Complex metal compound, preparation method thereof and application thereof

Abstract

The present invention discloses an N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex of Group IVB metal compound, its preparation method and application. The structure of the compound is shown in the following formula (I): wherein, M is selected from titanium, zirconium, hafnium; R is selected from tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; R 1 , R 2 are respectively selected from chlorine, fluorine, methyl, ethyl, isopropyl, methoxy, and R 1 , R 2 are the same or different. The N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex of Group IVB metal compound of the present invention synthesizes a novel nitrogen-oxygen-nitrogen tridentate coordinated Group IVB metal compound by designing and optimizing the ligand structure, so that it has good activity, thermal stability and controllability in the copolymerization reaction of α-olefins and cycloolefins.

Description

Technical Field

[0001] The present invention relates to a class of complex Group IV metal compounds, their preparation methods and applications, and particularly to N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex Group IV metal compounds, their preparation methods and applications in catalyzing the copolymerization reaction of α-olefins and cycloolefins. Background Art

[0002] Polyolefins are a class of materials widely used in life, and their market scale has reached billions of dollars annually. Various high-performance polymer products have been widely used in our daily lives. Among them, cycloolefin copolymer (COC) materials have received increasing attention due to their excellent optical properties, thermodynamic stability, water vapor tightness, and rigidity. They have been commercially applied in advanced optics, medical devices, containers, and packaging, etc., and have broad development prospects and have developed rapidly in recent years.

[0003] The physical and mechanical properties of polymers determine their potential applications, and the physical and mechanical properties mainly depend on the composition and structure of the polymers. Polymers formed by the addition polymerization of cycloolefins exhibit physical and mechanical properties different from those of acyclic polymers due to their large rigid rings. However, such polymers have poor solubility and high processing temperatures (close to the decomposition temperature), making it difficult to achieve industrial applications. Introducing α-olefins such as ethylene into the cycloolefin polymer chain through copolymerization to obtain cycloolefin copolymers. The polymer materials obtained in this way not only have the excellent physical and mechanical properties and optical properties of cycloolefin polymers, but the introduction of α-olefins can also significantly improve the processing properties of the polymers, thus becoming a special plastic with excellent properties.

[0004] The currently widely studied and applied COC materials are mainly prepared by addition polymerization of corresponding monomers. The development and utilization of catalysts are the key to the preparation of polyolefin materials. Traditional olefin polymerization catalysts such as Ziegler-Natta catalysts cannot be used to prepare COC materials. The commonly used catalysts are metallocene catalysts, which have complex synthesis routes and high costs. In recent years, non-metallocene catalysts have received extensive attention due to their diverse structures and simple synthesis. Such catalysts also exhibit excellent properties in the catalytic synthesis of COC materials. For example, by designing and adjusting the ligand structure, efficient and controllable polymerization of α-olefins and cycloolefins can be achieved, thereby preparing COC materials with controllable molecular weight, molecular weight distribution, and cycloolefin content. Moreover, by introducing specific functional groups on the ligand, the thermal stability and other properties of the catalyst can be significantly improved. Group IV metal organic compounds with nitrogen coordination exhibit unique properties in the catalytic synthesis of COC materials. Bis(pyridine-imine)titanium catalysts (PI catalysts) (J. Am. Chem. Soc., 2004, 126(38): 12023-12032; J. Organomet. Chem., 2005, 690(20): 4382-4397.) exhibit excellent catalytic activity in the polymerization of ethylene-norbornene and show the characteristics of living polymerization, obtaining an alternating copolymer of the two monomers with high molecular weight and narrow molecular weight distribution. However, the norbornene content of the ethylene-norbornene copolymer obtained by this catalyst is relatively low, and it is a completely alternating copolymer. Moreover, the thermal stability of this catalyst is general, and its activity decreases and controllability deteriorates at higher temperatures. Titanium catalysts with nitrogen-oxygen bidentate coordination (J. Organomet. Chem., 2005, 690: 3125-3133.) also exhibit excellent catalytic performance in the polymerization of ethylene and norbornene. The introduction of the strong electron-donating group oxygen has an important influence on the catalytic active center. Such catalysts can catalyze the living polymerization of ethylene and norbornene at room temperature with relatively high catalytic activity. However, the norbornene content of the polymers obtained by such catalysts is low, and the polymer properties are poor.

