A preparation method of a metal catalyst based on thioether-amine coordination and its synthesis of polyolefin elastomer POE

Abstract

The present invention reports the high-yield synthesis of a series of sulfide-amine coordinated titanium zirconium hafnium metal catalysts for high-temperature solution polymerization of olefins, successfully synthesizing polyolefin elastomer POE. By changing the groups on the catalyst structure, the performance of the catalyst is significantly changed. The sulfide-amine coordinated titanium zirconium hafnium metal catalyst reported in the present invention has the advantages of simple synthesis and high product yield. Under the combined action of the co-catalyst, it shows high activity (158500kg (POE) mol) at high temperature (160°C). ‑1 (M)h ‑1 ) and exhibits excellent α-olefin copolymerization ability (1-octene insertion rate reaches 42.7 mol%), making it suitable for high-temperature solution polymerization and capable of producing high-performance polyolefin elastomers (POE). Therefore, this invention demonstrates original innovation and enhances the competitiveness of my country's polyolefin materials technology market.

Description

Technical Field

[0001] The invention relates to the preparation of an olefin coordination polymerization metal catalyst and its application in the field of olefin polymerization. Background Art

[0002] In recent years, the production capacity and application of polyolefin materials have continued to rise. They are inexpensive and offer excellent mechanical properties, including stress / strain ratio, toughness, and strength, as well as corrosion resistance and chemical stability. These excellent properties have led to their widespread use in a wide range of applications, including packaging, pipes, electronics, and textiles, as well as in transportation vehicles such as automobiles, aircraft, and high-speed rail, and in military products. With the continuous development of society, the application range of polyolefin materials continues to expand. However, in this process, a single polyolefin material can no longer meet diverse needs. Consequently, high-performance polyolefin materials such as ultra-high molecular weight polyethylene (UHMWPE) and polyolefin elastomers have emerged. Among them, polyolefin elastomers (POE) are high-performance polyolefins that are random ethylene / α-olefin copolymers with a high α-olefin content (typically exceeding 20% ​​by weight). POE is typically synthesized via homogeneous solution olefin polymerization, which offers greater control over the process and polymer microstructure, thereby improving production efficiency. High-temperature solution polymerization reduces solution viscosity, increases yield, and reduces costs. However, it also poses significant challenges to olefin polymerization catalysts, as increasing polymerization temperature reduces catalyst activity and the molecular weight of the resulting polymer. Therefore, it is particularly important to develop homogeneous metal catalysts with enhanced performance at high temperatures.

[0003] To this end, researchers around the world designed and synthesized metallocenes and constrained geometry catalysts (CGCs) and began to successfully use them in the commercial production of POE in the early 1990s (Chem. Rev. 1998, 98, 2587-2598). However, CGC can cause a decrease in polymer molecular weight due to rapid elimination of β-H and chain transfer at high temperatures. In addition, non-metallocene catalysts have unique catalytic properties and can replace metallocene catalysts to a certain extent. Pyridine amine-based metal catalysts were originally screened by Dow Chemical Research through high-throughput means (Angew. Chem. Int. Ed. 2006, 45, 3278-3283). The resulting metal catalysts have high activity in the polymerization of ethylene and α-olefins and can achieve regulation of α-olefin content. Group IV metal complexes supported by bidentate ligands containing hard nitrogen electron donors are a representative class of catalysts and have important applications in the high-temperature copolymerization of ethylene and α-olefins. Numerous studies have shown that the addition of soft sulfur or phosphorus electron donors to the ligands may bring unexpected properties to metal complexes (Angew. Chem. Int. Ed. 2001, 40, 680-699).

[0004] In this invention, we synthesized sulfide-amine coordinated titanium zirconium hafnium metal catalysts with high yield and evaluated their catalytic performance in the copolymerization of ethylene and α-olefins. Under the combined action of the cocatalyst, the catalyst showed high activity (158500 kg (POE) mol) at high temperature (160 ° C). -1 (M)h -1 ) and excellent copolymerizability (maximum insertion rate of 42.7 mol%), making it suitable for high-temperature solution polymerization and capable of producing high-performance polyolefin elastomers. Therefore, this invention demonstrates original innovation and enhances the competitiveness of my country's polyolefin materials technology market. Summary of the Invention

[0005] The purpose of the present invention is to provide a synthesis of a sulfide-amine coordinated titanium zirconium hafnium metal catalyst and its application in preparing polyolefin elastomers.

[0006] The present invention provides a sulfide-amine coordinated titanium zirconium hafnium metal catalyst represented by formula (I):

[0007]

[0008] Wherein, M is selected from titanium, zirconium, and hafnium; and R is selected from C1-C8 straight-chain alkyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, and 2,6-difluorophenyl.

[0009] Preferably, the metal compound of the present invention is selected from any one of the metal catalysts shown in (II):

[0010]

[0011] The present invention provides a method for preparing the above-mentioned sulfide-amine coordinated titanium zirconium hafnium metal catalyst, comprising the following steps:

[0012] Under a nitrogen atmosphere, the metal salt is dissolved in 20-80 mL of anhydrous solvent, 4.0-5.0 molar equivalents of methylmagnesium bromide are added, and the reaction is carried out at low temperature for 2-6 hours under nitrogen protection, followed by adding 1 molar equivalent of a sulfide amine ligand and reacting for 5-12 hours. After the reaction is completed, the solvent is removed under reduced pressure, and the catalyst is extracted with a good solvent to obtain the sulfide-amine coordinated titanium zirconium hafnium metal catalyst according to claim 1.

