Preparation method of anthracene skeleton pyridyl amine binuclear metal titanium zirconium hafnium catalyst and synthesis of polyolefin elastomer

Abstract

This invention provides the preparation of an anthracene-skeletal pyridineamine-based binuclear titanium-zirconium-hafnium catalyst and its application in catalyzing the polymerization of olefins to synthesize elastomers. The anthracene-skeletal pyridineamine-based binuclear titanium-zirconium-hafnium catalyst reported in this invention features simple synthesis, readily available raw materials, and high product yield. It exhibits high catalytic activity in the copolymerization of ethylene and α-olefins (with a maximum activity reaching 9.02 × 10⁻⁶). 7 ·mol ‑1 ·h ‑1 It also exhibits better copolymerization properties (1-octene insertion rate up to 32.6 mol%); in propylene polymerization, efficient polymerization can be achieved by controlling the steric hindrance of different substituents (the highest activity can reach 8.56 × 10⁻⁶). 7 g·mol ‑1 ·h ‑1 Synthesize polymers with ultra-high molecular weight (polymer molecular weight reaches 4560 kg·mol⁻¹). ‑1 This invention relates to a random polypropylene elastomer; particularly in high-temperature solution polymerization, the catalyst maintains excellent polymerization performance for the preparation of high-quality, high-performance polyolefin materials. The metal catalyst provided by this invention is original and innovative, and can promote the development of my country's high-end polyolefin chemical industry.

Description

Technical Field

[0001] This invention relates to the preparation of metal catalysts for olefin coordination polymerization and their application in the synthesis of polyolefin elastomers. Background Technology

[0002] Polyolefin materials are widely used in everyday consumer goods and military products, ranging from toys and sports equipment to automobiles, airplanes, and rockets, due to their advantages such as light weight, high mechanical strength, impact resistance, and good processability.

[0003] With the continuous development of society, the application scope of polyolefin materials continues to expand. However, in this development process, single polyolefin materials can no longer meet diverse needs. Therefore, high-performance polyolefin materials such as polyolefin elastomers with ultra-high molecular weight and high monomer insertion rate have emerged. Among them, polyolefin elastomers (POE) are random copolymers formed by copolymerizing ethylene with 1-octene, 1-hexene, or 1-butene. When the content of higher α-olefins in the copolymer is high (usually exceeding 20 wt.%), it is a semi-crystalline, low-modulus polymer with excellent mechanical and elastic properties, attracting much attention in the automotive and photovoltaic industries. Ultra-high molecular weight atactic polypropylene (UHWMaPP), as a special type of elastomer with a molecular weight in the millions and a linear structure, has the characteristics of low hardness and high elongation. By adjusting the isotactic content of atactic polypropylene between 90% and 10%, the performance of the resin material can be controlled to change from high rigidity to high flexibility. Since it can overcome the deficiency of low strength of medium molecular weight atactic polypropylene, UHWMaPP is expected to be used in some special material fields. However, ultra-high molecular weight atactic polypropylene is difficult to synthesize. Under normal polymerization conditions, only a molecular weight of several hundred thousand can be obtained, and there is still a challenge in preparing ultra-high molecular weight atactic polypropylene.

[0004] Generally, polyolefin elastomers are synthesized via solution polymerization, a technique that allows for more efficient synthesis and better control over the polymer's microstructure, resulting in materials with superior performance. Solution polymerization is best performed at high temperatures (typically above 120°C) to prevent polymer precipitation during polymerization. Furthermore, high-temperature solution polymerization reduces viscosity, increases product yield, and thus lowers costs. However, these limitations pose significant challenges to catalysts used in olefin polymerization, as the activity of polyolefin catalysts and the molecular weight (Mws) of the resulting polymer typically decrease with increasing polymerization temperature. Therefore, developing homogeneous metal catalysts with superior catalytic performance at high temperatures is essential.

[0005] To address this, researchers worldwide designed and synthesized metallocene and constrained geometry (CGC) catalysts, which were successfully used in the commercial production of POE starting in the early 1990s (Chem. Rev. 1998, 98, 2587-2598). In addition, many non-metallocene transition metal catalysts have also been developed. Among them, pyridine-amine metal catalysts were initially screened by Dow Chemical using high-throughput methods (Angew. Chem. Int. Ed. 2006, 45, 3278-3283). The resulting metal catalysts exhibited high activity in the polymerization of ethylene and α-olefins and could control the α-olefin content, and could achieve highly isomeric polypropylene in propylene polymerization. However, these pyridine-amine metal catalysts performed poorly in the preparation of ultra-high molecular weight polymers.