[0005] Therefore, it is necessary to provide a new compound to solve the problems existing in the prior art. Summary of the Invention

[0006] To solve the problems existing in the prior art, the present invention provides a complex metal compound, its preparation method and application. The complex metal compound is an N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex Group IV metal compound. By designing and optimizing the ligand structure, a novel nitrogen-oxygen-nitrogen tridentate coordination Group IV metal compound is synthesized, which has good activity, thermal stability, and controllability in the catalytic copolymerization reaction of α-olefins and cycloolefins.

[0007] To achieve the above object, the present invention provides a complex metal compound, which is an N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex of a Group IVB metal compound, and the structure of the compound is shown in the following formula (I):

[0008]

[0009] Wherein, M is selected from titanium, zirconium, hafnium; R is selected from tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; R 1 、R 2 are respectively selected from chlorine, fluorine, methyl (Me), ethyl, isopropyl, methoxy, and R 1 、R 2 are the same or different.

[0010] Preferably, the compound of the present invention is selected from any one of the following:

[0011] Compound C1: L1TiCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine;

[0012] Compound C2: L1TiMe2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine;

[0013] Compound C3: L1ZrCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine;

[0014] Compound C4: L1HfCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine; or

[0015] Compound C5: L2TiCl2, where L2 = N,N-bis(2,6-dimethylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine.

[0016] The present invention also provides a preparation method of the complex metal compound, and the preparation method includes the following steps:

[0017] (1) Under an argon atmosphere, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane and amine lithium salt are respectively dissolved in an anhydrous solvent, and mixed at a molar ratio of 0.8 - 1.2:2, and reacted at room temperature for 10 - 18 hours; the anhydrous solvent is removed under reduced pressure, an anhydrous alkane solvent is added for sedimentation and then filtration, and n-hexane is removed under reduced pressure to obtain the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand;

[0018] (2) Under an argon atmosphere, the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand is dissolved in an anhydrous solvent, 2.0 - 3.0 equivalents of n-butyllithium are added, and the reaction is carried out at room temperature for 12 - 24 h, followed by sedimentation and filtration, and washing with a poor solvent to obtain the ligand lithium salt;

[0019] (3) Under an argon atmosphere, the ligand lithium salt and the Group IVB metal chloride are mixed at a molar ratio of 0.8 - 1.5:1, and then reacted at room temperature for 18 - 36 hours in an anhydrous alkane solvent; sedimentation and filtration are carried out, and n-hexane is removed under reduced pressure to obtain the corresponding nitrogen-oxygen-nitrogen tridentate coordinated Group IVB metal chloride;

[0020] (4) Under an argon atmosphere, the corresponding nitrogen-oxygen-nitrogen tridentate coordinated Group IVB metal chloride and the Grignard reagent are mixed at a molar ratio of 0.5 - 1.2:3, and then reacted at room temperature for 10 - 18 hours in an ether solvent; the ether solvent is removed under reduced pressure, added to toluene solvent for sedimentation and filtration, and the toluene solvent is removed under reduced pressure to obtain the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex Group IVB metal compound.

[0021] In the preparation method of the present invention, in step (1), the molar ratio of the 1,3-dichloro-1,1,3,3-tetramethyldisiloxane to the amine lithium salt is 0.9:2; the reaction at room temperature is for 12 - 16 hours.

[0022] In the preparation method of the present invention, the anhydrous solvent is at least one of benzene, toluene, xylene, ether and tetrahydrofuran; the anhydrous alkane solvent is n-hexane; the poor solvent is at least one of n-hexane, n-pentane, n-heptane and cyclohexane.

[0023] Preferably, the anhydrous solvent is toluene and ether; the poor solvent is n-hexane and n-pentane.

