Mono-titanocene metal complex, catalyst composition, propylene and 5-vinyl-2-norbornene copolymer and preparation method

Abstract

The invention provides a mono-titanocene metal complex, a catalyst composition, a propylene and 5-vinyl-2-norbornene copolymer and a preparation method, and the mono-titanocene metal complex has a structure as shown in a formula (I). The mono-titanocene metal catalytic system provided by the invention has the characteristic of high catalytic activity; and the propylene and 5-vinyl-2-norbornene copolymer with high molecular weight, narrow molecular weight distribution and high glass transition temperature can be prepared.

Description

Technical Field

[0001] This invention belongs to the field of metallocene catalyst technology, specifically relating to a monotitanium metal complex, a catalyst composition, a copolymer of propylene and 5-vinyl-2-norbornene, and a preparation method thereof. Background Technology

[0002] Olefin polymerization catalysts directly determine the internal structure and morphology of polyolefin products and are the core technology in the development of the polyolefin industry. Their development has generally gone through three stages: a) Ziegler-Natta catalysts; b) metallocene catalysts; and c) non-metallocene catalysts. The latter two are homogeneous catalysis, and compared to metallocene catalysts, non-metallocene catalysts have developed a series of bidentate or multidentate ligands, including N^N, N^O, N^P, N^N^N, and N^N^P. SHOPs catalysts based on P^O ligands have been proven to be effective olefin polymerization catalysts.

[0003] Combining the advantages of Group IV metallocene catalysts (Ti, Ti, Hf) and P^O ligands, the designed catalysts possess well-defined structures, single active centers, and customizable structures, resulting in superior performance in polymerization activity and product structure control. This has made them a rapidly developing catalytic system for industrial applications. Furthermore, by modifying the ligands and thus controlling the spatial structure and central metal charge of the monometallocene catalyst, olefins such as ethylene, propylene, 1-octene, norbornene, and 5-vinyl-2-norbornene (VNB) can be coordinated and inserted at specific angles and in specific ways, yielding polyolefin materials with different compositions, sequence structures, and stereostructures, greatly enriching the variety of polyolefin products.

[0004] Amorphous thermoplastic materials prepared from olefin-cyclic olefin copolymers (COCs) exhibit excellent properties, such as transparency, high glass transition temperature, and heat resistance. The copolymerization reaction of ethylene and norbornene has been described and introduced in detail in the literature. In contrast, there are few reports on the copolymerization of propylene with norbornene and its derivatives. Introducing polar groups into the molecular backbone of the copolyolefin remains one of the major challenges in the field of olefin polymerization.

[0005] The direct copolymerization of olefins using polar monomers typically yields minimal results. This is because transition metal-based catalysts are usually electrophilic strong Lewis acids, which are easily poisoned in the presence of heteroatom-containing monomers. Although some attempts have been made and progress has been achieved in catalyzing the copolymerization of olefins with polar monomers using post-transition metal catalysts, other synthetic routes are still needed to obtain functionalized polyolefin materials. One approach to circumvent this key problem of catalyst poisoning is to copolymerize olefins with bifunctional monomers, where one functional group is inert to the catalyst but can subsequently undergo various functionalization reactions during post-polymerization. Examples include the polymerization of ethylene with asymmetrically substituted α,w-dienes, the copolymerization of propylene with 7-methyl-1,6-octadiene, and the copolymerization of the non-conjugated diene 5-vinyl-2-norbornene (VNB) with ethylene using Cp2ZrCl2 / MAO and Ph2C(Flu)(Cp)ZrCl2 / MAO catalytic systems. Summary of the Invention

[0006] To overcome the problem of low polymerization activity in the existing technology for copolymerization systems of propylene and 5-vinyl-2-norbornene (VNB), the present invention provides a monotitanium metal complex, a catalyst composition, a copolymer of propylene and 5-vinyl-2-norbornene, and a method for preparing them, so as to obtain a highly efficient olefin copolymerization catalyst.

