CN114853930B - Synthesis of NNO-coordinated titanium zirconium hafnium metal catalyst and application of NNO-coordinated titanium zirconium hafnium metal catalyst in preparation of polyolefin elastomer - Google Patents

Abstract

The invention reports the synthesis of NNO-coordinated titanium zirconium hafnium metal catalyst and the application of the NNO-coordinated titanium zirconium hafnium metal catalyst in preparing polyolefin elastomer by high-temperature solution polymerization. The invention reports NNO-coordinated titanium zirconium hafnium metal catalyst with salicylaldimine-amine skeleton, and the three-dimensional effect and electronic effect of the model metal catalyst can be conveniently regulated and controlled by changing substituent groups, so that different catalytic performances are realized, and polyolefin polymer materials with various structures and various performances are prepared. The novel NNO-coordinated titanium zirconium hafnium metal catalyst reported by the invention has the characteristics of simple synthesis and high product yield; exhibits extremely high activity up to 1.35X 10 in the presence of a suitable amount of a cocatalyst such as MAO or the like ⁸ g(PE)·mol ^‑1 (Ti)·h ^‑1 The method comprises the steps of carrying out a first treatment on the surface of the The polyethylene produced has a high degree of linearity and a high molecular weight. In addition, the NNO-coordinated titanium zirconium hafnium metal catalyst reported by the invention has excellent high temperature resistance and copolymerization performance, and is suitable for olefin high-temperature solution polymerization to prepare high-performance polyolefin elastomer with high molecular weight and high comonomer content. Therefore, the invention reports that the method has original innovation and can enhance the competitive capacity of the technical market of polyolefin polymer materials in China.

Description

Synthesis of an NNO-coordinated titanium-zirconium-hafnium metal catalyst and its preparation of polyolefin elasticity body application

Technical field

The present invention relates to the preparation of coordination polymerization metal catalysts and their application in the field of polyolefins.

Background technique

The global annual output of polyolefin materials is nearly 200 million tons, accounting for about 65% of general plastic production. It is the largest type of synthetic polymer material; it has the advantages of high cost performance, good mechanical properties, and stable thermal properties, and is widely used in industrial production and Various areas of daily life have improved and improved people's quality of life (Science 2017,814-816). The polyolefin field is highly technology-driven and its development relies heavily on the rapid development of metal catalysts. Benefiting from structural diversity and tunable catalysts, non-transition metal catalysts enable chemists to design polymer compositions and microstructures. Solution olefin polymerization has now been successfully achieved using these soluble non-transition metal catalysts, allowing for more flexible operation and production of a wider range of products. In 1999, Fujita et al. reported NO bidentate coordination salicylaldimine titanium and zirconium metal catalyst (FI catalyst) (Chem. Rev. 2011, 2363-2449). Among them, FI-Zr catalyst has very high polymerization activity and is suitable for high-temperature solution polymerization. Tang Yong et al. found that introducing an additional coordination atom (NOX catalyst, X=O, S, Se or P) into the FI-Ti catalyst model can significantly regulate its catalytic properties, such as high temperature resistance and copolymerization properties. et al. (Sci.China:Chem.2014,1144-1149.). Ma Yuguo et al. reported that a catalyst containing two different FI ligands (with different substituents on the two FI ligands) can simultaneously achieve high activity and high copolymerization performance (Macromolecules 2014, 8164-8170.). In 2000, Murray et al. from Union Carbide Company reported NN bidentate coordination pyridine-amine zirconium and hafnium metal catalysts, which are suitable for high-temperature solution polymerization (Acc. Chem. Res. 2015, 48, 2004-2016) and can prepare high Performance polyolefin elastomer materials. However, high-temperature solution polymerization requires catalysts with high thermal stability, as well as high activity and high copolymerization ability at high temperatures. Therefore, the development of new high-temperature-resistant non-transition metal catalysts is the key to the preparation of high-performance polyolefin elastomers by high-temperature solution polymerization.