[0024] In the preparation method of the present invention, in step (2), 2.2 - 3.0 equivalents of butyllithium are added; the temperature condition for adding butyllithium is -50 - -100 °C; the reaction at room temperature is for 15 - 20 h.

[0025] In the preparation method of the present invention, in step (3), the molar ratio of the ligand lithium salt to the Group IVB metal chloride is 1.0 to 1.2:1; the reaction is carried out at room temperature for 24 to 30 hours.

[0026] In the preparation method of the present invention, in step (4), the molar ratio of the corresponding N,O,N tridentate coordinated Group IVB metal chloride to the Grignard reagent is 0.8 to 1.0:3, and the reaction is carried out at room temperature for 12 to 18 hours.

[0027] The present invention also provides an application of a complex metal compound in the copolymerization reaction of α-olefins and cycloolefins.

[0028] In the application of the present invention, preferably, the α-olefin is selected from ethylene, propylene, 1-octene; the cycloolefin is selected from cyclobutene, cyclopentene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON).

[0029] In the application of the present invention, most preferably, the α-olefin is ethylene; the cycloolefin is norbornene.

[0030] In the application of the present invention, the molar ratio of the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound to (the total amount of the α-olefin and cycloolefin) is 1:50 to 10000.

[0031] Preferably, the molar ratio of the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound to (the total amount of the α-olefin and cycloolefin) is 1:1500 to 3000.

[0032] In the application of the present invention, the solvent for the copolymerization reaction is selected from benzene, toluene, n-hexane, tetrahydrofuran and dichloromethane, preferably toluene.

[0033] In the application of the present invention, the temperature of the copolymerization reaction is 0°C to 110°C, preferably 60 to 80°C.

[0034] In the application of the present invention, the time of the copolymerization reaction is 1 to 60 minutes, preferably 10 to 30 minutes.

[0035] In the application of the present invention, methylaluminoxane (MAO) is added as a cocatalyst in the copolymerization reaction, and the molar ratio of the methylaluminoxane to the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound is 100 to 2000:1, preferably 400 to 1000:1.

[0036] The present invention can also be described in detail as follows:

[0037] The present invention provides a method for preparing an N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IV metal compound, and the preparation method includes the following steps:

[0038] (1) Under an argon atmosphere, dissolve 1,3-dichloro-1,1,3,3-tetramethyldisiloxane in 3 - 10 mL of an anhydrous solvent (preferably 5 - 10 mL), dissolve the amine lithium salt in 30 - 80 mL of an anhydrous solvent (preferably 50 - 80 mL), mix them at a molar ratio of 0.8 - 1.2:2 (preferably 0.9:2) under the condition of -78°C, and react at room temperature in an ether solvent for 10 - 18 hours (preferably 12 - 16 hours). Remove the ether solvent under reduced pressure, add 10 - 30 mL of an anhydrous solvent (preferably 15 - 30 mL) of n-hexane for sedimentation and then filtration, and remove the n-hexane solvent under reduced pressure to obtain the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand.

[0039] (2) Dissolve the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand in 30 - 100 mL of an anhydrous solvent (preferably 50 - 90 mL), add 2.0 - 3.0 equivalents (preferably 2.2 - 3.0 equivalents) of butyllithium under the condition of -78°C, stir at room temperature for 12 - 24 hours (preferably 15 - 20 hours) under argon protection, filter, and wash three times with a poor solvent to obtain the corresponding lithium salt.

[0040] (3) Under an argon atmosphere, mix the ligand lithium salt with titanium / zirconium / hafnium tetrachloride at a molar ratio of 0.8 - 1.5:1 (preferably 1.0 - 1.2:1), and react at room temperature in an n-hexane solvent for 18 - 36 hours (preferably 24 - 30 hours); after filtration, remove the n-hexane solvent under reduced pressure to obtain the corresponding Group IV metal chloride with a nitrogen-oxygen-nitrogen tridentate coordination.

