Preparation and application of mono-zirconocene metal compound

Abstract

The invention provides preparation and application of a mono-zirconocene metal compound. The mono-zirconocene metal compound has a structure as shown in a formula 1, wherein in the formula 1, X is independently selected from one of F, Cl, Br and I; r1, R2, R3 and R4 are independently selected from H, halogen, C1-C6 alkyl groups, C1-C6 alkoxy groups, C3-C10 heterocyclic groups, C6-C20 aryl groups or C6-C20 or C6-C20 heteroatom aryl groups, and C1-C6 alkyl group substituted or unsubstituted silicon groups; in the formula, R1, R2, R3 and R4 are independently selected from H, halogen, C1-C6 alkyl groups, C1-C6 alkoxy groups, C3-C10 heterocyclic groups, C6-C20 aryl groups or C6-C20 heteroatom aryl groups; and R5 is selected from cyclopentadienyl which is substituted or unsubstituted by a C1-C20 alkyl group, indenyl which is substituted or unsubstituted by a C1-C20 alkyl group, and fluorenyl which is substituted or unsubstituted by a C1-C20 alkyl group. The mono-zirconocene metal compound is used for catalyzing an olefin monomer, so that a cycloolefin copolymer with high molecular weight and high glass transition temperature can be synthesized.

Description

Technical Field

[0001] This invention relates to the field of petrochemicals, and more particularly to the preparation and application of a monoceramic zirconium metal compound. Background Technology

[0002] Polyolefin materials have found wide application in various fields due to their excellent physicochemical properties, processability, and cost-effectiveness. Among them, cyclic olefin copolymers (COCs) not only possess good processability but also excellent thermal, optical, and mechanical properties, such as excellent heat and chemical resistance, excellent transparency, high refractive index, high hardness or flexibility, and low permeability to gases and water. These superior properties make COCs a novel type of engineering plastic with enormous potential applications in optical lenses, optical fibers, medical devices, and capacitors.

[0003] The copolymerization of ethylene and norbornene is the most common method for producing cyclic olefin copolymers. Metallocene catalysts are widely used in the preparation of cyclic olefin polymers due to their single active center and good copolymerization performance. Metallocene catalysts are an important class of organometallic compounds, typically containing one or more cyclopentadienyl (Cp) ligands bound to a transition metal center. The most common metallocene catalyst is the dimerocene catalyst, which contains two cyclopentadienyl (Cp) ligands bound to a transition metal center. However, in dimerocene catalysts, the active metal ligand is tightly surrounded by two cyclopentadienyl groups, resulting in a relatively limited space. This makes it difficult for larger comonomers to approach the active metal center for copolymerization, thus limiting the performance of the resulting copolymers. Monocyclic metallocene catalysts are created by replacing one cyclopentadienyl ligand in a bis(cyclopentadienyl) metal with a non-cyclopentadienyl ligand (such as an alkoxy group, halogen group, or amino group), resulting in a monocyclic metallocene structure where the metal center forms a bridged or unbridged connection with only one cyclopentadienyl ligand. The structural formula can be represented as Cp'M(R)X, where Cp is the cyclopentadienyl ligand, R is the non-cyclopentadienyl ligand, M is the transition metal center, and X is a halogen. In metallocene catalysts, monocyclic metal complexes retain the catalytic properties of metallocene while increasing the stability of the complex.

[0004] Currently, monocerometallic metal complexes have been reported to have applications in the preparation of cyclic olefin copolymers. For example, thiophenol-phosphonyl ligands can be used as the R ligand in the above formula to form monocerometallic catalysts. However, the synthesis steps of the thiophenol-phosphonyl ligands are cumbersome, and the preparation process uses odorous thiophenol and highly toxic phosphorus-containing compounds, making it unsuitable for large-scale industrial production. To address these issues, it has been reported to use nitrogen-containing heterocyclic borooxy ligands as the R ligand in the above formula to form monocerometallic catalysts. However, these catalysts have limited polymerization activity, cannot increase the molecular weight of the copolymer, and the glass transition temperature of the resulting copolymer is also relatively low. Furthermore, the preparation cost of this catalyst is high, limiting the application of the copolymers catalyzed by this catalyst in production and daily life.

[0005] Therefore, there is an urgent need for a catalyst suitable for mass production that can enable cyclic olefin copolymers to have high molecular weight and high glass transition temperature. Summary of the Invention

[0006] This invention provides a method for preparing the above-mentioned mono-zirconium metal compound. The mono-zirconium metal compound prepared by this method can participate in the efficient copolymerization of olefin monomers to generate cyclic olefin copolymers with both high molecular weight and high glass transition temperature. Furthermore, the preparation method is simple, does not produce toxic substances, and is conducive to mass production in industry.

[0007] This invention provides a monoceramic catalyst that can efficiently catalyze the copolymerization of olefin monomers, resulting in cyclic olefin copolymers with both high molecular weight and high glass transition temperature, thereby improving the quality of the cyclic olefin copolymers.

[0008] This invention provides a method for preparing cyclic olefin copolymers. The cyclic olefin copolymers prepared by this method have high molecular weight and high glass transition temperature, and are of good quality, which can be widely used in daily life.

[0009] This invention provides a cyclic olefin copolymer with high molecular weight and high glass transition temperature, exhibiting high chemical stability and mechanical properties, and has significant advantages in numerous applications.

[0010] The first aspect of this invention provides a monoceramic zirconium metal compound having the structure shown in Formula 1:

[0011]

[0012] In Formula 1, X is independently selected from one of F, Cl, Br, and I;

[0013] R1, R2, R3, and R4 are independently selected from H, halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, C3-C10 heterocyclic groups, C6-C20 aryl or C6-C20 heteroatom aryl groups, and C1-C6 alkyl-substituted or unsubstituted silyl groups.