[0007] To achieve the above objectives, the present invention provides a monotitanium metal complex having a structure as shown in formula (I):

[0008]

[0009] In formula (I), each X is the same or different, and is independently selected from F, Cl, Br, and I;

[0010] R1, R2, R3, and R4 may be the same or different, and each is independently selected from H, halogen, monosubstituted or polysubstituted or unsubstituted C1-C6 alkyl, monosubstituted or polysubstituted or unsubstituted C1-C6 alkoxy, monosubstituted or polysubstituted or unsubstituted C3-C10 heterocyclic, monosubstituted or polysubstituted or unsubstituted C6-C20 aryl or C6-C20 heteroatomic aryl;

[0011] R5 is selected from cyclopentadienyl or unsubstituted cyclopentadienyl groups with 1-20 carbon atoms that are monosubstituted or polysubstituted indenyl or unsubstituted indenyl groups with 1-20 carbon atoms, or fluorenyl or unsubstituted fluorenyl groups with 1-20 carbon atoms that are monosubstituted or polysubstituted fluorenyl groups with 1-20 carbon atoms.

[0012] The monotitanium metal complex of this invention, as a catalyst, can solve the problems of low polymerization activity and high preparation cost in the copolymerization system of propylene and 5-vinyl-2-norbornene (VNB), and the inability to simultaneously obtain high molecular weight, high glass transition temperature, and high polymerization activity in the resulting copolymer. The purpose of this invention is to provide a method for preparing and applying a monotitanium metal complex to obtain a highly efficient olefin copolymerization catalyst.

[0013] This invention designs and synthesizes asymmetric metallocene catalysts for the copolymerization reaction of propylene and polar monomer VNB to prepare polyolefin materials with polar functional groups.

[0014] In the above-mentioned monocyclic titanium metal complexes, preferably, R1 is selected from H, C1-C4 alkyl, halogen, C6 aryl or silyl.

[0015] In the above-mentioned monolithocene titanium metal complex, preferably, R2 is selected from H, C1-C4 alkyl or C1-C4 alkoxy.

[0016] In the above-mentioned monolithocene titanium metal complex, preferably, R3 and R4 are each independently selected from H or C1-C6 alkyl groups.

[0017] In the above-mentioned monoceramic titanium metal complex, preferably, R5 is selected from cyclopentadienyl, indene, fluorenyl, pentamethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl or tert-butyl-cyclopentadienyl.

[0018] In the above-mentioned monolithocene titanium metal complex, preferably, X is Cl.

[0019] In the above-mentioned monolithocene titanium metal complexes, preferably, in formula (I),

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

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

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

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

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

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

[0026] R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethylcyclopentadienyl; or

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

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

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

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

[0031] In this invention, the term "C1-C6 alkyl" refers to a straight-chain or branched alkyl group having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, and neopentyl.

[0032] The term "C1-C6 alkoxy" should be understood as preferably referring to a straight-chain or branched saturated monovalent hydrocarbon group of the formula -O-alkyl having 1-6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, or isomers thereof.

[0033] The term "C3-C10 heterocyclic group" should be understood to preferably refer to a group of the formula -N / O / S-cycloalkyl having 3-10 carbon atoms. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). In particular, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirrobutyl, oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group can be benzofused. The 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, such as 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, or it can be benzofused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic.

[0034] The term "C6-C20 aryl" should be understood to preferably refer to a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms with monovalent aromaticity or partial aromaticity, preferably "C6-C14 aryl". The term "C6-C14 aryl" should be understood to preferably refer to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C6-C14 aryl") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms, particularly a ring having 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C9 aryl"), such as indenyl or indenyl, or a ring having 10 carbon atoms ("C10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or a ring having 13 carbon atoms ("C13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C14 aryl"), such as anthracene.

[0035] The term "C6-C20 heteroatom aryl" should be understood to preferably refer to a group having the formula -N-aryl or -N-heteroaryl having 6 to 20 carbon atoms. Monocyclic examples of heteroaryl groups include, but are not limited to, thiopheneyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[a] derivatives, such as benzofuranyl, benzothiopheneyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, and indazole. Indoyl, isoindoyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylonitrile, indazinyl, purine, etc., and their benzo[derivatives]; or cyclophosphinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphridinyl, pteridinyl, carbazoyl, acridineyl, phenazinyl, phenothiazinyl, phenotoxazinyl, etc.

