C 1-20 Alkoxy, C 6-20 Aryl, C 6-20 Aryl C 1-20 alkyl;

[0027] Each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-20 Alkyl, C 6-20 Aryl, 5-20 heteroaryl;

[0028] Each Rc may be the same or different, and is independently selected from halogens, C 1-20 Alkyl, C 6-20 Aryl, 5-20 heteroaryl.

[0029] According to some implementation schemes, Cy can be selected from cyclopentadienyl or pentamethylcyclopentadienyl;

[0030] Each R1 and R2 may be the same or different, and is independently selected from hydrogen, unsubstituted or optionally substituted by one, two or more Rb groups of the following groups: 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 or 2; n is selected from 0, 1 or 2;

[0031] Alternatively, two adjacent R1s can be connected by end groups to form a fused ring C with the benzene ring. 10-14The aryl group, and / or two adjacent R2 groups, can be connected by end groups to form a fused ring C with the benzene ring. 10-14 Aryl;

[0032] R3 is selected from C3 that is unsubstituted or optionally substituted by one, two or more Rc. 1-6 alkyl;

[0033] Each R4 may be the same or different, and is independently selected from hydrogen, halogen, unsubstituted or optionally substituted by one, two or more Rc groups of the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 6-8 Aryl, C 6-8 Aryl C 1-6 alkyl;

[0034] Each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-6 Alkyl, C 6-8 Aryl, 5-8 quinone heteroaryl;

[0035] Each Rc may be the same or different, and is independently selected from halogens, C 1-6 Alkyl, C 6-8 Aryl, 5-8 heteroaryl.

[0036] According to some implementation schemes, R1 and R2 can be selected from C. 1-6 Alkyl, C 6-8 Aryl;

[0037] Alternatively, two adjacent R1s may be connected by end groups to form naphthyl or anthracene with the benzene ring, and / or two adjacent R2s may be connected by end groups to form naphthyl or anthracene with the benzene ring.

[0038] R3 can be selected from C. 1-6 alkyl;

[0039] R4 can be selected from C4 that is unsubstituted or optionally substituted by one, two or more Rc. 6-8 Aryl;

[0040] Each Rc may be the same or different, and is independently selected from halogens, C 1-6 alkyl.

[0041] According to some implementation schemes, R1 and R2 can be selected from H, methyl, and phenyl;

[0042] Alternatively, two adjacent R1s can be connected by end groups to form a naphthyl group with the benzene ring, and / or two adjacent R2s can be connected by end groups to form a naphthyl group together with the benzene ring.

[0043] R3 can be selected from methyl; R4 can be selected from pentafluorophenyl.

[0044] According to some implementation schemes, the bulky anionic and cationic complexes represented by formula (I) are selected from:

[0045]

[0046] This article also provides a method for preparing the large-volume anionic and cationic complex represented by formula (I), including the following steps:

[0047]

[0048] 1) Compound I-2 reacts with R3-MgX to give alkylated complex I-1;

[0049] 2) Compound I-1 reacts with B(R4)3 to give the large-volume anionic and cationic complex shown in formula (I);

[0050] Among them, M, Cy, R1, R2, R3, R4, m, and n have the definitions described above; X, X1, and X2 may be the same or different, and are independently selected from Cl, Br, and I.

[0051] 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;

[0052] According to some implementation schemes, in step 2), the reaction can be carried out in an organic solvent, which may be selected from toluene;

[0053] 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 and obtain a large-volume anionic and 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.

[0054] This article also provides the application of the bulky anionic and cationic complex of formula (I) as a catalyst for catalyzing olefin polymerization, such as for catalyzing the polymerization of ethylene and α-olefins.

[0055] Preferably, the large-volume anionic and cationic complexes shown in formula (I) are used to catalyze the solution copolymerization of ethylene and α-olefins to prepare polyethylene elastomers.

[0056] According to some embodiments, the α-olefin may be 1-propylene, 1-butene, 1-pentene, and / or 1-hexene.

[0057] According to some implementation schemes, when the large-volume anionic and 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℃.

[0058] According to some implementation schemes, when the bulky anionic and 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.

[0059] Beneficial effects

[0060] This invention provides a type of diketone-semi-ceramic metal bulk anion-cation 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.

[0061] When used as a catalyst, the complex prepared according to the present 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. It provides a novel and better catalytic system for the polymerization of ethylene and other olefins (such as α-olefins).