[0006] Subsequently, Marks et al. introduced a naphthyl framework to construct a pyridineamine-based binuclear hafnium metal catalyst. The synergistic effect of the binuclear framework effectively improved the polymer molecular weight and monomer insertion rate (ACS Catal. 2015, 5, 5272-5282). In propylene polymerization, steric hindrance and intramolecular intermetallic chain transfer can cause 2,1-insertion of monomers, leading to regiodefects and reducing the stereoregularity of the polymer. Although the bispyridineamine ligand can provide good copolymerization performance for the metal catalyst, it does not significantly improve the catalyst's high-temperature resistance; the optimal polymerization performance is at 80℃ (Macromolecules 2018, 51, 2401-2410).

[0007] In this invention, rigid anthracene is introduced as a bridging binuclear metal framework to improve the high-temperature resistance of the metal catalyst. A series of novel binuclear pyridine imine ligands are directly synthesized through the amine-aldehyde condensation catalyzed by p-toluenesulfonic acid (p-TsOH) between 1,8-diaminoanthracene and 2-pyridine-formaldehyde with different substituents. Subsequently, an anthracene-framework pyridine-amine binuclear metal titanium-zirconium-hafnium catalyst is obtained by a one-pot reaction of the obtained ligands with in-situ synthesized MMe4 (M = Ti, Zr, or Hf), exhibiting high yield and significant economic benefits. The obtained anthracene-framework pyridine-amine binuclear metal titanium-zirconium-hafnium catalyst is used in the synthesis of polyolefin elastomers. Through the synergistic effect between the binuclear metals and the steric hindrance and electronic effects in the catalyst structure, the molecular weight, α-olefin co-intercalation rate, and monomer regularity of the resulting polymers can be effectively improved to prepare polyolefin elastomers (POE) and ultra-high molecular weight random propylene elastomers (UHMWaPP). The anthracene-skeletal pyridine-amine binuclear titanium-zirconium-hafnium catalyst reported in this invention has the advantages of simple synthesis, readily available raw materials, and high product yield. In the presence of a co-catalyst, the catalyst exhibits excellent activity (9.02 × 10⁻⁶). 7 g(POE)·mol -1 (M)·h -1High molecular weight polyolefin elastomer POE (polymer molecular weight Mw up to 820 kg·mol⁻¹) was prepared by selectively processing α-olefins (insertion rate up to 32.6 mol%). -1 In propylene polymerization, the regularity of polypropylene segments can be effectively controlled by adjusting the steric hindrance and electronic effects of the catalyst, achieving high activity (8.56 × 10⁻⁶). 7 g(PP)·mol -1 (M)·h -1 Preparation of ultra-high molecular weight (molecular weight up to 4560 kg·mol⁻¹) -1 Random polypropylene elastomers. Furthermore, the anthracene-framework pyridineamine-based binuclear titanium-zirconium hafnium metal catalyst reported in this invention also exhibits excellent high-temperature resistance (greater than 160°C), making it suitable for high-temperature solution polymerization and capable of preparing high-performance polyolefin elastomers. As a comparison, the anthracene-framework pyridineamine-based binuclear titanium-zirconium hafnium metal catalyst reported in this invention outperforms the similarly structured pyridineamine-based mononuclear metal catalyst Ar-Hf1 (2,6- i Pr2-phenyl-N-(2- i Pr-phenyl)[6-(naphthalenyl)-2-pyridyl]HfMe2), Me-Hf1(2,6- i Pr2-phenyl-N-methyl[6-(naphthalenyl)-2-pyridyl]HfMe2) and anthracene-skeletal mononuclear hafnium metal mono-Hf1 (N-anthracenyl-1-(6-naphthy-2-pyridineyl)HfMe2) catalysts exhibit better catalytic performance. Therefore, this invention is original and provides a new direction for the development of polyolefin materials. Summary of the Invention

[0008] The purpose of this invention is to provide a method for preparing an anthracene skeleton pyridineamine-based binuclear metal titanium zirconium hafnium catalyst and its application in the synthesis of polyolefin elastomers.