[0036] The present invention also provides a method for preparing the above-mentioned monotitanium metal complex, comprising:

[0037] The ligand shown in formula (II) is reacted with NaH in the first reaction to obtain a sodium salt compound;

[0038]

[0039] The sodium salt compound is reacted with a metallocene chloride, such as R5-TiX3, to obtain the monotitanium metal complex.

[0040] In the above method for preparing mono-titanium metal complexes, preferably, the ligand shown in formula (II) is a 2-(dimethylamino)-phenol ligand or a substituted 2-(dimethylamino)-phenol ligand, and the metallocene chloride shown in R5-TiX3 is a mono-metallocene chloride.

[0041] In the above method for preparing monotitanium metal complexes, preferably, the molar ratio of the ligand shown in formula (II), NaH and the metallocene chloride shown in R5-TiX3 is 1:(1-1.15):(1-2).

[0042] In the above-mentioned method for preparing monolithocene titanium metal complexes, preferably, the reaction temperature of the first reaction is 25-50℃; the reaction temperature of the second reaction is -78℃ to 0℃; and both the first and second reactions are carried out in tetrahydrofuran.

[0043] The present invention also provides a catalyst composition comprising a main catalyst and a co-catalyst, wherein the main catalyst is the above-mentioned monotitanium metal complex, and the co-catalyst is an alkylaluminoxane; wherein the molar ratio of aluminum in the co-catalyst to titanium in the main catalyst is 200-10000:1, more preferably 1100-10000.

[0044] In the above catalyst composition, preferably, the alkylaluminoxane includes methylaluminoxane (MAO) and / or triisobutyl-modified methylaluminoxane (MMAO).

[0045] In the above catalyst composition, preferably, when the co-catalyst is methylaluminoxane, the molar ratio of aluminum in methylaluminoxane to titanium in the monotitanium metal complex is 1000-5000:1, more preferably 2500:1, for example 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 4000:1, 5000:1;

[0046] When the cocatalyst is triisobutyl-modified methylaluminoxane, the molar ratio of aluminum in the triisobutyl-modified methylaluminoxane to titanium in the monotitanium metal complex is 1000-5000:1, more preferably 2500:1, for example 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 4000:1, 5000:1.

[0047] This invention provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising: copolymerizing propylene and 5-vinyl-2-norbornene (VNB) in a solvent under the action of a catalyst to obtain the copolymer of propylene and 5-vinyl-2-norbornene; wherein the catalyst comprises the above-mentioned monotitanium metal complex or the above-mentioned catalyst composition.

[0048] In the above method for preparing the copolymer of propylene and 5-vinyl-2-norbornene, preferably, the molar ratio of 5-vinyl-2-norbornene to the monotitanium metal complex is 4000-40000.

[0049] In the above method for preparing the copolymer of propylene and 5-vinyl-2-norbornene, preferably, the ratio of 5-vinyl-2-norbornene to propylene is 20-200 mmol / atm.

[0050] In the above-mentioned method for preparing the copolymer of propylene and 5-vinyl-2-norbornene, preferably, the copolymerization temperature is 0-200℃ and the reaction time is 1-300 min; more preferably, the copolymerization temperature is 50-160℃ and the reaction time is 60-120 min.

[0051] In the above method for preparing the copolymer of propylene and 5-vinyl-2-norbornene, preferably, the copolymerization reaction is carried out in a solvent, wherein the solvent is selected from one or more combinations of toluene, xylene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, and n-octane, and more preferably toluene.

[0052] In the above method for preparing the copolymer of propylene and 5-vinyl-2-norbornene, preferably, the polymerization reaction is carried out in an inert atmosphere; the inert atmosphere is selected from argon.

[0053] The present invention also provides a copolymer of propylene and 5-vinyl-2-norbornene, which is obtained by the above-mentioned preparation method of the copolymer of propylene and 5-vinyl-2-norbornene.

[0054] In the above-mentioned copolymer of propylene and 5-vinyl-2-norbornene, preferably, based on the total molar number of each structural unit in the copolymer of propylene and 5-vinyl-2-norbornene, the content of structural units from propylene is 63-79 mol%, and the content of structural units from 5-vinyl-2-norbornene (VNB) is 21-37 mol%.