[0041] (4) Under an argon atmosphere, mix the ligand titanium chloride with a Grignard reagent at a molar ratio of 0.5 - 1.2:3 (preferably 0.8 - 1.0:3), and react at room temperature in an ether solvent for 10 - 18 hours (preferably 12 - 18 hours); remove the ether solvent under reduced pressure, add 10 - 30 mL of an anhydrous solvent (preferably 15 - 25 mL) of toluene for sedimentation and then filtration, and remove the toluene solvent under reduced pressure to obtain the corresponding titanium alkylide.

[0042] In the above preparation method, the anhydrous solvent is selected from benzene, toluene, xylene, ether, and tetrahydrofuran, preferably toluene and ether; the poor solvent is selected from n-hexane, n-pentane, n-heptane, and cyclohexane, preferably n-hexane and n-pentane.

[0043] The present invention also provides the application of the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine titanium / zirconium / hafnium chloride / methylide shown in the above formula (I) in the copolymerization reaction of ethylene and norbornene.

[0044] In the above application, the α-olefins and cycloolefins include ethylene, propylene, 1-octene, cyclobutene, cyclopentene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON), preferably ethylene and norbornene.

[0045] In the above application, the molar ratio of the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine titanium / zirconium / hafnium chloride / methylide to the α-olefins and cycloolefins is 1:(50 - 10000), preferably 1:1500 - 3000.

[0046] In the above application, the solvent for the polymerization reaction can be benzene, toluene, n-hexane, tetrahydrofuran and dichloromethane, preferably toluene.

[0047] In the above application, the temperature of the polymerization reaction is 0°C - 110°C, preferably 60 - 80°C.

[0048] In the above application, the time of the polymerization reaction is 1 - 60 minutes, preferably 10 - 30 minutes.

[0049] In the above application, methylaluminoxane (MAO) is added as a cocatalyst in the polymerization reaction, and the molar ratio of the methylaluminoxane to the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine titanium / zirconium / hafnium chloride / methylide is 100 - 2000:1, preferably 400 - 1000:1.

[0050] Compared with the prior art, the present invention has the following advantages and effects:

[0051] The N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound provided by the present invention provides a brand-new system for the COC polymer catalyst. The ligand structure of the nitrogen-oxygen-nitrogen tridentate coordination and the large substituent steric hindrance endow the catalytic active center with good stability.

[0052] The preparation method of the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complex of Group IV metal compounds provided by the present invention is simple, low in cost, stable in nature, and has high catalytic activity and thermal stability. It can catalyze the copolymerization of α-olefins and cycloolefins, is particularly suitable for catalyzing the copolymerization of ethylene and norbornene, and by controlling the polymerization reaction conditions, the molecular weight of the polymer and the norbornene content of the polymer can be regulated. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 1H NMR spectrum of Example 1 (ligand L1).

[0054] Figure 2 1H NMR spectrum of Example 3 (compound C1).

[0055] Figure 3 13C NMR spectrum of Example 3 (compound C1).

[0056] Figure 4 1H NMR spectrum of Example 4 (compound C2).

[0057] Figure 5 13C NMR spectrum of Example 4 (compound C2). DETAILED DESCRIPTION OF THE INVENTION

[0058] The present invention will be specifically described below by way of examples. It is necessary to point out here that the following examples are only for further illustration of the present invention and should not be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention according to the above content of the present invention.

[0059] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0060] The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0061] Example 1. Preparation of Ligand L1 (N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine)

[0062] Under an argon atmosphere, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane (1.6 g, 8.0 mmol) was dissolved in 5 mL of anhydrous diethyl ether, and lithium 2,6-diisopropylanilide (3.5 g, 19.2 mmol) was dissolved in 50 mL of anhydrous diethyl ether. The 1,3-dichloro-1,1,3,3-tetramethyldisiloxane diethyl ether solution was slowly added dropwise to the lithium 2,6-diisopropylanilide solution at -78 °C, and the reaction was carried out at room temperature for 12 hours. The diethyl ether solvent was removed under reduced pressure. After adding 20 mL of n-hexane, the mixture was allowed to settle and then filtered. The n-hexane solvent was removed under reduced pressure to obtain 3.0 g (6.24 mmol) of the orange-yellow oily ligand L1 with a yield of 78.1%. 1 H NMR (C6D6): δ 7.14 - 7.11 (m, 6H, Ar-H), 4.10 (m, 4H, J = 6.8 Hz, CH3-CH), 2.63 (br, 2H, N-H), 1.24 (d, 24H, J = 6.9 Hz, CH-CH3), 0.17 (s, 12H, Si-CH3).