[0013] In the above preparation method, the anhydrous solvent is selected from toluene, n-hexane, xylene, and benzene; and the good solvent is selected from n-hexane, toluene, pentane, heptane, and cyclohexane.

[0014] In the above preparation method, the metal salt MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

[0015] The present invention also provides application of the sulfide-amine coordinated titanium zirconium hafnium metal catalyst in catalyzing olefin polymerization.

[0016] In the above application, the olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene and 1-octene.

[0017] The sulfide-amine coordinated titanium zirconium hafnium metal catalyst requires a co-catalyst for catalysis. The co-catalyst is one or more of trispentafluorophenyl boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum, and alkyl aluminum chloride. The aluminoxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkyl aluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkyl aluminum chloride is diethylaluminum monochloride, diethylaluminum sesquichloride, or ethylaluminum dichloride.

[0018] In the above polymerization reaction, the polymerization temperature is 0-200° C., the polymerization pressure is 0.1-5 MPa, and the polymerization solvent is one or more of n-hexane, heptane, pentane, and toluene.

[0019] The present invention provides the preparation of a sulfide-amine coordinated titanium zirconium hafnium metal catalyst and the application of the catalyst in catalyzing olefin polymerization. The sulfide-amine coordinated titanium zirconium hafnium metal catalyst reported in the present invention has the advantages of simple synthesis, easy availability of raw materials, high product yield, high temperature resistance (160°C), high catalytic activity (the activity can reach up to 158500kg (POE) mol -1 (M)h -1 The metal catalyst provided by the present invention has the advantages of good copolymerization performance (1-octene insertion rate can reach 42.7 mol%) and is particularly suitable for the preparation of high-quality, high-performance polyolefin materials through high-temperature solution polymerization. The metal catalyst provided by the present invention is original and innovative and can promote the development of my country's high-end polyolefin chemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the H NMR spectrum of catalyst C1.

[0021] Figure 2 This is the H NMR spectrum of catalyst C2.

[0022] Figure 3 This is the H NMR spectrum of catalyst C3.

[0023] Figure 4 This is the H NMR spectrum of catalyst C4.

[0024] Figure 5 This is the H NMR spectrum of catalyst C5.

[0025] Figure 6 This is the H NMR spectrum of catalyst C6.

[0026] Figure 7 This is the H NMR spectrum of catalyst C7.

[0027] Figure 8 This is the infrared spectrum of polyolefin elastomer POE with a 1-octene insertion rate of 42.7.

[0028] Figure 9 This is the infrared spectrum of polyolefin elastomer POE with a 1-octene insertion rate of 36.9%.

[0029] Figure 10 This is the infrared spectrum of polyolefin elastomer POE with a 1-octene insertion rate of 34.1%.

[0030] Figure 11 This is the infrared spectrum of polyolefin elastomer POE with a 1-octene insertion rate of 30.1%.

[0031] Figure 12 This is a crystal diagram of catalyst C4.

[0032] Figure 13 This is a crystal diagram of catalyst C7. DETAILED DESCRIPTION

[0033] The present invention is further described by way of examples, but the present invention is not limited thereto. The examples of the present invention can enable those skilled in the art to more fully understand the present invention.

[0034] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0035] Unless otherwise specified, the following raw materials and reagents were purchased from commercial products.

[0036] The sulfide-amine ligand 2,6- i Pr2-C6H3-NH-C6H4-S-Me(C1-L), 2,6- i Pr2-C6H3-NH-C6H4-S-C6H5(C2-L), 2,6- i Pr2-C6H3-NH-C6H4-S-C6H3-2,6-Me2(C3-L), 2,6- i Pr2-C6H3-NH-C6H4-S-C6H2-2,4,6-Me3(C4-L) and C6H5-NH-C6H4-S-Me(C7-L) were synthesized according to literature methods (Tetrahedron 2008, 64, 6281-6288, J.Mol.Catal.A:Chem.2002, 182-183, 515-523).

[0037] The present invention is described below with reference to specific embodiments.

[0038] Example 1. Preparation of Catalyst C1

[0039] 2-Bromothioanisole (5.08 g, 25.0 mmol), 2,6-diisopropylaniline (7.09 g, 40.0 mmol), sodium tert-butoxide (3.84 g, 40.0 mmol), palladium acetate (0.028 g, 0.125 mmol), and n-butyldi(1-adamantyl)phosphine (0.090 g, 0.25 mmol) were dissolved in 30 mL of toluene and stirred at 120°C under a nitrogen atmosphere for 12 hours. The mixture was cooled to room temperature, diluted with dichloromethane, and washed three times with water. The organic phase was dried over anhydrous magnesium sulfate. After separation by column chromatography and removal of the solvent, C1-L (4.23 g, 56% yield) was obtained as a white solid. 1 H NMR (400MHz, CDCl3): δ7.47(d,J=7.6Hz,1H),7.30(dd,J=8.5,6.7Hz,1H),7.23(d,J=7.5Hz,2H),7.03(t,J=7.7Hz,1H),6.67(t,J=7 .4Hz,1H),6.39(s,1H),6.15(d,J=8.1Hz,1H),3.11(hept,J=6.9Hz,2H),2.44(s,3H),1.20(d,J=6.9Hz,6H),1.14(d,J=6.9Hz,6H). 13 C NMR (100MHz, CDCl3): δ148.48,147.59,135.38,134.50,129.60,127.49,123.98,119.01,117.63,111.40,28.50,24.77,23.09,18.42ppm.Anal.Calcd for C 19 H 25 NS:C,76.20;H,8.41;N,4.68.Found:C,76.31;H,8.51;N,4.45.