[0055] In the above-mentioned copolymer of propylene and 5-vinyl-2-norbornene, preferably, the copolymer of propylene and 5-vinyl-2-norbornene has a weight-average molecular weight of 600,000-800,000, a molecular weight distribution index of 2.0-3.0, and a glass transition temperature of 110-140°C.

[0056] The technical solution provided by this invention has the following beneficial effects:

[0057] The monotitanium metal catalytic system provided by this invention has the characteristics of high catalytic activity and can produce copolymers of propylene and 5-vinyl-2-norbornene with high molecular weight, narrow molecular weight distribution, and high glass transition temperature. Furthermore, by adjusting the type of metallocene catalyst, the type and amount of methylaluminoxane, and the polymerization conditions in the catalytic system, the molecular weight and glass transition temperature of the copolymer can be controlled. Detailed Implementation

[0058] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0059] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0060] The molecular weight of the polymer was determined by gel permeation chromatography (GPC) at 150 °C on a PL-GPC220 column using three PLgel 10 μm MIXED-B columns in series, with 1,2,4-trichlorobenzene as the solvent.

[0061] The content of 5-vinyl-2-norbornene (VNB) in the polymer was determined by solution analysis. 13 C nuclear magnetic resonance (C 13 The C-NMR (C-NMR) assay was performed on a Bruker AVANCE III-400MHz spectrometer.

[0062] The glass transition temperature of the polymer was measured using a Q2000 DSC-7 instrument, with a test range of -30℃ to +300℃ (10℃ / min). Approximately 5.0 mg of the sample was heated to 300℃ at a heating rate of 10℃ / min and held at 300℃ for 5 minutes to remove thermal history, then cooled to -30℃ under N2 at a rate of 20℃ / min. This heating and cooling process was repeated twice. g The value is selected from the second loop, and the data is recorded.

[0063] The present invention provides 11 monotitanium metal complexes, denoted as monotitanium metal complexes Ti1-Ti11, with the following corresponding groups in (I):

[0064] Monolithic titanium metal complex Ti1: R1 and R2 are both hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl.

[0065] Monolithic titanium metal complex Ti2: R1 is F, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl.

[0066] Monolithic titanium metal complex Ti3: R1 is phenyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl;

[0067] Monolithic titanium metal complex Ti4: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl.

[0068] Monolithic titanium metal complex Ti5: R1 is tert-butyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl.

[0069] Monolithic titanium metal complex Ti6: R1 and R2 are both tert-butyl, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl;

[0070] Monolithic titanium metal complex Ti7: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethyl-cyclopentadienyl.

[0071] Monolithic titanium metal complex Ti8: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is trimethylsilyl-cyclopentadienyl.

[0072] Monolithic titanium metal complex Ti9: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is tert-butyl-cyclopentadienyl.

[0073] Monolithic titanium metal complex Ti10: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is indenyl;

[0074] Monolithic titanium metal complex Ti11: R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is fluorene.

[0075] The present invention will now be described in detail with reference to specific preparation examples and embodiments.

[0076] Preparation Example 1

[0077] This preparation example provides a method for preparing a monotitanium metal complex, including the following steps:

[0078] 2-(dimethylamino)phenol (0.137 g, 1 mmol) and sodium hydride (24 mg, 1 mmol) were reacted at 25 °C for 5 h in the presence of argon atmosphere and 20 mL of anhydrous tetrahydrofuran.

[0079] At a temperature of -78℃, cyclopentadienyl titanium trichloride (0.219 g, 1 mmol) was added 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 (0.263 g, Fw = 325.08) as the monotitanium metal complex Ti1, with a yield of 81%. 1 H NMR (C6D6): δ7.55-7.49 (dd, J=7.4Hz, 1H), 7.20-7.16 (m, J=7.5Hz, 1H), 6.98-6 .89(m,J=7.6Hz,1H),6.58-6.6.51(dd,J=7.5Hz,1H),5.75(s,5H),2.51(s,6H).

[0080] Preparation Example 2

[0081] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-fluorophenol, while the other conditions remain the same. This preparation example yielded a yellow solid (0.271 g, Fw = 343.07) as the monotitanium metal complex Ti2, with a yield of 79%. 1H NMR (C6D6) δ7.18-7.12(m,J=7.5Hz,1H),7.08-7.04(m,J=7.7Hz,1H),6.52-6.47(dd,J=7.5Hz,1H),5.71(s,5H),3.05(s,6H).