The present invention reports the synthesis of an NNO-coordinated titanium-zirconium-hafnium metal catalyst and its application in preparing polyolefin elastomer. The present invention reports an NNO-tridentate ligand with a salicylaldimine-amine skeleton and its titanium-zirconium-hafnium metal catalyst. By changing the substituents, the three-dimensional effect and electronic effect of the model metal catalyst can be easily controlled, thereby achieving different Catalytic performance, preparation of polyolefin polymer materials with various structures and properties. The new NNO-coordinated titanium-zirconium-hafnium metal catalyst reported in the present invention has the characteristics of simple synthesis and high product yield; in the presence of an appropriate amount of cocatalyst (such as MAO, etc.), it shows extremely high activity, up to 1.35×10 ⁸ g(PE)·mol ^-1 (Ti)·h ^-1 ; the prepared polyethylene has high linearity and high molecular weight. In addition, the NNO-coordinated titanium-zirconium-hafnium metal catalyst reported in the present invention has excellent high-temperature resistance and copolymerization performance, and is suitable for high-temperature solution polymerization of olefins to prepare high-performance polyolefin elastomers with high molecular weight and high comonomer content. Therefore, the report of this invention is original and innovative and can enhance the competitiveness of my country's polyolefin polymer material technology market.

Contents of the invention

The object of the present invention is to provide a synthesis of an NNO-coordinated titanium-zirconium-hafnium metal catalyst and its application in preparing polyolefin elastomers.

The invention provides an NNO-coordinated titanium-zirconium-hafnium metal catalyst represented by formula (I):

Among them, R is selected from methyl, chlorine, dimethylamino; R ¹ is selected from methyl, ethyl, hydrogen, isopropyl, chlorine, fluorine; R ² is selected from methyl, methoxy, hydrogen, tert-butyl base, benzyl; R ³ is selected from methyl, ethyl, hydrogen, isopropyl, chlorine, fluorine; R ⁴ is selected from methyl, ethyl, hydrogen, isopropyl.

Preferably, the metal compound of the present invention is selected from any of the following complexes:

Ti1:L1TiCl ₂ ,LH1＝2,6-( ⁱ Pr) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^tBu ) ₂ -C ₆ H ₂ -OH

Ti2:L2TiCl ₂ ,LH2＝2,6-(Me) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^tBu ) ₂ -C ₆ H ₂ -OH

Ti3:L3TiCl ₂ ,LH3＝2,6-(H) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^t Bu) ₂ -C ₆ H ₂ -OH

Ti4:L4TiCl ₂ ,LH4＝2,6-(Cl) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^tBu ) ₂ -C ₆ H ₂ -OH

Zr1:L1ZrCl ₂ ,LH1＝2,6-( ⁱ Pr) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^tBu ) ₂ -C ₆ H ₂ -OH

Hf1:L1HfCl ₂ ,LH1＝2,6-( ⁱ Pr) ₂ -C ₆ H ₃ -NH-C ₆ H ₄ -N＝C-3,5-( ^tBu ) ₂ -C ₆ H ₂ -OH

The invention provides a preparation method for the above-mentioned NNO-coordinated titanium-zirconium-hafnium metal catalyst, which includes the following steps:

The synthesis of NNO-tridentate ligands LH1-LH4 refers to the literature method (Polym. Chem., 2022, 1852–1860). Under a nitrogen atmosphere, stir 1 molar equivalent of NNO-tridentate ligand LH1-LH4 and 1 molar equivalent of M(NMe) ₄ in toluene and reflux for 1-5 days, drain the solvent, and wash with 5 mL of anhydrous n-hexane. Then, dissolve the filter residue in an appropriate amount of toluene, gradually drop 10 molar equivalents of dimethyldichlorosilane at -78°C, gradually heat to 60°C, and stir overnight. After removing the solvent, add a good solvent to dissolve and filter, and remove the filtrate. After removing the solvent, a poor solvent is added for washing to obtain the NNO-coordinated titanium-zirconium-hafnium metal catalyst.

The good solvent is selected from dichloromethane and toluene, and the poor solvent is selected from n-hexane, n-pentane, and cyclohexane.

The present invention also provides the application of the above-mentioned NNO-coordinated titanium, zirconium and hafnium metal catalyst in catalyzing olefin polymerization and copolymerization reactions.

In the above application, the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene and norbornene.

The above catalyst is also added with a cocatalyst, which is one of tripentafluorophenylboron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum and alkyl aluminum chloride. Or several. The aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-hexylaluminum; Alkyl aluminum chloride is diethyl aluminum monochloride, diethyl aluminum sesquichloride or ethylaluminum dichloride.

In the above polymerization reaction, the polymerization temperature is 0-200°C, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, hexane, and heptane.