[0040] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C1-L (0.3 g, 1 mmol) was then added. The reaction was incubated at -40°C in the dark for 2 hours, then returned to room temperature and continued for 5 hours. After the reaction, the solvent was removed, the product was extracted with toluene, and filtered to obtain 0.45 g of product C1 with an 86% yield. 1H NMR (400MHz, C6D6): δ7.29(t,J=8.0Hz,1H),7.19–7.16(m,3H),6.83(ddd,J=8.4,7.3,1.6Hz,1H),6.51(m,1H),6.01(dd, J=8.3,1.1Hz,1H),3.28(hept,J=6.8Hz,2H),2.07(s,3H),1.25(d,J=6.9Hz,6H),0.99(d,J=6.8Hz,6H),0.57(s,9H)ppm. 13 C NMR (100MHz, C6D6): δ159.79,149.27,134.10,133.28,130.54,128.98,125.5 2,121.54,118.73,116.80,63.11,28.49,25.57,24.37,23.45ppm.Anal.Calcd for C 22 H 33 HfNS:C,50.61;H,6.37;N,2.68.Found:C,50.89;H,6.56;N,2.49.

[0041] Example 2. Preparation of Catalyst C2

[0042] Weigh 2,6- i Pr2-C6H3-NH-C6H4-S-Me (3.78 g, 15.0 mmol), 2,6-diisopropylaniline (3.99 g, 22.5 mmol), sodium tert-butoxide (2.88 g, 30.0 mmol), palladium acetate (0.017 g, 0.075 mmol), and n-butyldi(1-adamantyl)phosphine (0.054 g, 0.15 mmol) were dissolved in 30 mL of toluene and stirred at 120°C under a nitrogen atmosphere for 12 hours. The mixture was cooled to room temperature, diluted with dichloromethane, and then washed three times with water. The organic phase was dried over anhydrous magnesium sulfate. Column chromatography was used to separate and remove the solvent to obtain C2-L (4.83 g, 89% yield) as a white solid. 1 H NMR (400MHz, CDCl3): δ7.67(dd,J=7.6,1.5Hz,1H),7.41–7.18(m,9H),6.80(td,J=7.5,1.2Hz,1H),6.31(br,1H ,N–H),6.26(dd,J=8.2,1.1Hz,1H),2.97(hept,J=6.9Hz,2H),1.15(d,J=6.9Hz,6H),1.04(d,J=6.9Hz,6H)ppm. 13C NMR (100MHz, CDCl3): δ149.44,147.83,137.93,137.07,134.63,131.43,129.07,127.71 ,126.74,125.68,123.92,117.42,113.25,111.75,28.35,24.48,23.17ppm.Anal.Calcd for C 24 H 27 NS:C,79.73;H,7.53;N,3.87.Found:C,79.59;H,7.38;N,3.67.

[0043] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C2-L (0.36 g, 1 mmol) was then added. The reaction was allowed to react at -40°C in the dark for 2 hours, then at room temperature for another 5 hours. After the reaction, the solvent was removed, the mixture was extracted with toluene, and filtered to obtain 0.45 g of product C2 in an 86% yield. 1 H NMR (400MHz, C6D6): δ7.32–7.24(m,2H),7.18(s,1H),7.13–7.07(m,2H),7.07–6.65(m,5H),6.46(td,J=7.6,1.2Hz,1H ),6.11(dd,J=8.4,1.1Hz,1H),3.34(hept,J=6.9Hz,2H),1.20(d,J=6.9Hz,6H),1.06(d,J=6.8Hz,6H),0.49(s,9H)ppm. 13 C NMR (100MHz, C6D6): δ161.19,149.83,137.17,136.22,132.19,131.58,129.52,129.32 ,127.45,125.62,119.27,118.10,117.15,64.20,28.51,25.69,24.19ppm.Anal.Calcd for C 27 H 35 HfNS:C,55.52;H,6.04;N,2.40.Found:C,55.79;H,6.37;N,2.53.