[0082] Preparation Example 3

[0083] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-phenylphenol, while the other conditions remain the same. This preparation example yielded a yellow solid (0.330 g, Fw = 395.03) as the monotitanium metal complex Ti3, with a yield of 82%. 1 H NMR(C6D6): δ7.45-7.40(m,4H),7.39-7.36(m,1H),7.20-7.16(dd,J=7.5Hz,1H),7 .13-6.98(m,J=7.4Hz,1H),6.91-6.86(dd,J=7.4Hz,1H),5.75(s,5H),3.08(s,6H).

[0084] Preparation Example 4

[0085] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol, while the other conditions remain the same. This preparation example yielded a yellow solid (0.338 g, Fw = 397.27) as the monotitanium metal complex Ti4, with a yield of 85%. 1 H NMR (C6D6): δ7.25-7.14(m,2H),6.82-6.74(dd,J=5.9Hz,1H),5.69(s,5H),3.11(s,6H),0.35(s,9H).

[0086] Preparation Example 5

[0087] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-tert-butylphenol, while the other conditions remain the same. This preparation example yielded a yellow solid (0.316 g, Fw = 381.19 g) as the monotitanium metal complex Ti5, with a yield of 83%. 1H NMR (C6D6): δ7.32-7.29(dd,J=7.5Hz,1H),7.22-7.15(t,J=7.5Hz,1H),6.61-6.57(dd,J=9.0Hz,1H),5.83(s,5H),3.09(s,6H),1.39(s,9H).

[0088] Preparation Example 6

[0089] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-4,6-di-tert-butylphenol, while the other conditions remain the same. This preparation example yielded a yellow solid (0.35 g, Fw = 437.3) as the monotitanium metal complex Ti6, with a yield of 80%. 1 H NMR (C6D6): δ6.98-6.94(d,J=1.4Hz,1H),6.88-6.80(d,J=1.4Hz,1H),5.62(s,5H),3.05(s,6H),1.43(s,9H),1.30(s,9H).

[0090] Preparation Example 7

[0091] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol; and the metal ligand cyclopentadienyl titanium trichloride is replaced with pentamethylcyclopentadienyl titanium trichloride, with all other conditions remaining the same. This preparation example yielded a yellow solid (0.402 g, Fw = 467.41) as the monotitanium metal complex Ti7, with a yield of 86%. 1 H NMR (C6D6): δ7.42-7.34(m,2H),7.04-6.95(dd,J=5.9Hz,1H),1.88(s,15H),2.96(s,6H),0.38(s,9H).

[0092] Preparation Example 8

[0093] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol; and the metal ligand cyclopentadienyltitanium trichloride is replaced with trimethylsilylcyclopentadienyltitanium trichloride, with all other conditions remaining the same. This preparation example yielded a yellow solid (0.385 g, Fw = 469.455) as the monotitanium metal complex Ti8, with a yield of 82%. 1H NMR (C6D6): δ7.35-7.27(m,2H),6.97(dd,J=5.9Hz,1H),6.15-6.08(t,2H),5.81-5.66(m,2H)3.08(s,6H),0.35(s,9H),0.27(s,9H).

[0094] Preparation Example 9

[0095] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol; and the metal ligand cyclopentadienyl titanium trichloride is replaced with tert-butylcyclopentadienyl titanium trichloride, with all other conditions remaining the same. This preparation example yielded a yellow solid (0.354 g, Fw = 453.37) as the monotitanium metal complex Ti9, with a yield of 78%. 1 H NMR (C6D6): δ7.24-7.17(m,2H),6.84-6.76(dd,J=5.9Hz,1H),6.04-5.98(m,2H),5.74-5.69(m,2H),3.14(s,6H),0.39(s,9H),0.32(s,9H).