[0009] This invention provides an anthracene skeleton pyridineamine-based binuclear metal titanium zirconium hafnium catalyst of formula (I):

[0010]

[0011] Where M is selected from titanium, zirconium, and hafnium; R 1 -R 4 R 1’ -R 4’ Each is independently selected from hydrogen, C1-C 20 Alkyl, C1-C 20 Alkoxy, C6-C 20 Aryl, C6-C 20Aryl alkyl groups, or phenyl groups, form a ring of 4-20 carbon atoms with surrounding substituents by any two adjacent carbon atoms; R 1’ -R 4’ respectively with R 1 -R 4 Same or different;

[0012] R 5 R 5’ Selected from C1-C6 linear alkyl, tert-butyl, phenyl, benzyl, or isopropylphenyl.

[0013] Preferably, the metal compound of the present invention is selected from any of the metal catalysts shown in (II):

[0014]

[0015] The above-mentioned anthracene skeleton pyridineamine-based binuclear metal titanium zirconium hafnium catalyst is characterized by containing a bifunctional pyridineamine ligand.

[0016] This invention provides a method for preparing the above-mentioned anthracene skeleton pyridineamine-based binuclear metallic titanium zirconium hafnium catalyst, comprising the following steps:

[0017] Under a nitrogen atmosphere, the metal salt was dissolved in 20-80 mL of anhydrous solvent, and 4.0-5.0 molar equivalents of methyl magnesium bromide were added. The reaction was carried out at low temperature for 2 hours under nitrogen protection, followed by the addition of 0.5 molar equivalents of pyridineamine ligand and the reaction was carried out for 5 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the product was extracted with a good solvent to obtain the anthracene skeleton pyridineamine binuclear metal titanium zirconium hafnium catalyst of claim 1.

[0018] In the above preparation method, the anhydrous solvent is selected from toluene, n-hexane, xylene, and benzene; the good solvent is selected from n-hexane, toluene, pentane, heptane, and cyclohexane.

[0019] In the above preparation method, the metal salt MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

[0020] This invention also provides the application of the above-mentioned anthracene skeleton pyridine amino dinuclear metal titanium zirconium hafnium catalyst in catalytic olefin polymerization.

[0021] In the above applications, the olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene, 4-methyl-1-pentene, and 1-octene.

[0022] The aforementioned anthracene-skeletal pyridineamine-based binuclear titanium-zirconium-hafnium catalyst requires a co-catalyst for catalysis. The co-catalyst is one or more of tripentafluorophenylboron, triphenylcarbium tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum, and alkylaluminum chloride. The aluminoxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum chloride, sesqui-diethylaluminum chloride, or ethylaluminum dichloride.

[0023] In the above polymerization reaction, the polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5.0MPa, and the polymerization solvent is one or more of n-hexane, heptane, pentane, and toluene.

[0024] This invention provides the preparation of anthracene-skeletal pyridineamine-based binuclear titanium-zirconium-hafnium catalyst and its application in catalyzing the polymerization of olefins to synthesize elastomers. The anthracene-skeletal pyridineamine-based binuclear titanium-zirconium-hafnium catalyst reported in this invention features simple synthesis, readily available raw materials, and high product yield. It exhibits high catalytic activity in the copolymerization of ethylene and α-olefins (with an activity reaching up to 9.02 × 10⁻⁶). 7 ·mol -1 ·h -1 It also exhibits better copolymerization properties (1-octene insertion rate up to 32.6 mol%); in propylene polymerization, efficient polymerization can be achieved by controlling the steric hindrance of different substituents (the highest activity can reach 8.56 × 10⁻⁶). 7 g·mol -1 ·h -1 Synthesized with ultra-high molecular weight (polymer molecular weight reaches 4560 kg·mol⁻¹) -1 This invention relates to a random polypropylene elastomer; particularly in high-temperature solution polymerization, the catalyst maintains excellent polymerization performance for the preparation of high-quality, high-performance polyolefin materials. The metal catalyst provided by this invention is original and innovative, and can promote the development of my country's high-end polyolefin chemical industry. Attached Figure Description

[0025] Figure 1 This is the 1H NMR spectrum of catalyst C1.