[0044] Example 3. Preparation of Catalyst C3

[0045] Weigh 2,6- iPr2-C6H3-NH-C6H4-S-Me (4.40 g, 15.0 mmol), 2,6-diisopropylaniline (3.99 g, 22.5 mmol), sodium tert-butoxide (2.88 g, 30.0 mmol), palladium acetate (0.017 g, 0.075 mmol), and n-butyldi(1-adamantyl)phosphine (0.054 g, 0.15 mmol) were dissolved in 30 mL of toluene and stirred at 120°C under a nitrogen atmosphere for 12 hours. The mixture was cooled to room temperature, diluted with dichloromethane, and then washed three times with water. The organic phase was dried over anhydrous magnesium sulfate. Column chromatography was used to separate and remove the solvent to obtain C3-L (5.14 g, 88% yield) as a white solid. 1 H NMR (400MHz, CDCl3): δ7.33(dd,J=8.4,6.8Hz,1H),7.25–7.14(m,5H),6.90–6.85(m,2H),6.60–6.53(m,1H),6.12(d,J= 7.4Hz,1H),5.73(br,1H,N–H),3.08(hept,J=6.8Hz,2H),2.52(s,6H),1.19(d,J=6.9Hz,6H),1.13(d,J=6.9Hz,6H)ppm. 13 C NMR (100MHz, CDCl3): δ147.56,146.52,142.93,135.34,131.85,129.88,128.81,127.4 4,127.34,123.95,119.17,118.08,111.77,28.35,24.74,23.25,22.14ppm.Anal.Calcd for C 26 H 31 NS:C,80.16;H,8.02;N,3.60.Found:C,79.94;H,8.13;N,3.69.

[0046] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C3-L (0.39 g, 1 mmol) was then added. The reaction was allowed to react at -40°C in the dark for 2 hours, then at room temperature for another 5 hours. After the reaction, the solvent was removed, the mixture was extracted with toluene, and filtered to obtain 0.53 g of product C3 in an 87% yield. 1H NMR (400MHz, C6D6): δ7.37–7.29(m,1H),7.22(d,J=7.7Hz,2H),6.99–6.72(m,5H),6.39(t,J=7.3Hz,1H),6.07(d,J =8.1Hz,1H),3.38(hept,J=6.9Hz,2H),2.28(s,6H),1.28(d,J=6.9Hz,6H),1.02(d,J=6.7Hz,6H),0.61(s,9H)ppm. 13 C NMR (100MHz, C6D6): δ157.43,150.04,141.94,132.56,131.66,129.95,129.49,129.45,129.3 8,128.73,125.61,121.76,118.93,116.72,62.91,28.52,25.68,24.25,21.95ppm.Anal.Calcd for C 29 H 39 HfNS:C,56.90;H,6.42;N,2.29.Found:C,57.07;H,6.31;N,2.49.

[0047] Example 4. Preparation of Catalyst C4

[0048] Weigh 2,6- i Pr2-C6H3-NH-C6H4-S-Me (4.61 g, 15.0 mmol), 2,6-diisopropylaniline (3.99 g, 22.5 mmol), sodium tert-butoxide (2.88 g, 30.0 mmol), palladium acetate (0.017 g, 0.075 mmol), and n-butyldi(1-adamantyl)phosphine (0.054 g, 0.15 mmol) were dissolved in 30 mL of toluene and stirred at 120°C under a nitrogen atmosphere for 12 hours. The mixture was cooled to room temperature, diluted with dichloromethane, and then washed three times with water. The organic phase was dried over anhydrous magnesium sulfate. Column chromatography was used to separate and remove the solvent to obtain C4-L (5.51 g, 93% yield) as a white solid. 1H NMR (400MHz, CDCl3): δ7.29(dd,J=8.4,6.8Hz,1H),7.25–7.18(m,2H),6.99(s,2H),6.88(t,J=7.3Hz,2H),6.55(td,J=7.6,1.2Hz,1H) ,6.07(s,1H),5.68(br,1H,N–H),3.03(hept,J=6.9Hz,2H),2.45(s,6H),2.31(s,3H),1.13(d,J=6.9Hz,6H),1.07(d,J=6.9Hz,6H)ppm. 13 C NMR (100MHz, CDCl3): δ147.56,146.44,142.79,138.78,135.43,129.72,129.65,128.18,127.3 9,127.15,123.93,119.54,118.05,111.74,28.34,24.71,23.26,22.00,21.18ppm.Anal.Calcd for C 27 H 33 NS:C,80.35;H,8.24;N,3.47.Found:C,80.26;H,8.38;N,3.56.

[0049] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C4-L (0.40 g, 1 mmol) was then added. The reaction was allowed to react at -40°C in the dark for 2 hours, then at room temperature for another 5 hours. After the reaction, the solvent was removed, the mixture was extracted with toluene, and filtered to obtain 0.55 g of product C4 in an 87% yield. 1 H NMR (400MHz, C6D6): δ7.34(t,J=7.5Hz,1H),7.23(d,J=7.7Hz,2H),6.86(dd,J=7.7,1.3Hz,1H),6.80–6.75(m,1H),6.71(s,2H),6.45–6.39(m, 1H), 6.10 (d, J = 8.3Hz, 1H), 3.41 (hept, J = 6.8Hz, 2H), 2.29 (s, 6H), 2.03 (s, 3H), 1.29 (d, J = 6.9Hz, 6H), 1.04 (d, J = 6.8Hz, 6H), 0.63 (s, 9H) ppm. 13CNMR (100MHz, C6D6): δ157.35,149.99,141.82,139.46,132.86,130.42,129.65,129.32,128. 59,125.60,122.18,118.87,116.67,62.84,28.53,25.73,24.28,21.84,20.92ppm.Anal.Calcd forC 30 H 41 HfNS:C,57.54;H,6.60;N,2.24.Found:C,57.67;H,6.36;N,2.44.