[0063] Example 2: Preparation of ligand L2 (N,N-bis(2,6-dimethylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine)

[0064] Under an argon atmosphere, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane (1.6 g, 8.0 mmol) was dissolved in 5 mL of anhydrous diethyl ether, and lithium 2,6-dimethylanilide (2.5 g, 19.8 mmol) was dissolved in 50 mL of anhydrous diethyl ether. The 1,3-dichloro-1,1,3,3-tetramethyldisiloxane diethyl ether solution was slowly added dropwise to the lithium 2,6-dimethylanilide solution at -78 °C, and the reaction was carried out at room temperature for 12 hours. The diethyl ether solvent was removed under reduced pressure. After adding 20 mL of n-hexane, the mixture was allowed to settle and then filtered. The n-hexane solvent was removed under reduced pressure to obtain 2.68 g (7.2 mmol) of the orange-yellow oily ligand L2 with a yield of 90%. 1 H NMR (C6D6): δ 7.26 - 7.18 (m, 6H, Ar-H), 2.78 (br, 2H, N-H), 2.32 (s, 12H, Ph-CH3), 0.13 (s, 12H, Si-CH3).

[0065] Example 3: Preparation of compound C1 (L1TiCl2)

[0066] Under an argon atmosphere, ligand L1 (N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine, 0.484 g, v1 mmol) was dissolved in 15 mL of anhydrous n-hexane. n-Butyllithium (1 mL, 2.4 M, 2.4 mmol) was slowly added dropwise, and the reaction was carried out at room temperature for 18 h. After sedimentation, filtration was performed, and it was washed three times with n-hexane and then dried by suction to obtain the lithium salt of the ligand. Then, titanium tetrachloride tetrahydrofuran complex (0.332 g, 1 mmol) was added and dissolved in 30 mL of anhydrous n-hexane, and the reaction was carried out at room temperature for 24 hours. After sedimentation, filtration was performed, and the solvent n-hexane was removed under reduced pressure to obtain 378 mg of yellow solid compound C1, 0.63 mmol, with a yield of 63.0%. 1 HNMR(C6D6): δ7.16 - 7.08(m, 6H, Ar-H), 3.84(m, 4H, J = 6.7Hz, CH3-CH), 1.47(d, 24H, J = 6.6Hz, CH-CH3), 1.26(d, 24H, J = 6.8Hz, CH-CH3), 0.28(s, 12H, Si-CH3). 13 C NMR(C6D6): δ148.76, 140.88, 127.34, 124.68, 28.54, 27.59, 24.18.

[0067] Example 4. Preparation of Compound C2 (L1TiMe2)

[0068] Under an argon atmosphere, compound C1 (L1TiCl2, 0.2 g, 0.33 mmol) was dissolved in 15 mL of anhydrous diethyl ether. Methylmagnesium bromide (0.8 mL, 1.6 M, 1.3 mmol) was slowly added dropwise, and the reaction was carried out at room temperature for 12 h. The solvent diethyl ether was removed under reduced pressure, 10 mL of anhydrous toluene was added for extraction, and then sedimentation and filtration were performed. The solvent toluene was removed under reduced pressure, and 5 mL of pentane was added for washing to obtain 112 mg of yellow solid compound C2, 0.2 mmol, with a yield of 62.0%. 1 H NMR(C6D6): δ7.18 - 7.10(m, 6H, Ar-H), 3.99(m, 4H, J = 6.8Hz, CH3-CH), 1.47(s, 6H, Ti-CH3), 1.32(dd, 24H, J = 7.0Hz, 7.1Hz, CH-CH3), 0.21(s, 12H, Si-CH3). 13 C NMR(C6D6): δ114.76, 142.51, 125.52, 124.64, 67.05, 28.24, 27.73, 24.47, 1.98.