[0014] R5 is selected from C1-C20 substituted or unsubstituted cyclopentadienyl, C1-C20 substituted or unsubstituted indenyl, and C1-C20 substituted or unsubstituted fluorenyl.

[0015] The monoceramic zirconium metal compound described above, wherein R1 is selected from H, C1-C4 alkyl, halogen, C6 aryl, and silyl; and / or,

[0016] R2 is selected from H, C1-C4 alkyl, C1-C4 alkoxy; and / or,

[0017] R3 and R4 are each independently selected from H or C1-C6 alkyl groups; and / or,

[0018] R5 is selected from cyclopentadienyl, indene, fluorenyl, pentamethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, and tert-butyl-cyclopentadienyl.

[0019] The monoceramic zirconium metal compounds described above include the following compounds:

[0020] Zr1, where R1 and R2 are both hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or,

[0021] Zr₂, where R₁ is F, R₂ is hydrogen, X is Cl, R₃ and R₄ are both hydrogen, and R₅ is cyclopentadienyl; or...

[0022] Zr3, wherein R1 is phenyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0023] Zr4, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0024] Zr5, wherein R1 is tert-butyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0025] Zr6, wherein R1 and R2 are both tert-butyl, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or,

[0026] Zr7, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethyl-cyclopentadienyl; or,

[0027] Zr8, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is trimethylsilyl-cyclopentadienyl; or

[0028] Zr9, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is tert-butyl-cyclopentadienyl; or

[0029] Zr10, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is indenyl; or,

[0030] Zr11, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is fluorene.

[0031] A second aspect of the present invention provides a method for preparing the monoceramic zirconium metal compound as described above, comprising the following steps:

[0032] 1) 2-(dimethylamino)-phenol, including R1, R2, R3, and R4, is reacted with NaH in a solvent to obtain a sodium salt compound;

[0033] 2) The sodium salt compound is reacted with the monoceramic zirconium metal salt in a solvent to obtain the monoceramic zirconium metal compound.

[0034] In the preparation method of the monoceramic zirconium metal compound as described above, in step 1), the molar ratio of 2-(dimethylamino)-phenol comprising R1, R2, R3, and R4 to NaH is 1:(1-3); and / or,

[0035] In step 2), the molar ratio of the sodium salt compound to the monocerozirconium metal salt is 1:(1-3).

[0036] In the preparation method of the monoceramic zirconium metal compound as described above, the reaction temperature in step 1) is 25–50 °C, and the reaction time is 2–8 h; and / or,

[0037] The reaction temperature in step 2) is -78 to 0℃, and the reaction time is 5 to 12 hours.

[0038] In another aspect, the present invention provides a catalyst comprising a monoceramic zirconium metal compound as described above or a monoceramic zirconium metal compound prepared by the method described above.

[0039] The catalyst as described above further includes a co-catalyst, which includes at least one of alkylaluminoxane and / or modified alkylaluminoxane.

[0040] In the monoceramic metal catalyst described above, the molar ratio of aluminum in the alkylaluminoxane to zirconium in the monoceramic zirconium metal compound is (200-10000):1.

[0041] In another aspect, the present invention provides a method for preparing a cyclic olefin copolymer, wherein the copolymerization catalysis of olefin monomers is carried out using the catalyst described above.

[0042] The present invention also provides a cyclic olefin copolymer, wherein the content of structural units derived from ethylene is 46-53 mol%, and the content of structural units derived from norbornene is 47-54 mol%.

[0043] The mono-zirconium metal compound of this invention, constructed by introducing a 2-(dimethylamino)-phenol ligand, allows the central metal to have a large open angle, which is beneficial for catalyzing the copolymerization of olefin monomers with larger molecular weights. Furthermore, the 2-(dimethylamino)-phenol ligand has a strong electron-donating ability, effectively catalyzing the copolymerization of olefin monomers. Therefore, using the mono-zirconium metal compound for olefin monomer copolymerization can synthesize cyclic olefin copolymers with high molecular weight and high glass transition temperature, improving the quality of cyclic olefin copolymers. In addition, this invention uses 2-(dimethylamino)-phenol as a ligand, which is inexpensive and has low industrial costs. The preparation of the mono-zirconium metal compound does not generate toxic or irritating gases, making it suitable for industrial mass production. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0045] The use of metallocene catalysts for the catalytic synthesis of olefin monomers is a common method in industry for the preparation of cyclic olefin copolymers. Currently, the use of bismetallocene catalysts for the catalytic synthesis of cyclic olefin copolymers has been reported; however, the catalytic performance of bismetallocene catalysts is limited due to the presence of two cyclopentadienyl groups. To address this issue, the use of monometallocene catalysts for the catalytic synthesis of cyclic olefin copolymers has been reported. However, these monometallocene catalysts suffer from high preparation costs, limited activity in the copolymerization reaction, and the copolymers obtained using these catalysts cannot simultaneously achieve high molecular weight and high glass transition temperature characteristics, thus limiting the application of the resulting copolymers in production and daily life.

[0046] Therefore, the preparation of cyclic olefin copolymers with both high molecular weight and high glass transition temperature using efficient catalysts, while reducing industrial costs, is an urgent problem to be solved in the preparation of cyclic olefin copolymers.

[0047] Based on this, the first aspect of the present invention provides a monoceramic zirconium metal compound having the structure shown in Formula 1:

[0048]

[0049] In Formula 1, X is independently selected from one of F, Cl, Br, and I;

[0050] R1, R2, R3, and R4 are independently selected from H, halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, C3-C10 heterocyclic groups, C6-C20 aryl or C6-C20 heteroatom aryl groups, and C1-C6 alkyl-substituted or unsubstituted silyl groups.