[0050] Example 5. Preparation of Catalyst C5

[0051] Zirconium tetrachloride (0.256 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C1-L (0.30 g, 1 mmol) was then added. The reaction was incubated at -40°C in the dark for 2 hours, then returned to room temperature and continued for 5 hours. After completion of the reaction, the solvent was removed, the mixture was extracted with toluene, and filtered to yield 0.38 g of product C5 in an 87% yield. 1 H NMR (400MHz, C6D6): δ7.32–7.24(m,1H),7.19(dd,J=7.7,1.5Hz,1H),7.14(d,J=2.1Hz,2H),6.84(ddd,J=8.4,7.3,1.6Hz,1H),6.55(td,J=7.5 ,1.2Hz,1H),6.01(dd,J=8.4,1.1Hz,1H),3.19(hept,J=6.9Hz,2H),2.07(s,3H),1.19(d,J=6.9Hz,6H),0.96(d,J=6.8Hz,6H),0.80(s,9H)ppm. 13 CNMR (100MHz, C6D6): δ158.06,150.56,133.71,130.70,130.18,129.79,125.6 8,122.31,118.84,115.47,50.63,28.49,25.66,24.30,22.96ppm.Anal.Calcd for C 22 H 33 NSZr:C,60.77;H,7.65;N,3.22.Found:C,60.45;H,7.59;N,3.41.

[0052] Example 6. Preparation of Catalyst C6

[0053] Weigh C6-Cl (0.45 g, 1.0 mmol) and dissolve it in 20 mL of anhydrous toluene. Add 1.5 mL / 4.5 mmol of methylmagnesium bromide at -40 °C (acetonitrile-liquid nitrogen bath) and stir at room temperature for 12 hours. Extract with n-hexane and remove the solvent to obtain a brown solid C6 (0.36 g, yield 92%). 1 H NMR (400MHz, C6D6): δ7.28(dd,J=8.7,6.5Hz,1H),7.23–7.20(m,2H),7.17(m,1H),6.83(ddd,J=8.7,7.3,1.6Hz,1H),6.56(td,J=7.4,1.2 Hz,1H),6.00(dd,J=8.3,1.1Hz,1H),3.36(hept,J=6.8Hz,2H),1.99(s,3H),1.78(s,9H),1.26(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H)ppm. 13 C NMR (100MHz, C6D6): δ159.22,147.83,137.78,133.80,130.06,128.83,125.3 3,123.11,119.47,114.94,72.20,28.54,25.86,24.10,24.08ppm.Anal.Calcd for C 22 H 33 NSTi:C,67.51;H,8.50;N,3.58.Found:C,67.89;H,8.63;N,3.76.

[0054] Example 7. Preparation of Catalyst C7

[0055] 2-Aminothioanisole (3.48 g, 25.0 mmol), iodobenzene (5.10 g, 25.0 mmol), sodium tert-butoxide (3.84 g, 40.0 mmol), palladium acetate (0.028 g, 0.125 mmol), and 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.156 g, 0.25 mmol) were dissolved in 30 mL of toluene and stirred at 120°C under a nitrogen atmosphere for 12 hours. The mixture was cooled to room temperature, diluted with dichloromethane, and washed three times with water. The organic phase was dried over anhydrous magnesium sulfate. After column chromatography and solvent removal, a yellow oil, C7-L (2.43 g, 46% yield), was obtained. 1H NMR (400MHz, CDCl3): δ7.39 (dd, J=7.7, 1.4Hz, 1H), 7.26–7.16 (m, 3H), 7.09 (t, J=8.0Hz ,3H),6.93(t,J=7.7Hz,1H),6.80(t,J=7.7Hz,1H),6.49(br,1H,N–H),2.32(s,3H)ppm. 13 C NMR (100MHz, CDCl3): δ143.68,142.56,132.98,129.47,128.45,124.22,121.98,120.64,119.47,115.35,18.02ppm.Anal.Calcd forC 13 H 13 NS:C,72.52;H,6.09;N,6.51.Found:C,72.16;H,6.27;N,6.46.

[0056] Zirconium tetrachloride (0.256 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. At -40°C (in an acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol of 3 M methylmagnesium bromide solution was slowly added and stirred for 2 hours. Ligand C7-L (0.43 g, 2 mmol) was then added. The reaction was in the dark at -40°C for 2 hours, then returned to room temperature and continued for 5 hours. After the reaction, the solvent was removed, the product was extracted with toluene, and filtered to obtain 0.54 g of product C7 in an 85% yield. 1 H NMR (400MHz, C6D6): δ7.11–7.05(m,6H),6.98(t,J=8.1Hz,6H),6.90–6.85(m,2 H), 6.53 (t, J = 7.8Hz, 2H), 6.18 (d, J = 8.1Hz, 2H), 2.09 (s, 6H), 0.37 (s, 6H) ppm. 13 C NMR (100MHz, C6D6): δ159.26,143.50,131.45,129.70,129.49,129.11,124.86,119.12,116.97,114.52,48.35,21.41ppm.Anal.Calcd for C 28 H 30 HfN2S2:C,52.78;H,4.75;N,4.40.Found:C,52.84;H,4.55;N,4.48.