The invention provides the preparation of an NNO-coordinated titanium-zirconium-hafnium metal catalyst and the application of the catalyst to catalyze olefin polymerization. The new NNO-coordinated titanium zirconium and hafnium metal catalyst reported in this invention has high activity, good high temperature resistance, good copolymerization activity, original innovation, and can enhance the competitiveness of my country's polyolefin polymer material technology market.

Description of drawings

Figure 1 is a crystal structure diagram of catalyst Ti2; Figure 2 is a crystal structure diagram of catalyst Ti4.

Detailed ways

The present invention is further illustrated by examples, but the present invention is not limited thereto. The embodiments of the present invention can enable those skilled in the art to understand the present invention more comprehensively.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

In the present invention, the NNO-tridentate ligands LH1-LH4 are synthesized by referring to the literature method (Polym. Chem., 2022, 1852-1860).

The present invention is described below with specific embodiments.

Example 1. Preparation of catalyst Ti1

To a 20 mL toluene solution of ligand LH1 (0.970 g, 2.00 mmol), Ti(NMe ₂ ) ₄ (0.448 g, 2.00 mmol) was added using a syringe under nitrogen atmosphere. The reaction mixture was stirred at 110°C for 48 hours, resulting in a reddish-brown suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure to obtain red powder L1Ti(NMe ₂ ) ₂ . To the toluene solution of the red powder L1Ti(NMe ₂ ) ₂ (0.619g, 1.00mmol), Me ₂ SiCl ₂ (1.29g, 10mmol) was slowly added using a syringe at -78°C. The reaction mixture was stirred at 60°C overnight to obtain a brown-black suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure, washed and purified with hexane (3×5 mL) and dried under reduced pressure to obtain Ti1 as a brown-black solid (0.475g, 0.79mmol, yield 79%) . ¹ H NMR (C ₆ D ₆ ): δ8.22 (s, 1H, N=CH), 7.70 (d, J=2.4Hz, 1H, Ar-H), 7.35–7.26 (m, 3H, Ar-H ),6.99(d,J＝2.3Hz,1H,Ar-H),6.83(d,J＝8.1Hz,1H,Ar-H),6.77(t,J＝7.2Hz,1H,Ar-H), 6.60(t,J＝7.2Hz,1H,Ar-H),5.97(dd,J＝8.2,0.8Hz,1H,Ar-H),3.55(sept,J＝6.8Hz,2H,CHMe ₂ ),1.62 (d,J＝6.8Hz,6H,CHCH ₃ CH ₃ ),1.58(s,9H,CMe ₃ ),1.28(s,9H,CMe ₃ ),1.10(d,J＝6.8Hz,6H,CHCH ₃ CH ₃ ). ¹³ C NMR (400MHz, C ₆ D ₆ ): δ166.19 (N＝CH), 157.98, 155.07, 152.36, 144.71, 142.01, 139.06, 138.39, 131.71, 129.54, 129.34, 128.57, 124.83, 123 .23, 121.20,114.99,112.99,35.53,34.61,31.35,29.58,28.93,25.25,24.71.Anal.Calcd for C ₃₃ H ₄₂ Cl ₂ N ₂ OTi:C,65.90;H,7.04;N,4.66.Found:C, 65.71;H,6.89;N,4.36.

Example 2, Preparation of Catalyst Ti2

The experimental procedures were the same as in Example 1, and the catalyst Ti2 was obtained as a brown-black solid (0.47g, 0.86mmol, yield 86%). ¹ H NMR (400MHz, C ₆ D ₆ ): δ8.20 (s, 1H, N＝CH), 7.70 (d, J＝2.4Hz, 1H, Ar-H), 7.16–7.08 (m, 3H, Ar -H),6.99(d,J＝2.4Hz,1H,Ar-H),6.76–6.70(m,2H,Ar-H),6.56(ddd,J＝8.3,7.2,1.2Hz,1H,Ar- H), 5.85 (d, J = 8.1Hz, 1H, Ar-H), 2.45 (s, 6H, Ar-Me), 1.57 (s, 9H, CMe ₃ ), 1.28 (s, 9H, CMe ₃ ). ¹³ C NMR (400MHz, C ₆ D ₆ ): δ165.80 (N＝CH), 158.27, 154.71, 153.15, 144.76, 139.73, 138.37, 132.09, 130.17, 128.65, 128.18, 127.94, 127.54, 123.27, 121.18,114.99 ,111.27,35.51,34.61,31.34,29.66,19.13.Anal.Calcd for C ₂₉ H ₃₄ Cl ₂ N ₂ OTi:C,63.87;H,6.28;N,5.14.Found:C,63.57;H,6.03;N ,4.99.