[0026] Figure 2 This is the 1H NMR spectrum of catalyst C2.

[0027] Figure 3 This is the 1H NMR spectrum of catalyst C3.

[0028] Figure 4 This is the 1H NMR spectrum of catalyst C4.

[0029] Figure 5 The image shows the carbon NMR spectrum of a polyolefin elastomer with a 1-octene insertion rate of 4.9%.

[0030] Figure 6 The POE carbon NMR spectrum of a polyolefin elastomer with a 1-octene insertion rate of 12.7%.

[0031] Figure 7 The image shows the carbon NMR spectrum of a polyolefin elastomer with a 1-octene insertion rate of 32.6%.

[0032] Figure 8 With a molecular weight of 4560 kg·mol -1 GPC spectrum of ultra-high molecular weight random polypropylene elastomer.

[0033] Figure 9 The molecular weight is 3890 kg·mol -1 GPC spectrum of ultra-high molecular weight random polypropylene elastomer.

[0034] Figure 10 The image shows the carbon NMR spectrum of an ultra-high molecular weight atactic polypropylene elastomer with a stereoregularity of 9.8 mm.

[0035] Figure 11 The image shows the carbon NMR spectrum of an ultra-high molecular weight atactic polypropylene elastomer with a stereoregularity of 18.8 mm.

[0036] Figure 12 This is a stress-strain tensile curve of ultra-high molecular weight random polypropylene elastomer.

[0037] Figure 13 The tensile cycle curve of the elastic recovery experiment of ultra-high molecular weight random polypropylene elastomer is shown.

[0038] Figure 14 This is a crystal diagram of catalyst C2. Detailed Implementation

[0039] The present invention is further illustrated by examples, but is not limited thereto. These examples will enable those skilled in the art to gain a more comprehensive understanding of the invention.

[0040] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0041] The anthracene skeleton bifunctional pyridine amino ligands C1-L, C2-L, and C3-L in this invention are shown in (III), and the corresponding synthesis methods are given in Examples 1, 2, and 3. The pyridineamine-based mononuclear metal hafnium catalysts used for control experiments, as shown in (IV), were synthesized using the Ar-Hf1 catalyst (2,6-iPr2-phenyl-N-(2-iPr-phenyl)[6-(naphthalenyl)-2-pyridyl]HfMe2) according to the literature (Angew. Chem., Int. Ed. 2006, 45, 3278-3283). The corresponding synthetic methods for Me-Hf1 (2,6-iPr2-phenyl-N-methyl[6-(naphthalenyl)-2-pyridyl]HfMe2) and the anthracene-based mononuclear hafnium metal mono-Hf1 (N-anthracenyl-1-(6-naphthy-2-pyridineyl)HfMe2) are given in Examples 5 and 6.

[0042]

[0043] The present invention is described below with reference to specific embodiments.

[0044] Example 1: Preparation of Catalyst C1

[0045] Weigh 0.208 g / 1 mmol of 1,8-diaminoanthracene and 2 equivalents of 6-phenyl-2-pyridinaldehyde (0.366 g / 2 mmol) into a round-bottom flask, add 20 mL of anhydrous ethanol, add 2 mg of p-toluenesulfonic acid as a catalyst, and react at room temperature for 4 hours to obtain a yellow suspension. Filter the suspension and wash with a small amount of ice-cold ethanol to obtain 0.482 g of orange-yellow ligand C1-L, with a yield of 90%. 1 H NMR (400MHz, CDCl3): δ8.72(s,2H),8.49(t,J=2.1Hz,1H),8.44(s,1H),8.12–8.06(m,4H),7.92(dt,J=6.2, 2.2Hz, 2H), 7.70 (dd, J=14.3, 7.0, 1.3Hz, 4H), 7.59 (t, J=7.1Hz, 2H), 7.53–7.46 (m, 8H), 7.49–7.38 (m, 2H). 13C NMR (125MHz, Common NMR Solvents)δ160.04,158.59,155.37,148.60,138.72,137.62,134.20,130.09,128.90 ,127.77,127.75,127.67,125.59,124.59,122.74,122.68,122.36,120.93ppm.Calcd for C 38 H 26 N4:C,84.73;H,4.87;N,10.40.Found:C,84.65;H,4.32;N,10.71.