[0051] R5 is selected from C1-C20 substituted or unsubstituted cyclopentadienyl, C1-C20 substituted or unsubstituted indenyl, and C1-C20 substituted or unsubstituted fluorenyl.

[0052] The basic structure of the aforementioned mono-zirconium metal compound consists of a mono-metallocene ligand linked to a 2-(dimethylamino)-phenol ligand. The 2-(dimethylamino)-phenol ligand is substituted by R1, R2, R3, and R4. The active metal center in the metallocene ligand is coordinated with R5.

[0053] Specifically, C1-C6 alkyl refers to straight-chain or branched alkyl groups having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, and neopentyl.

[0054] The C1-C6 alkoxy group refers to a straight-chain or branched saturated monovalent hydrocarbon group of the formula -O-alkyl with 1-6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, or their isomers.

[0055] C3-C10 heterocyclic groups refer to groups of the formula -N / O / S-cycloalkyl having 3-10 carbon atoms. These heterocyclic groups can be connected to the rest of the molecule via any one carbon atom or nitrogen atom (if a nitrogen atom is present in the heterocyclic group). These heterocyclic groups can include, but are not limited to: 4-membered rings, such as azirrobutylyl and oxobutylyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolylyl, imidazoalkyl, pyrazolylyl, or pyrrololinyl; 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazineyl, or trithiaalkyl; and 7-membered rings, such as diazacycloheptyl. These heterocyclic groups can be benzofused. The aforementioned heterocyclic group can be bicyclic, such as, but not limited to, a 5,5-membered ring, like a hexahydrocyclopentano[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, like a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring can be partially unsaturated, i.e., it can contain one or more double bonds, such as, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl. Alternatively, it can be benzofused, such as, but not limited to, dihydroisoquinolinyl.

[0056] The C6-C20 aryl group refers to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably a C6-C14 aryl group. The aforementioned C6-C14 aryl group refers to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms, 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 (“C10 aryl”), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl; or a ring with 13 carbon atoms (“C13 aryl”), such as fluorenyl; or a ring with 14 carbon atoms (“C14 aryl”), such as anthraceneyl.

[0057] C6-C20 heteroatom aryl groups refer to groups having the formula -N-aryl or -N-heteroaryl with 6 to 20 carbon atoms. Monocyclic examples of heteroaryl groups include, but are not limited to, thiophene, furanyl, pyrrole, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[a] derivatives, such as benzofuranyl, benzothiophene, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, and indole. The group includes hydroxyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, etc., and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphridinyl, pteridinyl, carbazoyl, acridineyl, phenazinyl, phenothiazinyl, phenotoxazinyl, etc.

[0058] A C1-C20 substituted or unsubstituted cyclopentadienyl group refers to a cyclopentadienyl group in which any hydrogen atom is not substituted, or is substituted by a C1-C20 substituted cyclopentadienyl group. The hydrogen atoms on the cyclopentadienyl group may not be substituted by a C1-C20 substituted cyclopentadienyl group, or one or more hydrogen atoms may be substituted by a C1-C20 substituted cyclopentadienyl group.

[0059] A C1-C20 substituted or unsubstituted indenyl group refers to an indenyl group where none of the hydrogen atoms are substituted, or where any one of the hydrogen atoms is substituted by a C1-C20 substituted hydrocarbon group. The hydrogen atoms on the cyclopentadienyl group may not be substituted by a C1-C20 substituted hydrocarbon group, or one or more hydrogen atoms may be substituted by a C1-C20 substituted hydrocarbon group.

[0060] A C1-C20 substituted or unsubstituted fluorenyl group refers to a fluorenyl group in which any hydrogen atom is not substituted, or is substituted by a C1-C20 substituted fluorenyl group. The hydrogen atoms on the cyclopentadienyl group may not be substituted by a C1-C20 substituted fluorenyl group, or one or more hydrogen atoms may be substituted by a C1-C20 substituted fluorenyl group.

[0061] This invention utilizes a monozirconia metal compound having the above-described structural formula and defines its components R1, R2, R3, R4, and R5 to effectively enhance the activity of catalysts containing monozirconia metal compounds. This allows for the catalytic copolymerization of monomeric olefins to generate cyclic olefin copolymers with both high molecular weight and high glass transition temperature. The inventors speculate that this is because the unique structure of the monozirconia metal compound results in a large open angle at the active metal center, enabling the large olefin molecules to contact the active metal center effectively and catalyze their polymerization. By increasing the insertion of large olefin molecules into the copolymer, the glass transition temperature of the cyclic olefin copolymer can be significantly increased. Furthermore, the large open angle also implies high catalytic activity, enabling the copolymerization to produce cyclic olefin copolymers with higher molecular weights. Therefore, by using the invented monozirconia metal compound to prepare cyclic olefin copolymers, cyclic olefin copolymers with both high molecular weight and high glass transition temperature can be obtained. Furthermore, since no toxic or irritating gases are generated during the preparation of monoceramic zirconium metal compounds with the above-mentioned structural formula, and the raw materials for preparing monoceramic zirconium metal compounds with the above-mentioned structural formula are inexpensive and readily available, they can be applied to large-scale industrial production, thereby improving industrial economics.

[0062] Furthermore, R1 is selected from H, C1-C4 alkyl, halogen, C6 aryl, and silyl.

[0063] In another specific embodiment, R2 is selected from H, C1-C4 alkyl, and C1-C4 alkoxy.

[0064] In another specific embodiment, R3 and R4 are each independently selected from H or C1-C6 alkyl groups.

[0065] In another specific embodiment, R5 is selected from cyclopentadienyl, indene, fluorenyl, pentamethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, and tert-butyl-cyclopentadienyl.