Example 3, Preparation of Catalyst Ti3

The experimental procedures were the same as in Example 1, and the catalyst Ti3 was obtained as a brown-black solid (0.42g, 0.82mmol, yield 82%). ¹ H NMR (400MHz, CDCl ₃ ): δ9.04 (s, 1H, N=CH), 7.71 (d, J=2.2Hz, 1H, Ar-H), 7.55 (t, J=7.8Hz, 2H, Ar-H),7.47–7.40(m,3H,Ar-H),7.33(t,J＝6.8Hz,2H,Ar-H),6.93(t,J＝7.6Hz,1H,Ar-H), 6.76(t,J＝7.5Hz,1H,Ar-H),5.73(d,J＝8.0Hz,1H,Ar-H),1.45(s,9H,CMe ₃ ),1.37(s,9H,CMe ₃ ). ¹³ C NMR (101MHz, CDCl ₃ ) δ 164.13 (N＝CH), 159.84, 153.55, 151.67, 145.27, 141.63, 137.59, 134.20, 130.19, 129.78, 129.09, 126.99, 125.71, 123.50, 1 21.68,114.08, 111.42,35.20,34.74,31.34,29.67.Anal.Calcd for C ₂₇ H ₃₀ Cl ₂ N ₂ OTi:C,62.69;H,5.85;N,5.42.Found:C,62.33;H,5.76;N,5.32.

Example 4, Preparation of Catalyst Ti4

The experimental procedures were the same as in Example 1, and the catalyst Ti4 was obtained as a brown-black solid (0.44g, 0.75mmol, yield 75%). ¹ H NMR (400MHz, C ₆ D ₆ ): δ8.12 (s, 1H, N＝CH), 7.68 (d, J＝2.4Hz, 1H, Ar-H), 7.17–7.14 (m, 2H, Ar -H),6.95(d,J＝2.4Hz,1H,Ar-H),6.86–6.80(m,1H,Ar-H),6.78–6.72(m,1H,Ar-H),6.64–6.58( m,1H,Ar-H),6.56(t,J＝8.1Hz,1H,Ar-H),6.01(dd,J＝8.1,1.0Hz,1H,Ar-H),1.56(s,9H,CMe ₃ ), 1.26 (s, 9H, CMe ₃ ). ¹³ C NMR (400MHz, CDCl ₃ ): δ165.25 (N＝CH), 158.60, 152.02, 150.35, 145.96, 138.80, 137.83, 132.62, 132.20, 130.08, 128.78,128.54,128.13,123.39,121.49,114.77,111.59,35.40,34.84,31.42,29.63.anal.Calcd forc ₂₇ H ₂₈ CL ₄ n ₂ OTI: C, 55.32; H, 4.81; N, 4.78.founddd : C ,55.38;H,4.55;N,4.61.

Example 5. Preparation of catalyst Zr1

Zr(NMe ₂ ) ₄ (0.534 g, 2.00 mmol) was added to a 20 mL toluene solution of ligand LH1 (0.970 g, 2.00 mmol) under nitrogen atmosphere using a syringe. The reaction mixture was stirred at 110°C for 48 hours, resulting in a yellow-brown suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure to obtain yellow powder L1Zr(NMe ₂ ) ₂ . To the toluene solution of the yellow powder L1Zr(NMe ₂ ) ₂ (0.663g, 1.00mmol), Me ₂ SiCl ₂ (1.29g, 10mmol) was slowly added using a syringe at -78°C. The reaction mixture was stirred at 60°C overnight to obtain a brown suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure, washed and purified with hexane (3×5 mL) and dried under reduced pressure to obtain Zr1 as a yellow solid (0.570 g, 0.88 mmol, yield 88%). ¹ H NMR (C ₆ D ₆ ): δ8.25 (s, 1H, N=CH), 7.72 (d, J=2.4Hz, 1H, Ar-H), 7.36–7.28 (m, 3H, Ar-H ),6.95(d,J＝2.3Hz,1H,Ar-H),6.89(d,J＝8.1Hz,1H,Ar-H),6.66(t,J＝7.2Hz,1H,Ar-H), 6.61(t,J＝7.2Hz,1H,Ar-H),5.86(dd,J＝8.2,0.8Hz,1H,Ar-H),3.52(sept,J＝6.8Hz,2H,CHMe ₂ ),1.62 (d,J＝6.8Hz,6H,CHCH ₃ CH ₃ ),1.59(s,9H,CMe ₃ ),1.28(s,9H,CMe ₃ ),1.11(d,J＝6.8Hz,6H,CHCH ₃ CH ₃ ). ¹³ C NMR (400MHz, C ₆ D ₆ ): δ166.32 (N＝CH), 157.66, 155.02, 152.30, 144.70, 142.23, 139.32, 138.34, 131.70, 129.55, 129.33, 128.51, 124.76, 123 .20, 121.28,114.95,113.99,35.50,34.60,31.30,29.65,28.95,25.25,23.70.Anal.Calcd for C ₃₃ H ₄₂ Cl ₂ N ₂ OZr:C,61.37;H,6.71;N,4.34.Found:C, 61.11;H,6.65;N,4.30.