[0096] Preparation Example 10

[0097] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol; and the metal ligand cyclopentadienyl titanium trichloride is replaced with indene titanium trichloride, with all other conditions remaining the same. This preparation example yielded a yellow solid (0.362 g, Fw = 447.33) as the monotitanium metal complex Ti10, with a yield of 81%. 1 H NMR(C6D6): δ7.43-7.38(dd,J=6.8Hz,2H),6.87(s,2H),6.96-6.93(dd,2H),6.1 2-6.09(d,J=6.0Hz,2H),5.81-5.78(m,J=6.8Hz,2H),2.95(s,6H),0.35(s,9H).

[0098] Preparation Example 11

[0099] This preparation example provides a method for preparing a monotitanium metal complex, which is the same as that in Preparation Example 1, except that 2-(dimethylamino)phenol is replaced with 2-(dimethylamino)-6-trimethylsilylphenol; and the metal ligand cyclopentadienyl titanium trichloride is replaced with fluorenyl titanium trichloride, with all other conditions remaining the same. This preparation example yielded a yellow solid (0.413 g, Fw = 497.39) as the monotitanium metal complex Ti11, with a yield of 83%. 1 H NMR(C6D6): δ8.18-8.12(d,J=8.35Hz,2H),7.85-7.74(d,J=8.96Hz,2H),7.61 -7.55(t,2H),7.27-7.20(m,2H),6.98-6.86(m,4H),3.06(s,6H),0.42(s,9H).

[0100] Example 1

[0101] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0102] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 50 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0103] Example 2

[0104] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0105] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 60 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0106] Example 3

[0107] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0108] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0109] Example 4

[0110] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0111] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 80 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0112] Example 5

[0113] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0114] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 90 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0115] Example 6

[0116] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0117] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 80 °C. 2 μmol of Ti1 complex and 1.2 mL of methylaluminoxane (containing 2 mmol of methylaluminoxane) were added, and stirring was started and timed. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene was shut off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. The mixture was filtered to obtain the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0118] Example 7

[0119] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0120] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 3 μmol of Ti1 complex and 1.8 mL of methylaluminoxane (containing 3 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0121] Example 8

[0122] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0123] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 2.4 mL of methylaluminoxane (containing 4 mmol of methylaluminoxane) were added, and stirring was started and timed. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. The mixture was filtered to obtain the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0124] Example 9

[0125] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0126] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3.6 mL of methylaluminoxane (containing 6 mmol of methylaluminoxane) were added, and stirring was started and timed. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. The mixture was filtered to obtain the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0127] Example 10

[0128] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0129] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 6 mL of methylaluminoxane (containing 10 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0130] Example 11

[0131] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0132] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 30 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0133] Example 12

[0134] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0135] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 120 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0136] Example 13

[0137] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0138] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 240 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0139] Example 14

[0140] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0141] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti2 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0142] Example 15

[0143] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0144] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti3 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added, and stirring was started and timed. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene was shut off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. The mixture was filtered to obtain the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0145] Example 16

[0146] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0147] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti4 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0148] Example 17

[0149] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0150] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti5 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0151] Example 18

[0152] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0153] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti6 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added, and stirring was started and timed. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. The mixture was filtered to obtain the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0154] Example 19

[0155] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0156] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70°C. 2 μmol of Ti7 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60°C for 24 h to constant weight.

[0157] Example 20

[0158] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0159] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti8 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0160] Example 21

[0161] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0162] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70°C. 2 μmol of Ti8 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. Propylene was replenished as it dissolved in the solvent and was consumed in the reaction, maintaining a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60°C for 24 hours to constant weight.

[0163] Example 22

[0164] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0165] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti9 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0166] Example 23

[0167] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0168] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti10 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0169] Example 24

[0170] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0171] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti11 complex and 3 mL of methylaluminoxane (containing 5 mmol of methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0172] Example 25

[0173] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0174] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 1.8 mL of modified methylaluminoxane (containing 3 mmol of modified methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0175] Example 26

[0176] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0177] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 2.4 mL of modified methylaluminoxane (containing 4 mmol of modified methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0178] Example 27

[0179] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0180] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3 mL of modified methylaluminoxane (containing 5 mmol of modified methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0181] Example 28

[0182] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0183] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 3.6 mL of modified methylaluminoxane (containing 6 mmol of modified methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0184] Example 29