[0057] Example 8: C1 catalytic ethylene polymerization

[0058] A 350 mL glass reactor equipped with a magnet was used for the polymerization reaction. 2 μmol of catalyst C1, 2.2 μmol of triphenylcarbon tetrakis(pentafluorophenyl)borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization pipeline, and when the temperature rose to 80°C, 50 mL of toluene was added thereto. During the polymerization process, ethylene gas was continuously introduced to ensure that the reaction pressure was 5 atm. After reacting for 2 minutes, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large amount of ethanol for sedimentation, and the final polymer was obtained by filtration and drying. Polymerization activity: 32,000 kg·mol -1 (Hf)·h -1 , polymer Mw = 152 kg·mol -1 , Mw / Mn=2.1.

[0059] Example 9: C1 catalytic ethylene polymerization

[0060] The polymerization process and reaction conditions were the same as in Example 8, and the polymerization temperature was 120°C. Polymerization activity: 52600 kg·mol -1 (Hf)·h -1 Polymer Mw = 124 kg·mol -1 , Mw / Mn=2.3.

[0061] Example 10: C1 catalytic ethylene polymerization

[0062] A 100mL steel reactor equipped with a magnet was used for the polymerization reaction. 50mL of toluene was injected via syringe, the reactor contents were heated to 160°C, and the reactor was saturated with 1MPa of ethylene. In a glove box, 2μmol of catalyst C1, 100μmol of methylaluminoxane, and 2.2μmol of triphenylcarbon tetrakis(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube via syringe. Nitrogen gas (over 1MPa) was pressurized into the reactor. During the polymerization process, ethylene gas was continuously introduced to maintain a reaction pressure of 1MPa. After reaching the set reaction time of 2 minutes, 2mL of ethanol was pressurized into the reactor under nitrogen gas (over 1MPa). The reactor was cooled and vented, and the contents of the reactor were poured into a large amount of ethanol. The polymer precipitated and was filtered to obtain the polymer, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 116,000kg·mol -1 (Hf)·h -1 , polymer Mw = 173 kg·mol -1 , Mw / Mn=2.3.

[0063] Example 11: C1 catalytic ethylene polymerization

[0064] The polymerization process and reaction conditions were the same as in Example 10, and the polymerization temperature was 180° C. Polymerization activity: 97900 kg·mol -1 (Hf)·h -1 Polymer Mw = 162 kg·mol -1 , Mw / Mn=2.4.

[0065] Example 12: C1 catalytic ethylene polymerization

[0066] A 350 mL glass reactor equipped with a magnet was used for the polymerization reaction. 2 μmol of catalyst C1 and 1000 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization line. When the temperature rose to 120°C, 50 mL of toluene was added. During the polymerization process, ethylene gas was continuously introduced to ensure that the reaction pressure was 5 atm. After reacting for 2 minutes, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large amount of ethanol for sedimentation, and the final polymer was obtained by filtration and drying. Polymerization activity: 154 kg·mol -1 (Hf)·h -1 , polymer Mw = 115 kg·mol -1 , Mw / Mn=2.2.

[0067] Example 13: C2 catalytic ethylene polymerization

[0068] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C2. Polymerization activity: 46800 kg·mol -1 (Hf)·h -1 Polymer Mw = 134 kg·mol -1 , Mw / Mn=2.0.

[0069] Example 14: C3 catalytic ethylene polymerization

[0070] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C3. Polymerization activity: 45200 kg·mol -1 (Hf)·h -1 Polymer Mw = 176 kg·mol -1 , Mw / Mn=2.1.

[0071] Example 15: C4 catalytic ethylene polymerization

[0072] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C4. Polymerization activity: 24220 kg·mol -1 (Hf)·h -1 Polymer Mw = 196 kg·mol -1 , Mw / Mn=2.2.

[0073] Example 16: C5 catalytic ethylene polymerization

[0074] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C5. Polymerization activity: 20600 kg·mol -1 (Zr)·h -1 Polymer Mw = 217 kg·mol -1 , Mw / Mn=2.3.

[0075] Example 17: C6 catalytic ethylene polymerization

[0076] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C6. Polymerization activity: 18600 kg·mol -1 (Ti)·h -1 Polymer Mw = 2150 kg·mol -1 , Mw / Mn=2.3.

[0077] Example 18: C7 catalytic ethylene polymerization

[0078] The polymerization process and reaction conditions were the same as in Example 9, and the catalyst used was C7. Polymerization activity: 18300 kg·mol -1 (Hf)·h -1 Polymer Mw = 250 kg·mol -1 , Mw / Mn=2.2.

[0079] Example 19: C1 catalyzed ethylene / 1-octene copolymerization

[0080] A 350 mL glass reactor equipped with a magnet was used for the polymerization reaction. 2 μmol of catalyst C1, 2.2 μmol of triphenyl carbon tetrakis (pentafluorophenyl) borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was then connected to the polymerization pipeline. When the temperature rose to 120°C, 26.6 mL of toluene and 23.4 mL of 1-octene were added thereto. During the polymerization, ethylene gas was continuously introduced to ensure that the reaction pressure was 5 atm. After reacting for 2 minutes, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large amount of ethanol for sedimentation, and the final polymer was obtained by filtration and drying. Polymerization activity: 21060 kg·mol -1 (Hf)·h -1 , polymer Mw = 63 kg·mol -1 , Mw / Mn=2.4, the content of 1-octene in the copolymer is 34.1 mol%.