[0069] Example 5. Preparation of Compound C3 (L1ZrCl2)

[0070] Using ligand L1, after obtaining the lithium salt of the ligand, zirconium tetrachloride (167 mg, 0.5 mmol) was added. The remaining experimental steps were the same as in Example 3. The yield of compound C3 (L1ZrCl2) was 186 mg, 0.29 mmol, 58%. 1 HNMR (C6D6): δ 7.16 - 7.07 (m, 6H, Ar-H), 3.83 (m, 4H, J = 6.6 Hz, CH3-CH), 1.46 (d, 24H, J = 6.7 Hz, CH-CH3), 1.29 (d, 24H, J = 6.8 Hz, CH-CH3), 0.24 (s, 12H, Si-CH3). 13 C NMR (C6D6): δ 142.27, 141.78, 125.64, 124.49, 28.46, 27.40, 24.09, 1.82.

[0071] Example 6, Preparation of Compound C4 (L1HfCl2)

[0072] Using ligand L1, after obtaining the lithium salt of the ligand, hafnium tetrachloride (160 mg, 0.5 mmol) was added. The remaining experimental steps were the same as in Example 3. The yield of compound C4 (L1HfCl2) was 108 mg, 0.27 mmol, 53%. 1 HNMR (C6D6): δ 7.14 - 7.02 (m, 6H, Ar-H), 3.86 (m, 4H, J = 6.6 Hz, CH3-CH), 1.44 (d, 24H, J = 6.7 Hz, CH-CH3), 1.30 (d, 24H, J = 6.8 Hz, CH-CH3), 0.22 (s, 12H, Si-CH3). 13 C NMR (C6D6): δ 143.02, 141.27, 125.35, 124.34, 28.32, 27.45, 24.12, 2.06.

[0073] Example 7, Preparation of Compound C5 (L2TiCl2)

[0074] Using ligand L2, after obtaining the lithium salt of the ligand, titanium tetrachloride tetrahydrofuran complex (0.166 g, 0.5 mmol) was added. The remaining experimental steps were the same as in Example 3. The yield of compound C5 (L2TiCl2) was 156 mg, 0.32 mmol, 64%. 1 H NMR (C6D6): δ 7.24 - 7.19 (m, 6H, Ar-H), 2.47 (s, 12H, Ph-CH3), 0.19 (s, 12H, Si-CH3). 13 C NMR (C6D6): δ 151.98, 144.27, 126.35, 124.74, 26.31, 4.69.

[0075] Example 8: Copolymerization of Ethylene and Norbornene Catalyzed by Compound C1

[0076] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C. 0.01 mmol of Compound C1 (5.4 mg) was dissolved in 3 mL of anhydrous toluene and added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried in vacuo for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 194 kg(poly)mol -1 (Ti)h -1 。

[0077] Example 9: Copolymerization of Ethylene and Norbornene Catalyzed by Compound C2

[0078] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C. 0.01 mmol of Compound C2 (6.0 mg) was dissolved in 3 mL of anhydrous toluene and added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried in vacuo for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 109 kg(poly)mol -1 (Ti)h -1 。

[0079] Example 10: Copolymerization of Ethylene and Norbornene Catalyzed by Compound C3

[0080] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C. 0.01 mmol of Compound C3 (6.4 mg) was dissolved in 3 mL of anhydrous toluene and added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried in vacuo for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 146 kg(poly)mol -1 (Ti)h -1 。

[0081] Example 11: Copolymerization of Ethylene and Norbornene Catalyzed by Compound C4

[0082] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C, 0.01 mmol of compound C4 (7.8 mg) was dissolved in 3 mL of anhydrous toluene, and it was added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried under vacuum for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 248 kg(poly)mol -1 (Ti)h -1 。

[0083] Example 12: Copolymerization of ethylene and norbornene catalyzed by compound C5

[0084] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C, 0.01 mmol of compound C5 (4.9 mg) was dissolved in 3 mL of anhydrous toluene, and it was added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried under vacuum for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 183 kg(poly)mol -1 (Ti)h -1 。