[0066] By selecting R1, R2, R3, and R4, this invention can further enhance the electron-donating ability of the 2-(dimethylamino)phenol ligand, create a larger spatial open angle for the active metal center and reduce steric hindrance, thereby further improving the catalytic activity of catalysts including monoceramic zirconium metal compounds.

[0067] By selecting R5, the active metal center can be further stabilized, thereby improving the stability of monoceramic zirconium metal compounds.

[0068] Specifically, mono-zirconium metal compounds include the following compounds:

[0069] Zr1, where R1 and R2 are both hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or,

[0070] Zr₂, where R₁ is F, R₂ is hydrogen, X is Cl, R₃ and R₄ are both hydrogen, and R₅ is cyclopentadienyl; or...

[0071] Zr3, wherein R1 is phenyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0072] Zr4, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0073] Zr5, wherein R1 is tert-butyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or

[0074] Zr6, wherein R1 and R2 are both tert-butyl, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or,

[0075] Zr7, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethyl-cyclopentadienyl; or,

[0076] Zr8, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is trimethylsilyl-cyclopentadienyl; or

[0077] Zr9, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is tert-butyl-cyclopentadienyl; or

[0078] Zr10, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is indenyl; or,

[0079] Zr11, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is fluorene.

[0080] Through experiments, the inventors further discovered that when using the aforementioned monoceramic zirconium metal compound as a catalyst for the catalytic copolymerization of olefin monomers, the catalyst has high activity, and the resulting cyclic olefin copolymer has a high molecular weight and a high glass transition temperature.

[0081] A second aspect of this invention provides a method for preparing a mono-zirconium metal compound, comprising the following steps:

[0082] 1) 2-(dimethylamino)-phenol, including R1, R2, R3, and R4, is reacted with NaH in a solvent to obtain a sodium salt compound;

[0083] 2) The sodium salt compound is reacted with the monoceramic zirconium metal salt in a solvent to obtain the monoceramic zirconium metal compound.

[0084] Monocerozirconium metal salts are an important class of organometallic compounds, in which a cyclopentadienyl (Cp) ligand is bonded to a zirconium metal center. This invention does not specifically limit the monocerozirconium metal salts, as long as they can react with the aforementioned sodium salt compounds to form monocerozirconium metal compounds. For example, monocerozirconium metal salts include at least one of Cp₂ZrCl₂, CpZrCl₃, Cp₂ZrR₂, CpZrR₃ (where R can be an alkyl group such as methyl (-CH₃) or ethyl (-C₂H₅)), Cp₂Zr(OR)₂, CpZr(OR)₃ (where OR is an alkoxide ligand such as methoxy (-OMe), Cp₂Zr(NH₂)₂, CpZr(NH₂)₃ (where NH₂ is an amine ligand), and Cp₂ZrX₂ (where X can be a halogen such as fluorine (F), bromine (Br), or iodine (I)).

[0085] In step 1), R1, R2, R3, and R4 are selected from the groups described above. Sodium hydride (NaH) is a strong base that can abstract a proton (H+) from the hydroxyl group of 2-(dimethylamino)phenol. + This process generates corresponding anions and hydrogen gas, and the anions combine with sodium ions to form sodium salt compounds.

[0086] In step 2), the anion in the sodium salt compound is a strong nucleophile, which can attack the anion present in the monocerozirconium metal salt and undergo a nucleophilic substitution reaction to generate the monocerozirconium metal compound.

[0087] The present invention does not impose any special limitation on the solvent, as long as it can dissolve the monoceramic zirconium metal salt and sodium salt compound without reacting with them. For example, the solvent includes at least one of aromatic hydrocarbon solvents and alkane solvents. Specifically, the solvent includes at least one of toluene, xylene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane and n-octane, and tetrahydrofuran, more preferably tetrahydrofuran or toluene.

[0088] It should be noted that, in order to avoid the influence of air components on the synthesis of the above-mentioned mono-zirconium metal compounds, inert gases need to be used to protect the preparation of the mono-zirconium metal compounds during the preparation process.

[0089] To obtain a pure product, a monoceramic zirconium metal compound, a vacuum reduction operation and a recrystallization operation are included after step 2). This invention does not specifically limit the vacuum reduction operation, as long as the solvent can be removed; nor does it specifically limit the recrystallization operation, as long as a monoceramic zirconium metal compound can be obtained. For example, toluene, xylene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, and n-octane can be used for recrystallization.

[0090] By using the above-described preparation method, mono-zirconium metal compounds with good catalytic activity can be prepared, which can effectively catalyze olefin monomers. Furthermore, the raw materials used in this method are inexpensive and readily available, and the preparation process does not produce toxic or irritating gases, which is beneficial for industrial-scale production.

[0091] Furthermore, in the preparation method described above, the molar ratio of 2-(dimethylamino)-phenol (R1, R2, R3, R4) to NaH is 1:(1-3). For example, the above molar ratio includes, but is not limited to, 1:1, 1:2, 1:3, or any combination thereof. By further limiting the molar ratio of 2-(dimethylamino)-phenol (R1, R2, R3, R4) to NaH, this invention is advantageous in increasing the yield of the monoceramic zirconium metal compound while saving raw materials.

[0092] In another embodiment, the molar ratio of the sodium salt compound to the monoceramic zirconium metal salt is 1:(1 to 3). For example, the above molar ratio includes, but is not limited to, a range of 1:1, 1:2, 1:3, or any two of these. By further limiting the molar ratio of the sodium salt compound to the monoceramic zirconium metal salt, the present invention is advantageous in increasing the yield of the monoceramic zirconium metal compound while saving raw materials.