Example 6, Preparation of Catalyst Hf1

To a 20 mL toluene solution of ligand LH1 (0.970 g, 2.00 mmol), Hf(NMe ₂ ) ₄ (0.710 g, 2.00 mmol) was added using a syringe under nitrogen atmosphere. The reaction mixture was stirred at 110°C for 48 hours, resulting in a yellow-brown suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure to obtain yellow powder L1Hf(NMe ₂ ) ₂ . To the toluene solution of the yellow powder L1Hf(NMe ₂ ) ₂ (0.750g, 1.00mmol), Me ₂ SiCl ₂ (1.29g, 10mmol) was slowly added using a syringe at -78°C. The reaction mixture was stirred at 60°C overnight to obtain a brown suspension. The suspension was filtered at room temperature, and the filtrate was dried under reduced pressure, washed and purified with hexane (3×5 mL) and dried under reduced pressure to obtain Hf1 as a yellow solid (0.610 g, 0.83 mmol, yield 83%). ¹ H NMR (C ₆ D ₆ ): δ8.31 (s, 1H, N=CH), 7.79 (d, J=2.4Hz, 1H, Ar-H), 7.32–7.21 (m, 3H, Ar-H ),6.95(d,J＝2.2Hz,1H,Ar-H),6.81(d,J＝8.0Hz,1H,Ar-H),6.60(t,J＝7.1Hz,1H,Ar-H), 6.52(t,J＝7.0Hz,1H,Ar-H),5.86(dd,J＝8.2,0.8Hz,1H,Ar-H),3.55(sept,J＝6.8Hz,2H,CHMe ₂ ),1.66 (d,J＝6.5Hz,6H,CHCH ₃ CH ₃ ),1.59(s,9H,CMe ₃ ),1.22(s,9H,CMe ₃ ),1.10(d,J＝6.8Hz,6H,CHCH ₃ CH ₃ ). ¹³ C NMR (400MHz, C ₆ D ₆ ): δ163.30 (N＝CH), 158.26, 155.52, 152.11, 145.72, 143.23, 139.44, 138.56, 131.23, 129.12, 129.00, 128.50, 124.06, 123 .00, 121.24,115.90,113.56,36.53,34.22,31.23,29.33,28.94,25.20,23.67.Anal.Calcd for C ₃₃ H ₄₂ Cl ₂ N ₂ OHf:C,54.07;H,5.91;N,3.82.Found:C, 53.98;H,5.78;N,3.67.

Example 7, Ti1 catalyzed ethylene polymerization

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 3.4 mL of cocatalyst with a syringe to make Al/Ti = 2500, ethylene pressure 40 atm, and temperature 50°C. In the glove box, add 1.2 mg (2 μmol) Ti1 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to dissolve the above catalyst toluene. The solution was injected into the main catalytic feeding tank, and the main catalyst was pressed into the main catalyst with a nitrogen pressure of 45 atm (total volume 200 mL). At 50°C, the ethylene pressure of 40 atm was maintained, and the reaction was stirred vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 51×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=950kg·mol ^-1 , Mw/Mn=1.9.

Example 8, Ti2 catalyzed ethylene polymerization

The polymerization reaction process and reaction conditions were the same as in Example 7, and the catalyst used was Ti2. Polymerization activity: 129×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=526kg·mol ^-1 , Mw/Mn=1.8.

Example 9, Ti3 catalyzed ethylene polymerization

The polymerization reaction process and reaction conditions were the same as in Example 7, and the catalyst used was Ti3. Polymerization activity: 135×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=418kg·mol ^-1 , Mw/Mn=1.8.