[0085] Example 13: Copolymerization of ethylene and norbornene catalyzed by compound C5

[0086] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 58 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 0 °C, 0.01 mmol of compound C1 (5.4 mg) was dissolved in 3 mL of anhydrous toluene, and it was added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 1 minute, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried under vacuum for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 142 kg(poly)mol -1 (Ti)h -1 。

[0087] Example 14: Copolymerization of ethylene and norbornene catalyzed by compound C5

[0088] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 100 °C, 0.002 mmol of compound C1 (4.9 mg) was dissolved in 3 mL of anhydrous toluene, and it was added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 60 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried under vacuum for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 197 kg(poly)mol -1 (Ti)h -1 。

[0089] Comparative Example 1: Copolymerization of ethylene and norbornene catalyzed by an oxygen-nitrogen bidentate coordinated titanium compound (this oxygen-nitrogen bidentate coordinated titanium compound was disclosed in.Xiao-Fang, Li, et al. New Titanium Complexes with Twoβ-Enaminoketonato Chelate Ligands: Syntheses, Structures, and OlefinPolymerization Activities[J]. Organometallics, 2004, 23, 6, 1223-1230)

[0090] In a Schlenk flask, under anhydrous and anaerobic conditions, 1.41 g of norbornene was added, 232 mg of MAO was added, 22 mL of anhydrous toluene was added, ethylene gas was introduced, the pressure was maintained at 0.1 MPa, the temperature was controlled at 60 °C, 0.01 mmol of the oxygen-nitrogen bidentate coordinated titanium compound was dissolved in 3 mL of anhydrous toluene, and it was added to the Schlenk flask by syringe for catalytic polymerization. The reaction was carried out for 10 minutes, then poured into a mixed solution of ethanol and hydrochloric acid to precipitate the polymer. After filtration, it was dried under vacuum for 12 hours to obtain an ethylene-norbornene copolymer with an activity of 114 kg(poly)mol -1 (Ti)h -1 。

[0091] In summary, the N,N-bis(aryl / alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IV metal compound provided by the present invention is simple in synthesis, easy to obtain raw materials, and various catalysts with designed structures can be obtained only through four-step reactions. In addition, the catalyst structure can be adjusted, which can be favorably adjusted to adapt to different polymerization conditions such as different monomers. It shows excellent catalytic activity in the copolymerization of ethylene and norbornene, and this type of catalyst has good thermal stability and can still maintain high catalytic performance at higher temperature conditions.

[0092] Of course, the present invention may have many other 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. However, these corresponding changes and modifications should all fall within the protection scope defined by the appended claims of the present invention.

Claims

1. A complex metal compound, characterized in that, The complex metal compound is an N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IV metal compound, and the structure of the compound is shown in the following formula (I): （I） Among them, M is selected from titanium, zirconium, hafnium; R is selected from tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl; R 1 , R 2 are respectively selected from chlorine, fluorine, methyl (Me), ethyl, isopropyl, methoxy, and R 1 , R 2 are the same or different.

2. The compound according to claim 1, wherein The compound is selected from any one of the following: Compound C1: L1TiCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine; Compound C2: L1TiMe2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine; Compound C3: L1ZrCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine; Compound C4: L1HfCl2, where L1 = N,N-bis(2,6-diisopropylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine; or Compound C5: L2TiCl2, where L2 = N,N-bis(2,6-dimethylphenyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine.