[0185] This embodiment provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising the following steps:

[0186] The polymerization flask, equipped with a stirrer and thoroughly dried, was repeatedly cleaned three times with high-purity nitrogen. Propylene gas was introduced at 1 atm, followed by the addition of 20 mL toluene, 3.78 mL of a 0.5 g / mL 5-vinyl-2-norbornene (VNB) toluene solution, and the temperature was raised to 70 °C. 2 μmol of Ti1 complex and 6 mL of modified methylaluminoxane (containing 10 mmol of modified methylaluminoxane) were added. Stirring was started and the timer was established. As propylene dissolved in the solvent and was consumed in the reaction, propylene was replenished to maintain a constant 1 atm. After 60 minutes, the propylene concentration was turned off, and 1 mL of an ethanol solution containing 2,6-di-tert-butyl-4-methylphenol (1 wt / v-%) and hydrochloric acid (2 wt / v-%) was added to terminate the reaction. The reaction solution was poured into a beaker and washed with a large amount of ethanol. Filtration yielded the copolymer of propylene and 5-vinyl-2-norbornene, which was then vacuum dried at 60 °C for 24 h to constant weight.

[0187] Comparative Example 1

[0188] This comparative example provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, which differs from Example 15 only in that the main catalyst used in this comparative example is a phenol-phosphoryl titanium complex; the other conditions are the same as in Example 15.

[0189] The structure of the phenol-phosphoryl titanium complex used in this comparative example is as follows: It can be synthesized according to the method reported in CN105175596A (A method for catalytic copolymerization of ethylene and norbornene).

[0190] Comparative Example 2

[0191] This comparative example provides a method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, which differs from Example 5 only in that the main catalyst used in this comparative example is a silicon-bridged quinolino-stabilized metallocene compound; the other conditions are the same as in Example 5.

[0192] The structure of the main catalyst in this comparative example is as follows: It can be prepared according to the method reported in patent CN116854856A (a method for preparing a terpolymer of nobornene, long-chain olefin and methyl acrylate using a monotitanium catalyst).

[0193] Test case

[0194] The catalytic activity of the copolymerization reaction of Examples 1-29 and Comparative Examples 1-2 and the properties of the copolymer products were tested, and the results are shown in Table 1.

[0195] Table 1 Catalytic activity and properties of copolymers

[0196]

[0197]

[0198] As shown in Table 1, compared with other metallocene catalysts, the monotitanium metal catalytic system provided by the present invention has higher catalytic activity and can produce propylene-5-vinyl-2-norbornene copolymer with high molecular weight, narrow molecular weight distribution and high glass transition temperature.

[0199] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A monotitanium metal complex having the structure shown in formula (I): in, In formula (I), each X is the same or different, and is independently selected from F, Cl, Br, and I; R1, R2, R3, and R4 may be the same or different, and each is independently selected from H, halogen, monosubstituted or polysubstituted or unsubstituted C1-C6 alkyl, monosubstituted or polysubstituted or unsubstituted C1-C6 alkoxy, monosubstituted or polysubstituted or unsubstituted C3-C10 heterocyclic, monosubstituted or polysubstituted or unsubstituted C6-C20 aryl or C6-C20 heteroatomic aryl; R5 is selected from cyclopentadienyl or unsubstituted cyclopentadienyl groups with 1-20 carbon atoms that are monosubstituted or polysubstituted indenyl or unsubstituted indenyl groups with 1-20 carbon atoms, or fluorenyl or unsubstituted fluorenyl groups with 1-20 carbon atoms that are monosubstituted or polysubstituted fluorenyl groups with 1-20 carbon atoms.

2. The monotitanium metal complex according to claim 1, wherein, R1 is selected from H, C1-C4 alkyl, halogen, C6 aryl, or silyl.

3. The monotitanium metal complex according to claim 1, wherein, R2 is selected from H, C1-C4 alkyl, or C1-C4 alkoxy.

4. The monotitanium metal complex according to claim 1, wherein, R3 and R4 are each independently selected from H or C1-C6 alkyl groups.

5. The monotitanium metal complex according to claim 1, wherein, R5 is selected from cyclopentadienyl, indole, fluorenyl, pentamethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, or tert-butyl-cyclopentadienyl.