[0081] Example 20: C1 catalyzed ethylene / 1-octene copolymerization

[0082] The polymerization process and reaction conditions were the same as in Example 19, except that 34.4 mL of toluene and 15.6 mL of 1-octene were used. Polymerization activity: 18360 kg·mol -1 (Hf)·h -1 Polymer Mw = 67 kg·mol -1 , Mw / Mn=2.2, the content of 1-octene in the copolymer is 30.1 mol%.

[0083] Example 21: C1 catalyzed ethylene / 1-octene copolymerization

[0084] The polymerization process and reaction conditions were the same as in Example 19, except that 42.2 mL of toluene and 7.8 mL of 1-octene were used. Polymerization activity: 11940 kg·mol -1 (Hf)·h -1 Polymer Mw = 71 kg·mol -1 , Mw / Mn=2.7, the content of 1-octene in the copolymer is 10.0 mol%.

[0085] Example 22: C1 catalyzed ethylene / 1-octene copolymerization

[0086] A 100 mL steel reactor equipped with a magnet was used for the polymerization reaction. A mixture of 26.6 mL of toluene and 23.4 mL of 1-octene (50 mL total) was injected via syringe. The reactor contents were heated to 120°C and saturated with 1 MPa of ethylene. In a glove box, 2 μmol of catalyst C3, 100 μmol of methylaluminoxane, and 2.2 μmol of triphenyl tetrakis(pentafluorophenyl)borate were added, dissolved in toluene, and transferred via syringe to a catalyst storage tube. Nitrogen gas (over 1 MPa) was then pressurized into the reactor. Ethylene gas was continuously introduced to maintain a reaction pressure of 1 MPa during the polymerization. After the set reaction time of 2 min, 2 mL of ethanol was pressurized into the reactor under nitrogen (over 1 MPa). The reactor was cooled and vented, and the contents were poured into a large amount of ethanol. The polymer precipitated and was filtered, washed with a small amount of ethanol, and finally vacuum-dried overnight before being weighed. Polymerization activity: 67,300 kg·mol -1 (Hf)·h -1 , polymer Mw = 121 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the copolymer is 20.6 mol%.

[0087] Example 23: C1-catalyzed ethylene / 1-octene copolymerization

[0088] The polymerization process and reaction conditions were the same as in Example 22, and the polymerization pressure was 2 MPa. Polymerization activity: 96200 kg·mol -1 (Hf)·h-1 Polymer Mw = 168 kg·mol -1 , Mw / Mn=2.4, the content of 1-octene in the copolymer is 11.0 mol%.

[0089] Example 24: C1-catalyzed ethylene / 1-octene copolymerization

[0090] The polymerization process and reaction conditions were the same as in Example 23, and the polymerization pressure was 3 MPa. Polymerization activity: 14600036 kg·mol -1 (Hf)·h -1 Polymer Mw = 213 kg·mol -1 , Mw / Mn=2.2, the content of 1-octene in the copolymer is 5.1 mol%.

[0091] Example 25: C1 catalyzed ethylene / 1-octene copolymerization

[0092] The polymerization process and reaction conditions were the same as in Example 23, and the selected temperature was 140°C. Polymerization activity: 112000 kg·mol -1 (Hf)·h -1 Polymer Mw = 61 kg·mol -1 , Mw / Mn=2.4, the content of 1-octene in the copolymer is 19.8 mol%.

[0093] Example 26: C1 catalyzed ethylene / 1-octene copolymerization

[0094] The polymerization process and reaction conditions were the same as in Example 23, and the selected temperature was 160°C. Polymerization activity: 158500 kg·mol -1 (Hf)·h -1 Polymer Mw = 57 kg·mol -1 , Mw / Mn=2.4, the content of 1-octene in the copolymer is 19.4 mol%.

[0095] Example 27: C2 catalyzed ethylene / 1-octene copolymerization

[0096] The polymerization process and reaction conditions were the same as in Example 19, and the catalyst used was C2. Polymerization activity: 6240 kg·mol -1 (Hf)·h -1 Polymer Mw = 71 kg·mol -1 , Mw / Mn=2.3, the content of 1-octene in the copolymer is 36.4 mol%.

[0097] Example 28: C3 catalyzed ethylene / 1-octene copolymerization

[0098] The polymerization process and reaction conditions were the same as in Example 19, and the catalyst used was C3. Polymerization activity: 5100 kg·mol -1 (Hf)·h -1 Polymer Mw = 150 kg·mol -1 , Mw / Mn=2.3, the content of 1-octene in the copolymer is 31.6 mol%.

[0099] Example 29: C4-catalyzed ethylene / 1-octene copolymerization

[0100] The polymerization process and reaction conditions were the same as in Example 19, and the catalyst used was C4. Polymerization activity: 3120 kg·mol -1 (Hf)·h -1 Polymer Mw = 171 kg·mol -1 , Mw / Mn=2.5, the content of 1-octene in the copolymer is 3.0 mol%.

[0101] Example 30: C4-catalyzed ethylene / 1-octene copolymerization

[0102] The polymerization process and reaction conditions were the same as in Example 19, the catalyst used was C4, and the selected temperature was 80°C. Polymerization activity: 660 kg·mol -1 (Hf)·h -1 Polymer Mw = 311 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the copolymer is 1.5 mol%.