Example 10, Ti4 catalyzed ethylene polymerization

The polymerization reaction process and reaction conditions were the same as in Example 7, and the catalyst used was Ti4. Polymerization activity: 54.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=643kg·mol ^-1 , Mw/Mn=1.7.

Example 11, Zr1 catalyzed ethylene polymerization

The polymerization reaction process and reaction conditions were the same as in Example 7, and the catalyst used was Zr1. Polymerization activity: 111.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=850kg·mol ^-1 , Mw/Mn=1.9.

Example 12, Hf1 catalyzed ethylene polymerization

The polymerization reaction process and reaction conditions were the same as in Example 7, and the catalyst used was Hf1. Polymerization activity: 115.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=1105kg·mol ^-1 , Mw/Mn=1.8.

Example 13, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reactor to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 3.4 mL of cocatalyst with a syringe to make Al/Ti = 2500, ethylene pressure 5 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 8 atm nitrogen pressure, maintain the ethylene pressure at 5 atm at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 12.3×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=406kg·mol ^-1 , Mw/Mn=2.1.

Example 14, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reactor to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 3.4 mL of cocatalyst with a syringe to make Al/Ti = 2500, ethylene pressure 20 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 23 atm nitrogen pressure, maintain an ethylene pressure of 20 atm at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 63.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=850kg·mol ^-1 , Mw/Mn=1.4.

Example 15, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reactor to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 3.4 mL of cocatalyst with a syringe to make Al/Ti = 2500, ethylene pressure 40 atm, and temperature 120°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the ethylene pressure at 40 atm at 120°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 96×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=336kg·mol ^-1 , Mw/Mn=2.5.

Example 16, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reactor to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 3.4 mL of cocatalyst with a syringe to make Al/Ti = 2500, ethylene pressure 40 atm, and temperature 140°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the ethylene pressure at 40 atm at 140°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 97.5×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=295kg·mol ^-1 , Mw/Mn=3.3.

Example 17, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 0.68 mL of cocatalyst with a syringe to make Al/Ti = 500, ethylene pressure 40 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the 40 atm ethylene pressure at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 48.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=451kg·mol ^-1 , Mw/Mn=1.8.

Example 18, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reactor to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 1.7 mL of cocatalyst with a syringe to make Al/Ti = 1250, ethylene pressure 40 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the 40 atm ethylene pressure at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 104×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=443kg·mol ^-1 , Mw/Mn=1.5.

Example 19, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 5 mL of cocatalyst with a syringe to make Al/Ti = 3750, ethylene pressure 40 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the 40 atm ethylene pressure at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 127.5×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=419kg·mol ^-1 , Mw/Mn=1.6.

Example 20, Ti3 catalyzed ethylene polymerization

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene under an ethylene atmosphere, inject 6.8 mL of cocatalyst with a syringe to make Al/Ti = 5000, ethylene pressure 40 atm, and temperature 50°C. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain the 40 atm ethylene pressure at 50°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 93.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . Polymer Mw=399kg·mol ^-1 , Mw/Mn=2.1.

Example 21, Ti3 catalyzed copolymerization of ethylene and 1-octene

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene and 110 g of 1-octene under an ethylene atmosphere. Use a syringe to inject 3.4 mL of cocatalyst to make Al/Ti = 2500, ethylene pressure 40 atm, temperature 140℃. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain 40 atm ethylene pressure at 140°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 122.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . The polymer M _w =459kg·mol ^-1 , M _w /M _n =2.1, and the octene molar content is 8.5 mol%.

Example 22, Ti3 catalyzed copolymerization of ethylene and 1-octene

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene and 110 g of 1-octene under an ethylene atmosphere. Use a syringe to inject 3.4 mL of cocatalyst to make Al/Ti = 2500, ethylene pressure 20 atm, temperature 140℃. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 25 atm nitrogen pressure, maintain an ethylene pressure of 20 atm at 140°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 101.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . The polymer M _w =360kg·mol ^-1 , M _w /M _n =1.8, and the octene molar content is 12.8 mol%.

Example 23, Ti3 catalyzed copolymerization of ethylene and 1-octene

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene and 110 g of 1-octene under an ethylene atmosphere. Use a syringe to inject 3.4 mL of cocatalyst to make Al/Ti = 2500, ethylene pressure 40 atm, temperature 160℃. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain 40 atm ethylene pressure at 160°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 114.0×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . The polymer M _w =420kg·mol ^-1 , M _w /M _n =2.0, and the octene molar content is 10.2 mol%.