3. A method for preparing the complex metal compound according to any one of claims 1-2, characterized in that, Comprising the following steps: (1) Under an argon atmosphere, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane and amine lithium salt are respectively dissolved in an anhydrous solvent, and mixed at a molar ratio of 0.8 - 1.2:2, and reacted at room temperature for 10 - 18 hours; the anhydrous solvent is removed under reduced pressure, an anhydrous alkane solvent is added for sedimentation and then filtered, and the solvent is removed under reduced pressure to obtain an N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand; (2) Under an argon atmosphere, the N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine ligand is dissolved in an anhydrous solvent, 2.0 - 3.0 equivalents of n-butyllithium are added, and reacted at room temperature for 12 - 24 h, sedimented and then filtered, and washed with a poor solvent to obtain a ligand lithium salt; (3) Under an argon atmosphere, the ligand lithium salt and a Group IV metal chloride are mixed at a molar ratio of 0.8 - 1.5:1, and then reacted at room temperature for 18 - 36 hours in an anhydrous alkane solvent; sedimented and filtered, and the solvent is removed under reduced pressure to obtain the corresponding nitrogen-oxygen-nitrogen tridentate coordinated Group IV metal chloride; (4) Under an argon atmosphere, the corresponding nitrogen-oxygen-nitrogen tridentate coordinated Group IV metal chloride and a Grignard reagent are mixed at a molar ratio of 0.5 - 1.2:3, and then reacted at room temperature for 10 - 18 hours in an ether solvent; the ether solvent is removed under reduced pressure, added to a toluene solvent for sedimentation and filtration, and the toluene solvent is removed under reduced pressure to obtain an N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IV metal compound.

4. The preparation method according to claim 3, wherein The molar ratio of the 1,3-dichloro-1,1,3,3-tetramethyldisiloxane to the amine lithium salt is 0.9:2; the reaction at room temperature is for 12 - 16 hours.

5. The preparation method according to claim 3, wherein The anhydrous solvent is at least one of benzene, toluene, xylene, ether, and tetrahydrofuran; the anhydrous alkane solvent is n-hexane; the poor solvent is at least one of n-hexane, n-pentane, n-heptane, and cyclohexane.

6. The preparation method according to claim 5, characterized in that, The anhydrous solvents are toluene and ether; the poor solvents are n-hexane and n-pentane.

7. The preparation method according to claim 3, characterized in that, In step (2), 2.2 to 3.0 equivalents of butyllithium are added; the temperature condition for adding butyllithium is -50 to -100 °C; the reaction is carried out at room temperature for 15 to 20 h.

8. The preparation method according to claim 3, characterized in that, In step (3), the molar ratio of the ligand lithium salt to the Group IVB metal chloride is 1.0 to 1.2:1; the reaction is carried out at room temperature for 24 to 30 hours.

9. The preparation method according to claim 3, characterized in that, In step (4), the molar ratio of the corresponding N,O,N-tridentate coordinated Group IVB metal chloride to the Grignard reagent is 0.8 to 1.0:3, and the reaction is carried out at room temperature for 12 to 18 hours.

10. Use of the complex metal compound according to any one of claims 1-2 in the copolymerization reaction of α-olefins and cycloolefins.

11. The application according to claim 10, wherein The α-olefin is selected from ethylene, propylene, 1-octene; the cycloolefin is selected from cyclobutene, cyclopentene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

12. The application according to claim 10, characterized in that, The α-olefin is ethylene; the cycloolefin is norbornene.

13. The application according to claim 10, wherein, The molar ratio of the N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound to the total amount of the α-olefin and cycloolefin is 1:50 to 10000.

14. The application according to claim 13, characterized in that, The molar ratio of the N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound to the total amount of the α-olefin and cycloolefin is 1:1500 to 3000.

15. The application according to claim 10, characterized in that, The solvent for the copolymerization reaction is selected from benzene, toluene, n-hexane, tetrahydrofuran, and dichloromethane; the temperature of the copolymerization reaction is 0 °C to 110 °C, the time of the copolymerization reaction is 1 to 60 minutes; methylaluminoxane is added as a cocatalyst in the copolymerization reaction, and the molar ratio of methylaluminoxane to the N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound is 100 to 2000:

1.

16. The application according to claim 15, characterized in that, The solvent for the copolymerization reaction is toluene; the temperature of the copolymerization reaction is 60 to 80 °C; the time of the copolymerization reaction is 10 to 30 minutes; the molar ratio of methylaluminoxane to the N,N-bis(aryl or alkyl)-1,1,3,3-tetramethyldisiloxane-1,3-diamine complexed Group IVB metal compound is 400 to 1000:1.

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