[0093] To further improve the preparation efficiency of mono-zirconium metal compounds, the present invention further limits the reaction temperature and reaction time in the above preparation method.

[0094] In detail, the reaction temperature in step 1) of this invention is 25-50°C, and the reaction time is 2-8 hours. For example, the reaction temperature includes, but is not limited to, a range of 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or any combination thereof, and the reaction time includes, but is not limited to, a range of 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, or any combination thereof.

[0095] In another specific embodiment, the reaction temperature in step 2) is -78 to 0°C, and the reaction time is 5 to 12 hours. For example, the reaction temperature includes, but is not limited to, a range of 5°C, 7°C, 8°C, 10°C, 12°C, or any combination thereof, and the reaction time includes, but is not limited to, a range of 5 hours, 7 hours, 9 hours, 10 hours, 11 hours, 12 hours, or any combination thereof.

[0096] A third aspect of the present invention provides a catalyst comprising the above-described monoceramic zirconium metal compound.

[0097] To achieve both high molecular weight and high glass transition temperature properties in cyclic olefin copolymers, this invention uses the aforementioned monoceramic zirconium metal compound as a catalyst to catalyze olefin monomers. The catalyst exhibits high catalytic activity, and the resulting cyclic olefin copolymer possesses the aforementioned properties, making it widely applicable across various industries.

[0098] Further research by the inventors revealed that, to achieve better catalytic copolymerization of olefin monomers, the catalyst further includes a co-catalyst, which comprises at least one of alkylaluminoxanes and modified alkylaluminoxanes. For example, the co-catalyst includes at least one of methylaluminoxane, triisobutyl-modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane. Preferably, the co-catalyst comprises at least one of methylaluminoxane and triisobutyl-modified methylaluminoxane. By using the above co-catalyst, the formation of cyclic olefin copolymers can be effectively catalyzed. The inventors speculate that this may be because, on the one hand, the monozirconia metal compound can be alkylated, exposing the active metal center and thus exhibiting higher catalytic activity; on the other hand, moisture in the reaction system can be removed, avoiding the influence of moisture on the monozirconia metal compound.

[0099] Furthermore, the molar ratio of aluminum in the alkylaluminoxane to zirconium in the monoceramic zirconium metal compound is (200 to 10000):1. For example, the above molar ratio includes, but is not limited to, 200:1, 500:1, 1000:1, 5000:1, 10000:1, or any combination thereof.

[0100] Preferably, when the cocatalyst is methylaluminoxane, the molar ratio of aluminum in methylaluminoxane to zirconium in the monocerozirconium metal compound is 1000-5000:1, more preferably 2500:1, including but not limited to 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 4000:1, 5000:1 or any combination thereof.

[0101] When the above-mentioned cocatalyst is triisobutyl-modified methylaluminoxane, the molar ratio of aluminum in the triisobutyl-modified methylaluminoxane to zirconium in the monoceramic zirconium metal compound is (1000-5000):1, more preferably 2500:1, including but not limited to 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 4000:1, 5000:1 or any combination thereof.

[0102] A fourth aspect of the present invention provides a method for preparing a cyclic olefin copolymer, wherein the method uses the catalyst described above to carry out a copolymerization catalytic reaction of olefin monomers.

[0103] In this invention, the olefin monomer is not specifically limited, as long as it can copolymerize to form a cyclic olefin copolymer. For example, the olefin monomer includes at least one selected from ethylene, propylene, 1-butene, 1-hexene, norbornene, dicyclopentadiene, and tricyclodecene.

[0104] This invention does not impose any special limitation on the ratio of olefin monomers used, as long as they can copolymerize to form cyclic olefin copolymers. For example, the ratio of norbornene to ethylene can be 20-200 mmol / atm to prepare cyclic olefin copolymers.

[0105] The polymerization temperature of the copolymerization catalytic reaction of the present invention is 0-200℃ and the polymerization time is 1-300min. Preferably, for example, the conditions of the copolymerization catalytic reaction include: polymerization temperature of 50-160℃ and polymerization time of 60-120min.

[0106] Furthermore, the above-mentioned copolymerization catalytic reaction is carried out in the presence of a solvent. This invention does not specifically limit the solvent, as long as it can serve as a medium for the catalytic copolymerization of the monomeric olefin and does not react with the olefin monomer. For example, the solvent is selected from aromatic hydrocarbon solvents and alkane solvents. Preferably, the solvent is selected from at least one of toluene, xylene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, and n-octane, more preferably toluene.

[0107] The method for preparing cyclic olefin copolymers provided by this invention can effectively catalyze the copolymerization reaction of olefin monomers, and can prepare cyclic olefin copolymers with both high molecular weight and high glass transition temperature. These properties give the cyclic olefin copolymers strong mechanical properties and high chemical stability, enabling them to be widely used in various industries. Furthermore, in the above preparation method, the catalyst raw materials are inexpensive and readily available, and the catalyst has high catalytic activity towards olefin monomers, which is beneficial for achieving industrial mass production and has high industrial economic efficiency.

[0108] This invention also provides a cyclic olefin copolymer, wherein the content of structural units derived from ethylene is 46-53 mol%, and the content of structural units derived from norbornene is 47-54 mol%. Specifically, the cyclic olefin copolymer has a weight-average molecular weight of 200,000-400,000, a molecular weight distribution index of 2.0-2.6, and a glass transition temperature of 130-150°C. Therefore, the cyclic olefin copolymer possesses both high molecular weight and high glass transition temperature, exhibiting excellent mechanical properties and chemical stability, and has a wide range of applications. Specifically, this cyclic olefin copolymer can be prepared by the preparation method provided in the fourth aspect of this invention.

[0109] The present invention will be further described below through specific embodiments.