Example 24, Ti3 catalyzed copolymerization of ethylene and 1-octene

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene and 110 g of 1-octene under an ethylene atmosphere. Use a syringe to inject 3.4 mL of cocatalyst to make Al/Ti = 2500, ethylene pressure 40 atm, temperature 180℃. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 45 atm nitrogen pressure, maintain 40 atm ethylene pressure at 160°C, and stir vigorously for 2 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 105.5×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . The polymer M _w =386kg·mol ^-1 , M _w /M _n =1.8, and the octene molar content is 15.5 mol%.

Example 25, Ti3 catalyzed copolymerization of ethylene and norbornene

Connect the high-pressure reaction kettle to the high-pressure pipeline to remove nitrogen and replace ethylene three times. Add 195 mL of toluene and 100 g of norbornene under an ethylene atmosphere. Use a syringe to inject 3.4 mL of cocatalyst to make Al/Ti = 2500, ethylene pressure 5 atm, temperature 70 ℃. In the glove box, add 1.03 mg (2 μmol) Ti3 complex to a 10 mL sample bottle equipped with a magnetic stirrer. Use a syringe to take 5 mL of anhydrous toluene. Add it to the sample bottle and stir for 5 minutes to dissolve. Use a syringe to add the catalyst toluene solution. Inject it into the main catalyst feeding tank, press the main catalyst into it with 8atm nitrogen pressure, maintain 5atm ethylene pressure at 160°C, and stir vigorously for 10 minutes. The reaction solution was neutralized with 10 mL of ethanol solution acidified with hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol, dried in vacuum overnight, and weighed. Polymerization activity: 25×10 ⁶ g·mol ^-1 (Ti)·h ^-1 . The polymer M _w =210kg·mol ^-1 , M _w /M _n =1.9, and the norbornene molar content is 48 mol%.

Claims (8)

1. NNO-coordinated titanium zirconium hafnium metal catalysts have the structure shown in formula (I):

wherein R is selected from methyl, chlorine and dimethylamino; r is R ¹ Selected from methyl, ethyl, hydrogen, isopropyl, chloro, fluoro; r is R ² Selected from methyl, methoxy, hydrogen, t-butyl, benzhydryl; r is R ³ Selected from methyl, ethyl, hydrogen, isopropyl, chloro, fluoro; r is R ⁴ Selected from methyl, ethyl, hydrogen, isopropyl.

2. The method for preparing NNO-coordinated titanium zirconium hafnium metal catalyst according to claim 1, comprising the steps of: 1 molar equivalent of NNO-tridentate ligand and 1 molar equivalent of M (NMe) were combined under nitrogen atmosphere ₄ Reflux is carried out for 1-5 days under stirring, the solvent is pumped out, after washing with 5mL of anhydrous normal hexane, filter residues are dissolved in a proper amount of toluene, 10 molar equivalents of dimethyl dichlorosilane are gradually added dropwise at the temperature of minus 78 ℃, the mixture is gradually heated to 60 ℃, stirring is carried out overnight, after the solvent is removed, good solvent is added for dissolution and filtration, and after the solvent is removed from the filtrate, poor solvent is added for washing, the NNO-coordinated titanium zirconium hafnium metal catalyst is obtained.

3. The preparation method according to claim 2, characterized in that: the good solvent is selected from dichloromethane and toluene, and the poor solvent is selected from n-hexane, n-pentane and cyclohexane.

4. A process for carrying out an olefin polymerization reaction, characterized by: the catalyst for the reaction is the NNO-coordinated titanium zirconium hafnium metal catalyst in claim 1.

5. The method according to claim 4, wherein: the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene and norbornene.

6. The method according to claim 4, wherein: the catalyst is also added with a cocatalyst which is one or more of trifluorophenyl boron, triphenylcarbonium tetra (pentafluorophenyl) borate, aluminoxane, alkyl aluminum and alkyl aluminum chloride.

7. The method according to claim 6, wherein: the aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; the alkyl aluminum chloride is diethyl aluminum chloride, diethyl aluminum sesquichloride or ethyl aluminum dichloride.

8. The method according to claim 4, wherein: the polymerization temperature is 0-180 ℃, the polymerization pressure is 0.1-5Mpa, and the polymerization solvent is one or more of toluene, hexane and heptane.