[0062] Terminology Definitions and Explanations

[0063] 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.

[0064] 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.

[0065] The term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0066] 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.

[0067] 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. 6-14 Aryl), 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.

[0068] 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.

[0069] The term "spirocycle" refers to a ring system in which two rings share a single ring atom.

[0070] The term "fused ring" refers to a ring system in which two rings share two cyclic atoms.

[0071] The term "bridged ring" refers to a ring system in which two rings share three or more cyclic atoms. Detailed Implementation

[0072] 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.

[0073] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0074] The following embodiments involve testing the obtained product, and the testing process includes:

[0075] Density: The density of solids was tested according to GB / T 1033.1-2008 standard.

[0076] 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, and MFR(190 / 5) represents the melt flow index of the resin when the weight of the weight is 5kg.

[0077] Molecular weight (Mw): Tested according to GB / T 36214.4-2018 standard.

[0078] PDI (Polymer Dispersion Index): Tested according to GB / T 36214.4-2018 standard.

[0079] Elemental analysis: Tested using a German vario EL cube elemental analyzer.

[0080] Inductively Coupled Plasma Atomic Emission Spectrometer: Agilent 5800 Testing

[0081] Mass content of α-olefins: determined by NMR ( 1 The H NMR spectrum was used to determine the identity.

[0082] 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.

[0083] [Example 1]

[0084] Preparation of complex a and its polymerization reaction

[0085]

[0086] Dissolve 3 mmol of 2,2'-biphenyl in 100 mL of dry toluene with stirring. Add 6.2 mmol of triethylamine and react at room temperature for 3 h. Add 3 mmol of a toluene solution of CpTiCl3 (cyclopentadienyl titanium trichloride (IV)) dropwise at room temperature and reflux under nitrogen protection for 24 h. Filter hot under nitrogen protection and concentrate the filtrate under vacuum to approximately 5 mL. Add 10 mL of n-hexane, filter, and wash the solid twice with 10 mL of n-hexane to obtain 0.449 g of a dark red complex, which is [C]. 12 The yield (ω) of the H8O2]CpTiCl was 56%. Elemental analysis results were as follows: C%: measured value 53.89 (theoretical value 53.88); H%: 3.88 (theoretical value 3.91); Ti%: 17.69 (theoretical value 17.89). 1 ¹H NMR (δ, CDCl₃): 6.82 (5H, -C₅H₅, singlet); 7.02-7.05 (4H, -C₅H₅, singlet). 12 H8 (multimodal); 7.30 (2H, -C) 12 H8 (multimodal); 7.83 (2H, -C) 12 H8, double peaks).

[0087] [C] 121.5 mmol of [H8O2]CpTiCl was added to 30 mL of diethyl ether, followed by dropwise addition of 0.8 mL of methylmagnesium chloride (2M) reagent. The mixture was stirred at 25 °C for 2 h. The diethyl ether was removed by rotary evaporation, and the product was washed twice with n-hexane. The n-hexane was then removed by rotary evaporation to obtain 260 mg of a red oily product, which is [C]. 12 [H8O2]CpTiCH3, yield 70%. Elemental analysis results are as follows: C%: measured value 63.09 (theoretical value 63.19); H%: 4.40 (theoretical value 4.49); Ti%: 19.21 (theoretical value 19.37). 1 ¹H NMR (δ, CDCl₃): 0.92 (3H, -CH₃, singlet); 6.91 (5H, -C₅H₅, singlet); 7.00-7.03 (4H, -C₅H₅, singlet); 12 H8 (multimodal); 7.10 (2H, -C) 12 H8 (multimodal); 7.75 (2H, -C) 12 H8, double peaks).

[0088] [C] 12 [H8O2]CpTi CH3 0.5 mmol was added to a sample vial, followed by 1 ml of toluene and stirring to dissolve. Tris(pentafluorophenyl)borane (0.6 mmol) was then added, and the mixture was stirred for 0.5 h. 3 ml of diethyl ether was then 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 60%. Elemental analysis results were as follows: C%: measured value 52.42 (theoretical value 52.46); H%: 1.98 (theoretical value 1.96); Ti%: 5.79 (theoretical value 5.81). 1 ¹H NMR (δ, CDCl₃): 0.87 (3H, -CH₃, singlet); 7.11 (5H, -C₅H₅, singlet); 7.20-7.53 (4H, -C₅H₅, singlet). 12 H8 (multimodal); 7.70 (2H, -C) 12 H8 (multimodal); 7.85 (2H, -C) 12 H8, double peaks).