[0110] Example 1

[0111] The method for preparing the mono-zirconium metal compound in this embodiment includes the following steps:

[0112] 1) Under an argon atmosphere and in the presence of 20 mL of anhydrous tetrahydrofuran, 2-(dimethylamino)phenol (0.137 g, 1 mmol) and sodium hydride (24 mg, 1 mmol) were reacted at 25 °C for 5 h to obtain a sodium salt compound.

[0113] 2) At a temperature of -78℃, the metal ligand cyclopentadienyl zirconium trichloride (1 mmol) was added to the above sodium salt compound and reacted at 25℃ for 12 h. After removing tetrahydrofuran under reduced pressure, 15 mL of toluene was added and the mixture was recrystallized at -40℃ to precipitate a yellow solid as the metal complex Zr1.

[0114] Fw = 363.39 for Zr1;

[0115] The NMR results for Zr1 are as follows: 1 H NMR (C6D6): δ7.70-7.64 (dd, J=7.5Hz, 1 H),7.35-7.31(m,J=7.5Hz,1H),7.11-7.01(m,J=7.5Hz,1H),6.74-6.72(dd,J=7.5Hz,1H),5.81(s,5H),2.55(s,6H).

[0116] Example 2

[0117] This embodiment is basically the same as Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-phenylphenol to prepare Zr2.

[0118] The Fw of Zr2 is 381.38;

[0119] The NMR results for Zr2 are as follows: 1 H NMR(C6D6)δ7.15-7.08(m,J=7.5Hz, 1 H),7.08-7.04(m,J=7.7Hz,1H),6.50-6.45(dd,J=7.5Hz,1H),5.75(s,5H),3.00(s, 6 H).

[0120] Example 3

[0121] This embodiment is basically the same as Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-phenylphenol to prepare Zr3.

[0122] Fw = 439.49 for Zr3;

[0123] The NMR results for Zr3 are as follows: 1 H NMR(C6D6): δ7.47-7.40(m,4H),7.40-7.36(m,1H),7.18-7.16(dd,J=7.5Hz,1H),7 .12-6.98(m,J=7.4Hz,1H),6.92-6.88(dd,J=7.4Hz,1H),5.82(s,5H),3.01(s,6H).

[0124] Example 4

[0125] This embodiment is basically the same as that of Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol to prepare Zr4.

[0126] The Fw of Zr4 is 435.58;

[0127] The NMR results for Zr4 are as follows: 1 H NMR (C6D6): δ7.22-7.14 (m, 2H), 6.84-6.74 (dd, J = 5.9Hz, 1H), 5.71 (s, 5H), 3.02 (s, 6H), 0.39 (s, 9H).

[0128] Example 5

[0129] This embodiment is basically the same as that of Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-tert-butylphenol to prepare Zr5.

[0130] The Fw of Zr5 is 419.50;

[0131] The NMR results for Zr5 are as follows: 1 H NMR (C6D6): δ7.22-7.20(dd,J=7.5Hz,1H),7.12-7.08(t,J=7.5Hz,1H),6.54-6.48(dd,J=9.0Hz,1H),5.73(s,5H),3.02(s,6H),1.42(s,9H)

[0132] Example 6

[0133] This embodiment is basically the same as Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-4,6-di-tert-butylphenol to prepare Zr6.

[0134] Fw = 475.61 for Zr6;

[0135] The NMR results for Zr6 are as follows: 1 H NMR (C6D6): δ6.96-6.94 (d, J=1.4Hz, 1H), 6.70-6.80 (d, J=1.4Hz, 1H), 5.65 (s, 5H), 3.02 (s, 6H), 1.40 (s, 9H), 1.31 (s, 9H).

[0136] Example 7

[0137] This embodiment is basically the same as that of Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol to prepare Zr7.

[0138] The Fw of Zr7 is 505.71;

[0139] The NMR results for Zr7 are as follows: 1 H NMR (C6D6): δ7.32-7.24 (m, 2H), 6.94-6.88 (dd, J = 5.9Hz, 1H), 1.83 (s, 15H), 2.92 (s, 6H), 0.34 (s, 9H).

[0140] Example 8

[0141] This embodiment is basically the same as that of Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol to prepare Zr8.

[0142] Zr8's Fw = 507.765

[0143] The NMR results for Zr8 are as follows: 1 H NMR (C6D6): δ7.25-7.17(m,2H),6.87(dd,J=5.9Hz,1H),6.05-5.98(t,2H),5.71-5.65(m,2H)3.06(s,6H),0.35(s,9H),0.28(s,9H).

[0144] Example 9

[0145] This embodiment is basically the same as Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol, and the metal ligand cyclopentadienyl zirconium trichloride is replaced with tert-butylcyclopentadienyl zirconium trichloride to prepare Zr9.

[0146] The Fw of Zr9 is 491.68;

[0147] The NMR results for Zr9 are as follows: 1 H NMR (C6D6): δ7.34-7.27(m,2H),6.94-6.86(dd,J=5.9Hz,1H),6.11-6.05(m,2H),5.74-5.69(m,2H),3.06(s,6H),0.39(s,9H),0.32(s,9H).

[0148] Example 10

[0149] This embodiment is basically the same as Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol, and the metal ligand cyclopentadienyl zirconium trichloride is replaced with indene zirconium trichloride to prepare Zr10.

[0150] The Fw of Zr10 is 485.64;

[0151] The NMR results for Zr10 are as follows: 1 H NMR(C6D6): δ7.23-7.21(dd,J=6.8Hz,2H),6.87(s,2H),6.86-6.83(dd,2H),6.0 2-6.01(d,J=6.0Hz,2H),5.83-5.81(m,J=6.8Hz,2H),2.97(s,6H),0.35(s,9H).