[0103] Example 31: C5-catalyzed ethylene / 1-octene copolymerization

[0104] The polymerization process and reaction conditions were the same as in Example 19, and the catalyst used was C5. Polymerization activity: 9900 kg·mol -1 (Hf)·h -1 Polymer Mw = 160 kg·mol -1 , Mw / Mn=2.2, the content of 1-octene in the copolymer is 2.8 mol%.

[0105] Example 32: C5-catalyzed ethylene / 1-octene copolymerization

[0106] The polymerization process and reaction conditions were the same as in Example 19, the catalyst used was C5, and the selected temperature was 80°C. Polymerization activity: 4740 kg·mol -1 (Hf)·h -1 Polymer Mw = 291 kg·mol -1 , Mw / Mn=2.8, the content of 1-octene in the copolymer is 2.5 mol%.

[0107] Example 33: C6-catalyzed ethylene / 1-octene copolymerization

[0108] The polymerization process and reaction conditions were the same as in Example 19, the catalyst used was C6, and the selected temperature was 80°C. Polymerization activity: 462 kg·mol -1 (Hf)·h -1 Polymer Mw = 1890 kg·mol -1 , Mw / Mn=2.5, the content of 1-octene in the copolymer is 2.0 mol%.

[0109] Example 34: C7-catalyzed ethylene / 1-octene copolymerization

[0110] The polymerization process and reaction conditions were the same as in Example 19, and the catalyst used was C7. Polymerization activity: 2460 kg·mol -1 (Hf)·h -1 Polymer Mw = 72 kg·mol -1 , Mw / Mn=3.1, the content of 1-octene in the copolymer is 1.2 mol%.

[0111] Example 35: C7-catalyzed ethylene / 1-octene copolymerization

[0112] The polymerization process and reaction conditions were the same as in Example 19, the catalyst used was C7, and the selected temperature was 80°C. Polymerization activity: 1500 kg·mol -1 (Hf)·h -1 Polymer Mw = 166 kg·mol -1 , Mw / Mn=2.9, the content of 1-octene in the copolymer is 1.4 mol%.

[0113] Example 36: C1 catalyzed ethylene / 1-hexene copolymerization

[0114] A 350 mL glass reactor equipped with a magnet was used for the polymerization reaction. 2 μmol of catalyst C1, 2.2 μmol of triphenyl carbon tetrakis (pentafluorophenyl) borate and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was then connected to the polymerization pipeline. When the temperature rose to 120°C, 31.6 mL of toluene and 18.4 mL of 1-hexene were added thereto. Ethylene gas was continuously introduced during the polymerization process to ensure that the reaction pressure was 5 atm. After reacting for 2 minutes, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large amount of ethanol for sedimentation, and the final polymer was obtained by filtration and drying. Polymerization activity: 19500 kg·mol -1 (Hf)·h -1 , polymer Mw = 15.2 kg·mol -1 , Mw / Mn=2.0, the content of 1-hexene in the copolymer is 32.1 mol%.

Claims

1. A sulfide-amine coordinated titanium zirconium hafnium metal catalyst, the structure of which is shown in formula (I): in, M is selected from titanium, zirconium, and hafnium; R is selected from C1-C8 straight-chain alkyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, and 2,6-difluorophenyl.

2. A method for preparing the sulfide-amine coordinated titanium zirconium hafnium metal catalyst according to claim 1, comprising the following steps: dissolving a metal salt in 20-80 mL of an anhydrous solvent under a nitrogen atmosphere, adding 4.0-5.0 molar equivalents of methylmagnesium bromide, reacting at low temperature for 2-6 hours under nitrogen protection, then adding 1 molar equivalent of a sulfide-amine ligand and reacting for 5-12 hours; after completion of the reaction, removing the solvent under reduced pressure, and extracting with a good solvent to obtain the sulfide-amine coordinated titanium zirconium hafnium metal catalyst according to claim 1.

3. The preparation method according to claim 2, wherein: The anhydrous solvent is selected from toluene, n-hexane, xylene, and benzene; and the good solvent is selected from n-hexane, toluene, pentane, heptane, and cyclohexane.

4. The preparation method according to claim 2, wherein: The metal salt is selected from one of TiCl4, ZrCl4 and HfCl4.

5. A method for olefin polymerization, characterized in that: The catalyst used is the sulfide-amine coordinated titanium zirconium hafnium metal catalyst according to claim 1.

6. The method according to claim 5, characterized in that: The olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene and 1-octene.

7. The method according to claim 5, characterized in that: The sulfide-amine coordinated titanium zirconium hafnium metal catalyst needs to be coordinated with a co-catalyst for catalysis, and the co-catalyst is one or more of trispentafluorophenyl boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, aluminoxane, alkyl aluminum and alkyl aluminum chloride.

8. The method according to claim 7, wherein: The aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum monochloride, diethylaluminum sesquichloride or ethylaluminum dichloride.

9. The method according to claim 5, characterized in that: The polymerization temperature is 0-200° C., the polymerization pressure is 0.1-5 MPa, and the polymerization solvent is one or more of n-hexane, n-heptane, n-pentane, and toluene.

Images