[0089] A 0.5 μmol / mL toluene solution of complex a was prepared in a glove box as the catalyst solution. 1 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 (triisobutylaluminum) / n-hexane solution (50 μmmol / mL) were added to the reactor. The temperature was raised to 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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.

[0090] [Example 2]

[0091] Preparation of complex b and its polymerization reaction

[0092]

[0093] Referring to Example 1, complex b was synthesized using 2,2'-biphenyl hydroquinone and pentamethylcyclopentadienyl titanium trichloride as starting materials, with an overall yield of 30%. The elemental analysis results were as follows: C%: measured value 55.11 (theoretical value 55.06); H%: 3.02 (theoretical value 2.93); Ti%: 5.13 (theoretical value 5.35). 1 ¹H NMR (δ, CDCl₃): 0.85 (3H, -CH₃, singlet); 2.20 (15H, -CH₃, singlet); 7.14–7.45 (4H, -C₂). 12 H8 (multimodal); 7.61 (2H, -C) 12 H8 (multimodal); 7.79 (2H, -C) 12 H8, double peaks).

[0094] A 0.5 μmol / mL toluene solution of catalyst b was prepared in a glove box as the catalyst solution. 1 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. The catalyst container was then 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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.

[0095] [Example 3]

[0096] Preparation of complex C and its polymerization reaction

[0097]

[0098] The synthesis was carried out as described in Example 1, using 2,2'-binaphthol and cyclopentadienyl titanium trichloride as starting materials to synthesize complex c, with an overall yield of 37%. Elemental analysis results were as follows: C%: measured value 57.32 (theoretical value 57.18); H%: 2.07 (theoretical value 2.19); Ti%: 5.14 (theoretical value 5.18). 1 ¹H NMR (δ, CDCl₃): 0.84 (3H, -CH₃, singlet); 6.95 (2H, -C₂) 20 H 12 7.04 (5H, -C5H5, single peak); 7.31-7.40 (4H, -C5H5, single peak); 20 H 12 (multi-peak); 7.78 (2H, -C) 20 H 12 (Multi-peak); 8.01-8.05 (2H, -C) 20 H 12 (Multi-peak); 8.85-8.93 (2H, -C) 20 H 12 (Multi-peak)

[0099] A 0.5 μmol / mL toluene solution of catalyst c was prepared in a glove box as the catalyst solution. 1 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. The catalyst container was then 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 min, the ethylene supply was stopped, and the mixture was cooled to room temperature. The reaction was then 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.

[0100] [Example 4]

[0101] Preparation of complex d and its polymerization reaction

[0102]

[0103] Referring to Example 1, using 2,2'-binaphthol and pentamethylcyclopentadienyl titanium trichloride as starting materials, complex d was obtained with an overall yield of 31%. The elemental analysis results were as follows: C%: measured value 59.22 (theoretical value 59.18); H%: 3.01 (theoretical value 3.04); Ti%: 4.90 (theoretical value 4.81). 1 ¹H NMR (δ, CDCl₃): 0.80 (3H, -CH₃, singlet); 2.15 (15H, -CH₃, singlet); 6.88 (2H, -C₂) 20 H 12 (double peak); 7.12-7.31 (4H, -C) 20 H 12 (Multi-peak); 7.70 (2H,-C) 20 H 12 (Multi-peak); 7.94-8.01 (2H, -C) 20 H 12 (Multi-peak); 8.78-8.88 (2H, -C) 20 H 12 (Multi-peak)

[0104] A 0.5 μmol / mL toluene solution of complex d was prepared in a glove box as the catalyst solution. 1 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. The catalyst container was then transferred from 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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 dried under vacuum. The polymerization results are shown in Table 1.

[0105] [Example 5]

[0106] Preparation of complex e and its polymerization reaction

[0107]

[0108] Referring to Example 1, using 2,2'-binaphthol and pentamethylcyclopentadienylzirconium trichloride as starting materials, complex e was obtained with an overall yield of 36%. Elemental analysis results were as follows: C%: measured value 52.55 (theoretical value 52.52); H%: 2.78 (theoretical value 2.80); Zr%: 9.71 (theoretical value 9.73). 1 ¹H NMR (δ, CDCl₃): 0.84 (3H, -CH₃, singlet); 2.17 (15H, -CH₃, singlet); 7.10–7.43 (4H, -C₂). 12 H8 (multimodal); 7.60 (2H, -C) 12 H8 (multimodal); 7.75 (2H, -C) 12 H8, double peaks).