6. The monotitanium metal complex according to claim 1, wherein, X is Cl.

7. The monotitanium metal complex according to any one of claims 1-6, wherein, In formula (I), R1 and R2 are both hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 is F, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 is phenyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 is tert-butyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 and R2 are both tert-butyl, X is Cl, R3 and R4 are both hydrogen, and R5 is cyclopentadienyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is pentamethylcyclopentadienyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is trimethylsilyl-cyclopentadienyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is tert-butyl-cyclopentadienyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is indenyl; or R1 is trimethylsilyl, R2 is hydrogen, X is Cl, R3 and R4 are both hydrogen, and R5 is fluorene.

8. A method for preparing a monotitanium metal complex according to any one of claims 1-7, comprising: The ligand shown in formula (II) is reacted with NaH in the first reaction to obtain a sodium salt compound; The sodium salt compound is reacted with a metallocene chloride, such as R5-TiX3, to obtain the monotitanium metal complex.

9. The method for preparing the monotitanium metal complex according to claim 8, wherein, The molar ratio of the ligand shown in formula (II), NaH and the metallocene chloride shown in R5-TiX3 is 1:(1-1.15):(1-2).

10. The method for preparing monotitanium metal complexes according to claim 8, wherein the reaction temperature of the first reaction is 25-50°C; the reaction temperature of the second reaction is -78°C to 0°C; and both the first and second reactions are carried out in tetrahydrofuran.

11. A catalyst composition comprising a main catalyst and a co-catalyst, wherein the main catalyst is a monotitanium metal complex according to any one of claims 1-7, and the co-catalyst is an alkylaluminoxane; wherein, The molar ratio of aluminum in the co-catalyst to titanium in the main catalyst is 200-10000:

1.

12. The catalyst composition according to claim 11, wherein, The alkylaluminoxanes include methylaluminoxanes and / or triisobutyl-modified methylaluminoxanes.

13. The catalyst composition according to claim 11, wherein, When the cocatalyst is methylaluminoxane, the molar ratio of aluminum in methylaluminoxane to titanium in the monotitanium metal complex is 1000-5000:1; When the cocatalyst is triisobutyl-modified methylaluminoxane, the molar ratio of aluminum in the triisobutyl-modified methylaluminoxane to titanium in the monotitanium metal complex is 1000-5000:

1.

14. A method for preparing a copolymer of propylene and 5-vinyl-2-norbornene, comprising: In the presence of a catalyst, propylene is copolymerized with 5-vinyl-2-norbornene to obtain the copolymer of propylene and 5-vinyl-2-norbornene; wherein the catalyst comprises the monotitanium metal complex according to any one of claims 1-7 or the catalyst composition according to any one of claims 11-13.

15. The method for preparing the copolymer of propylene and 5-vinyl-2-norbornene according to claim 14, wherein, The molar ratio of 5-vinyl-2-norbornene to the monotitanium metal complex is 4000-40000.

16. The method for preparing the copolymer of propylene and 5-vinyl-2-norbornene according to claim 14, wherein, The ratio of 5-vinyl-2-norbornene to propylene is 20-200 mmol / atm.

17. The method for preparing the copolymer of propylene and 5-vinyl-2-norbornene according to claim 14, wherein, The temperature for copolymerization is 0-200℃, and the reaction time is 1-300 min.

18. The method for preparing the copolymer of propylene and 5-vinyl-2-norbornene according to claim 14, wherein, The copolymerization reaction is carried out in a solvent selected from one or more of toluene, xylene, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, and n-octane.

19. A copolymer of propylene and 5-vinyl-2-norbornene, obtained by the method for preparing the copolymer of propylene and 5-vinyl-2-norbornene according to any one of claims 14-18.

20. The copolymer of propylene and 5-vinyl-2-norbornene according to claim 19, wherein, Based on the total molar number of each structural unit in the copolymer, the content of structural units from propylene is 63-79 mol%, and the content of structural units from 5-vinyl-2-norbornene is 21-37 mol%. The propylene-norbornene copolymer has a weight-average molecular weight of 600,000-800,000, a molecular weight distribution index of 2.0-3.0, and a glass transition temperature of 110-140℃.

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