[0152] Example 11

[0153] This embodiment is basically the same as that of Example 1, except that 2-(dimethylamino)phenol in step 1) of Example 1 is replaced with 2-(dimethylamino)-6-trimethylsilylphenol, and the metal ligand cyclopentadienyl zirconium trichloride is replaced with indene zirconium trichloride to prepare Zr11.

[0154] Fw = 535.70 for Zr11;

[0155] The NMR results for Zr11 are as follows: 1 H NMR(C6D6): δ8.15-8.10(d,J=8.35Hz,2H),7.81-7.77(d,J=8.96Hz,2H),7.58 -7.49(t,2H),7.27-7.18(m,2H),6.94-6.86(m,4H),3.11(s,6H),0.39(s,9H).

[0156] Example 12

[0157] The method for preparing the cyclic olefin copolymer in this embodiment includes the following steps:

[0158] 1) Clean the polymerization flask containing the stirrer and thoroughly dried three times with high-purity nitrogen;

[0159] 2) Charge the polymerization flask with 1 atm of ethylene gas, add 20 mL of toluene, then add 3.78 mL of 0.5 g / mL norbornene toluene solution. Mix well and heat to 30 °C. Then add 20 mL of Zr1 complex toluene solution (containing 2 μmol of Zr1 complex) and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane). Start stirring and start timing. As ethylene dissolves in the solvent and is consumed in the reaction, replenish ethylene to keep the ethylene level at 1 atm. The reaction time is 60 minutes. Then turn off the ethylene gas.

[0160] 3) The reaction was terminated by adding 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%). The reaction solution was poured into a beaker and washed with a large amount of ethanol. The polymer was obtained by filtration and vacuum drying at 60°C for 24 h to constant weight.

[0161] Example 13

[0162] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 40°C in step 2).

[0163] Example 14

[0164] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 50°C in step 2).

[0165] Example 15

[0166] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 60°C in step 2).

[0167] Example 16

[0168] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 70°C in step 2).

[0169] Example 17

[0170] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 80°C in step 2).

[0171] Example 18

[0172] This embodiment is basically the same as embodiment 12, except that the temperature is raised to 90°C in step 2).

[0173] Example 19

[0174] This embodiment is basically the same as that of embodiment 16, except that 1.2 mL of methylaluminoxane (containing 2 mmol of methylaluminoxane) was added in step 2).

[0175] Example 20

[0176] This embodiment is basically the same as that of embodiment 16, except that 1.8 mL of methylaluminoxane (containing 3 mmol of methylaluminoxane) was added in step 2).

[0177] Example 21

[0178] This embodiment is basically the same as that of embodiment 16, except that 2.4 mL of methylaluminoxane (containing 4 mmol of methylaluminoxane) was added in step 2).

[0179] Example 22

[0180] This embodiment is basically the same as that of embodiment 16, except that 3.6 mL of methylaluminoxane (containing 6 mmol of methylaluminoxane) was added in step 2).

[0181] Example 23

[0182] This embodiment is basically the same as that of embodiment 16, except that 6 mL of methylaluminoxane (containing 10 mmol of methylaluminoxane) was added in step 2).

[0183] Example 24

[0184] This embodiment is basically the same as Example 16, except that 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) was added in step 2), and the reaction time was 30 min.

[0185] Example 25

[0186] This embodiment is basically the same as that of Example 16, except that 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) was added in step 2), and the reaction time was 120 minutes.

[0187] Example 26

[0188] This embodiment is basically the same as Example 16, except that 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) was added in step 2), and the reaction time was 240 minutes.

[0189] Example 27

[0190] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr2.

[0191] Example 28

[0192] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr3.

[0193] Example 29

[0194] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr4.

[0195] Example 30

[0196] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr5.

[0197] Example 31

[0198] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr6.

[0199] Example 32

[0200] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr7.

[0201] Example 33

[0202] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr8.

[0203] Example 34

[0204] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr9.

[0205] Example 35

[0206] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr10.

[0207] Example 36

[0208] This embodiment is basically the same as embodiment 16, except that the monoceramic zirconium metal compound added in step 2) is Zr11.

[0209] Example 37

[0210] This embodiment is basically the same as that of embodiment 16, except that 1.2 mL of modified methylaluminoxane (containing 2 mmol of modified methylaluminoxane) was added in step 2).

[0211] Example 38

[0212] This embodiment is basically the same as that of embodiment 16, except that 1.8 mL of modified methylaluminoxane (containing 3 mmol of modified methylaluminoxane) was added in step 2).

[0213] Example 39

[0214] This embodiment is basically the same as that of embodiment 16, except that 2.4 mL of modified methylaluminoxane (containing 4 mmol of modified methylaluminoxane) was added in step 2).

[0215] Example 40

[0216] This embodiment is basically the same as that of embodiment 16, except that 3 mL of modified methylaluminoxane (containing 5 mmol of modified methylaluminoxane) was added in step 2).

[0217] Example 41

[0218] This embodiment is basically the same as that of embodiment 16, except that 3.6 mL of modified methylaluminoxane (containing 6 mmol of modified methylaluminoxane) was added in step 2).

[0219] Example 42

[0220] This embodiment is basically the same as embodiment 16, except that 6 mL of modified methylaluminoxane (containing 10 mmol of modified methylaluminoxane) was added in step 2).

[0221] Comparative Example 1

[0222] This comparative example is basically the same as Example 16, except that the complex in step 2) of this comparative example is a thiophenol-phosphoryl titanium complex, which has the following structure:

[0223]

[0224] Comparative Example 2

[0225] This comparative example is basically the same as Example 16, except that the complex in step 2) of this comparative example is a nitrogen-heterocyclic borooxy metallocene complex, which has the following structure:

[0226]

[0227] Test case

[0228] The molecular weights of the cyclic olefin copolymers prepared in Examples 12-42 and Comparative Examples 1-2 were determined by gel permeation chromatography (GPC) at 150 °C on a PL-GPC220 column using three tandem PLgel 10 μm MIXED-B columns and 1,2,4-trichlorobenzene as the solvent. The test data are shown in Table 1.