[0109] A 0.5 μmol / mL toluene solution of complex e was prepared in a glove box as the catalyst solution. 1 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. The catalyst container was then 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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.

[0110] [Example 6]

[0111] Preparation of complex f and its polymerization reaction

[0112]

[0113] Referring to Example 1, using 2,2'-binaphthylhydrin and pentamethylcyclopentadienyl hafnium trichloride as starting materials, complex f was obtained with an overall yield of 34%. Elemental analysis results were as follows: C%: measured value 48.01 (theoretical value 48.05); H%: 2.61 (theoretical value 2.56); Zr%: 17.45 (theoretical value 17.41). 1 ¹H NMR (δ, CDCl₃): 0.80 (3H, -CH₃, singlet); 2.15 (15H, -CH₃, singlet); 7.05-7.40 (4H, -C₂) 12 H8 (multimodal); 7.57 (2H, -C) 12 H8 (multimodal); 7.70 (2H, -C) 12 H8, double peaks).

[0114] A 0.5 μmol / mL toluene solution of complex f was prepared in a glove box as the catalyst solution. 1 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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.

[0115] [Example 7]

[0116] Preparation of complex g and its polymerization reaction

[0117]

[0118] The synthesis was carried out as described in Example 1, using 2,2'-binaphthol and indene-titanium trichloride as starting materials to synthesize a complex of g, with an overall yield of 37%. Elemental analysis results were as follows: C%: measured value 54.92 (theoretical value 54.96); H%: 2.07 (theoretical value 2.08); Ti%: 5.45 (theoretical value 5.48). 1 ¹H NMR (δ, CDCl₃): 0.87 (3H, -CH₃, singlet); 6.50 (1H, -C₉H₇, doublet); 6.65 (2H, -C₉H₇, doublet); 7.20-7.53 (8H, -C₉H₇, doublet). 12 H8, -C9H7, multi-peaked); 7.70 (2H, -C 12 H8 (multimodal); 7.85 (2H, -C) 12 H8, double peaks).

[0119] A 0.5 μmol / mL toluene solution of catalyst g was prepared in a glove box as the catalyst solution. 1 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. The catalyst container was then 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 80 °C, the rotation speed was adjusted to 1000 r / min, and ethylene was introduced to a pressure of 4 MPa. After the reaction temperature reached 100 °C, the catalyst in the catalyst container was transferred to the reactor, and the reaction temperature was controlled at 120 °C. After reacting for 30 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 dried under vacuum. The polymerization results are shown in Table 1.

[0120] [Example 8] Refer to Example 1, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0121] [Example 9] Refer to Example 2, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0122] [Example 10] Refer to Example 3, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0123] [Example 11] Refer to Example 4, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0124] [Example 12] Refer to Example 5, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0125] [Example 13] Refer to Example 6, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0126] [Example 14] Refer to Example 7, except that 23 mL of 1-butene was used instead of 1-hexene, and 1-butene was added continuously. The polymerization results are shown in Table 1.

[0127] [Example 15] Refer to Example 1, except that the amount of 1-hexene added was 40 mL. The polymerization results are shown in Table 1.

[0128] [Example 16] Refer to Example 1, except that the amount of 1-hexene added was 20 mL. The polymerization results are shown in Table 1.

[0129] [Example 17] Referring to Example 1, except that the polymerization temperature was controlled at 130°C. The polymerization results are shown in Table 1.

[0130] [Example 18] Refer to Example 1, except that the polymerization temperature was controlled at 100°C. The polymerization results are shown in Table 1.

[0131] [Example 19] Refer to Example 1, except that the polymerization pressure was controlled at 6 MPa. The polymerization results are shown in Table 1.

[0132] [Example 20] Refer to Example 1, except that the polymerization temperature was controlled at 2 MPa. The polymerization results are shown in Table 1.

[0133] Table 1. Aggregation Results

[0134]

[0135]

[0136] The embodiments of the technical solution of the present invention have been described above by way of example. It should be understood that the scope of protection 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 scope of protection of the claims of this application.