[0229] The norbornene content in the cyclic olefin copolymers prepared in Examples 12-44 and Comparative Examples 1-2 was determined by solution analysis. 13 C nuclear magnetic resonance (C 13 The C-NMR (carbon dioxide-to-hydrocarbon dioxide) measurements were performed using a Bruker AVANCE III-400MHz spectrometer. The test data are shown in Table 1.

[0230] The glass transition temperatures of the cyclic olefin copolymers prepared in Examples 12-42 and Comparative Examples 1-2 were measured using a Q2000 DSC-7 instrument, with a test range of -30 to +300 °C (10 °C / min). Approximately 5.0 mg of the sample was heated to 300 °C at a heating rate of 10 °C / min and held at 300 °C for 5 minutes to remove thermal history, then cooled to -30 °C under N2 at a rate of 20 °C / min. This heating and cooling process was repeated twice. g The values ​​are selected from the second loop, and the data is recorded. The test data is shown in Table 1.

[0231] Table 1 Catalytic activity of catalysts and properties of cyclic olefin copolymers

[0232]

[0233]

[0234]

[0235] As shown in the table, in the preparation process of cyclic olefin copolymers in Examples 12-42 compared to Comparative Examples 1-2, the catalysts used in Examples 12-42 exhibit better catalytic activity, resulting in copolymers with higher molecular weights. Examples 12-42 have higher norbornene content, leading to higher glass transition temperatures. Furthermore, Examples 12-42 have smaller molecular weight distributions, resulting in more uniform products.

[0236] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A monoceramic zirconium metal compound, characterized in that, It has the structure shown in Equation 1: In Formula 1, X is independently selected from one of F, Cl, Br, and I; R1, R2, R3, and R4 are independently selected from H, halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, C3-C10 heterocyclic groups, C6-C20 aryl or C6-C20 heteroatom aryl groups, and C1-C6 alkyl-substituted or unsubstituted silyl groups. R5 is selected from C1-C20 substituted or unsubstituted cyclopentadienyl, C1-C20 substituted or unsubstituted indenyl, and C1-C20 substituted or unsubstituted fluorenyl.

2. The monocerozirconium metal compound according to claim 1, characterized in that, In the monoceramic zirconium metal compound, R1 is selected from H, C1-C4 alkyl, halogen, C6 aryl, and silyl; and / or, R2 is selected from H, C1-C4 alkyl, C1-C4 alkoxy; and / or, R3 and R4 are each independently selected from H or C1-C6 alkyl groups; and / or, R5 is selected from cyclopentadienyl, indene, fluorenyl, pentamethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, and tert-butyl-cyclopentadienyl.

3. The monoceramic zirconium metal compound according to claim 1, characterized in that, Including the following compounds: Zr1, where R1 and R2 are both hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or, Zr₂, where R₁ is F, R₂ is hydrogen, X is Cl, R₃ and R₄ are both hydrogen, and R₅ is cyclopentadienyl; or... Zr3, wherein R1 is phenyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or Zr4, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or Zr5, wherein R1 is tert-butyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or Zr6, wherein R1 and R2 are both tert-butyl, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or, Zr7, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethyl-cyclopentadienyl; or, Zr8, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is trimethylsilyl-cyclopentadienyl; or Zr9, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is tert-butyl-cyclopentadienyl; or Zr10, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is indenyl; or, Zr11, wherein R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is fluorene.

4. A method for preparing a mono-zirconium metal compound according to any one of claims 1-3, characterized in that, Includes the following steps: 1) 2-(dimethylamino)-phenol, including R1, R2, R3, and R4, is reacted with NaH in a solvent to obtain a sodium salt compound; 2) The sodium salt compound is reacted with the monoceramic zirconium metal salt in a solvent to obtain the monoceramic zirconium metal compound.

5. The method for preparing a monoceramic zirconium metal compound according to claim 4, characterized in that, In step 1), the molar ratio of 2-(dimethylamino)-phenol comprising R1, R2, R3, and R4 to NaH is 1:(1-3); and / or, In step 2), the molar ratio of the sodium salt compound to the monocerozirconium metal salt is 1:(1-3).

6. The method for preparing a mono-zirconium metal compound according to claim 4 or 5, characterized in that, The reaction temperature in step 1) is 25–50°C, and the reaction time is 2–8 hours; and / or, The reaction temperature in step 2) is -78 to 0℃, and the reaction time is 5 to 12 hours.

7. A catalyst, characterized in that, The monoceramic zirconium metal compound includes the monoceramic zirconium metal compound according to any one of claims 1-3 or the monoceramic zirconium metal compound according to any one of claims 4-6.

8. The catalyst according to claim 7, characterized in that, The catalyst further includes a co-catalyst, which includes at least one of alkylaluminoxane and / or modified alkylaluminoxane.

9. The catalyst according to claim 7 or 8, characterized in that, The molar ratio of aluminum in the alkylaluminoxane to zirconium in the monocerozirconium metal compound is (200-10000):

1.

10. A method for preparing a cyclic olefin copolymer, characterized in that, The copolymerization catalysis of olefin monomers is carried out using the catalyst according to any one of claims 7-9.

11. A cyclic olefin copolymer, characterized in that, In the cyclic olefin copolymer, the content of structural units from ethylene is 46–53 mol%, and the content of structural units from norbornene is 47–54 mol%.

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