Claims

1. A bulky anion-cation complex of formula (I): （I） in, M is selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); Cy is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Ra: cyclopentadienyl, indenyl, fluorenyl; Each R1 and R2 may be the same or different, and is independently selected from hydrogen, and consists of the following groups that are unsubstituted or optionally substituted by one, two or more Rb groups: C 1-10 Alkyl, C 6-14 Aryl, 5-14 heteroaryl; m selected from 0, 1, 2, 3 or 4; n selected from 0, 1, 2, 3 or 4; Alternatively, two adjacent R1s can be connected by end groups to form a fused ring C with the benzene ring. 6-14 The aryl group, and / or two adjacent R2 groups, can be connected by end groups to form a fused ring C with the benzene ring. 6-14 Aryl; R3 is selected from C3 that is unsubstituted or optionally substituted by one, two or more Rc. 1-10 alkyl; Each R4 may be identical or different, and is independently selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rc groups: C 6-14 Aryl; Each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-6 alkyl; Each Rc may be the same or different, and is independently selected from halogens, C 1-6 alkyl.

2. The complex according to claim 1, characterized in that, Cy is selected from cyclopentadienyl or pentamethylcyclopentadienyl; Each R1 and R2 may be the same or different, and is independently selected from hydrogen, unsubstituted or optionally substituted by one, two or more Rb groups of the following groups: C 1-6 Alkyl, C 6-8 Aryl, 5-8 membered heteroaryl; m is selected from 0, 1 or 2; n is selected from 0, 1 or 2; Alternatively, two adjacent R1s can be connected by end groups to form a fused ring C with the benzene ring. 10-14 The aryl group, and / or two adjacent R2 groups, can be connected by end groups to form a fused ring C with the benzene ring. 10-14 Aryl; R3 is selected from C3 that is unsubstituted or optionally substituted by one, two or more Rc. 1-6 alkyl; Each R4 may be the same or different, and is independently selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rc: C 6-8 Aryl; Each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-6 alkyl; Each Rc may be the same or different, and is independently selected from halogens, C 1-6 alkyl.

3. The complex according to claim 1 or 2, characterized in that, R1 and R2 are selected from C 1-6 Alkyl, C 6-8 Aryl; Alternatively, two adjacent R1s may be connected by end groups to form naphthyl or anthracene with the benzene ring, and / or two adjacent R2s may be connected by end groups to form naphthyl or anthracene with the benzene ring. R3 is selected from C 1-6 alkyl; R4 is selected from C4 that is unsubstituted or optionally substituted by one, two or more Rc. 6-8 Aryl; Each Rc may be the same or different, and is independently selected from halogens, C 1-6 alkyl.

4. The complex according to claim 1, characterized in that, R1 and R2 are selected from H, methyl, and phenyl; Alternatively, two adjacent R1s can be connected by end groups to form a naphthyl group with the benzene ring, and / or two adjacent R2s can be connected by end groups to form a naphthyl group together with the benzene ring. R3 is selected from methyl; R4 is selected from pentafluorophenyl.

5. The complex according to claim 1, characterized in that, The large-volume anion-cation complexes shown in formula (I) are selected from: 、 、 、 、 、 、 。 6. A method for preparing the large-volume anionic-cationic complex according to any one of claims 1-5, 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 large-volume anionic and cationic complex shown in formula (I); Wherein, M, Cy, R1, R2, R3, R4, m, and n have the definitions described in any one of claims 1-5; X and X1 may be the same or different and are independently selected from Cl, Br, and I.

7. The preparation method according to claim 6, 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.

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

9. The preparation method according to claim 6, 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 and obtain a large-volume anionic and cationic complex of formula (I); the poor solvent is selected from at least one of diethyl ether, methyl tert-butyl ether, n-hexane, cyclohexane, and petroleum ether.

10. The use of the complex according to any one of claims 1-5 as a catalyst for catalyzing olefin polymerization.

11. The application according to claim 10, characterized in that, The application is to catalyze the polymerization of ethylene and α-olefins.

12. The application according to claim 10, characterized in that, The application is for the preparation of polyethylene elastomers by catalytic solution copolymerization of ethylene and α-olefins.

13. The application according to claim 11 or 12, characterized in that, The α-olefin is selected from 1-propylene, 1-butene, 1-pentene, and / or 1-hexene.

14. The application according to claim 10, characterized in that, When the complex according to any one of claims 1-5 is used to catalyze olefin polymerization, the polymerization temperature is 100℃-200℃; The polymerization pressure is 1-8 MPa.

15. The application according to claim 14, characterized in that, The polymerization temperature is 120℃-180℃; The polymerization pressure is 2-6 MPa.

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