[0046] Weigh 0.352 g (1.1 mmol) of hafnium tetrachloride (HfCl4) and add 10 mL of anhydrous toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), slowly add 1.6 mL / 4.8 mmol of methyl magnesium bromide solution (3 M) and stir for 2 hours. Then add ligand C1-L (0.285 g / 0.5 mmol) and react at -40 °C in the dark for 2 hours, then continue the reaction at room temperature for 5 hours. After the reaction is complete, remove the solvent, extract with toluene, and filter to obtain 0.37 g of product C1, with a yield of 75%. 1 H NMR (400MHz, C6D6): δ8.21(d,J=2.2Hz,1H),8.20(d,J=2.1Hz,2H),7.92(dd,J=8.8,1.5Hz,2H),7.86(dt,J=7.8,1.7Hz,2H),7.47(d ,J=7.5Hz,2H),7.41–7.31(m,10H),7.18(dd,J=8.6,7.0,1.5Hz,2H),6.72(s,2H),4.9(q,2H),1.56(d,J=8.4Hz,6H),2.33(s,12H). 13 C NMR (100MHz, C6D6) δ159.46,152.68,150.22,144.28,136.93,132.67,131.85,130.67,130.37,127.90,127.61,126.84 ,125.91,125.07,124.45,124.00,123.80,121.40,119.22,56.49,56.43,19.51,17.29,17.27,17.25,17.22ppm.Calcd for C 44 H 42Hf2N4:C,53.72;H,4.30;N,5.69.Found:C,53.78;H,4.32;N,5.71.

[0047] Example 2: Preparation of catalyst C2

[0048] Weigh 0.208 g / 1 mmol of 1,8-diaminoanthracene and 2 equivalents of 6-naphthyl-2-pyridinaldehyde (0.470 / 2 mmol) into a round-bottom flask, add 20 mL of anhydrous ethanol, add 2 mg of p-toluenesulfonic acid as a catalyst, and react at room temperature for 4 hours to obtain a yellow suspension. Filter the suspension and wash with a small amount of ice-cold ethanol to obtain 0.556 g of the orange-yellow product C2-L, with a yield of 87%. 1 H NMR (400MHz, CDCl3): δ9.64(s,1H),8.97(s,2H),8.66(d,J=7.9Hz,2H),8.48(s,1H),8.16(d,J=9.4Hz,2H ),8.04–7.90(m,8H),7.78–7.68(m,4H),7.65–7.57(m,2H),7.56–7.48(m,6H),7.21(d,J=6.2Hz,2H)ppm. 13 C NMR (100MHz, CDCl3): δ160.95,159.51,155.15,148.74,138.03,136.98,134.14,132.60,131.26,129.35,128.58,127.8 8,127.71,126.95,126.77,126.66,126.17,126.02,125.96,125.62,125.50,120.16,119.72,111.63ppm.Anal.Calcdfor C 46 H 30 N4:C,85.30;H,4.93;N,8.56.Found:C,85.10;H,4.63;N,8.67.

[0049] Weigh 0.352 g (1.1 mmol) of hafnium tetrachloride (HfCl4) and add 10 mL of dry toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), slowly add 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) and stir for 2 hours. Then add ligand C2-L (0.335 g / 0.5 mmol), and stir in the dark at -40 °C for two hours. After returning to room temperature, continue the reaction for 5 hours. After the reaction is complete, remove the solvent, extract with toluene, filter, and give product C2 0.37 g, yield 70%. 1H NMR (400MHz, C6D6): δ8.82(s,1H),8.43(d,J=7.6Hz,2H),8.37(s,1H),8.06(d,J =8.0Hz,2H),7.85(d,J=17.Hz,2H),7.81(d,J=8.1Hz,4H),7.56(d,J=6.7Hz,2H), 7.40–7.28(m,6H),7.04(d,J=8.0Hz,2H),6.24(d,J=7.6Hz,2H),6.04(t,J=7.8Hz ,2H),5.46(q,J=6.6Hz,2H),0.90(d,J=6.6Hz,6H),0.80(s,6H),0.27(s,6H)ppm. 13 C NMR (100MHz, C6D6): δ205.91,170.96,164.12,144.21,144.05,140.40,135.69,134.55,133.61,130.49,130.06,129.65,129.33 ,129.31,127.08,126.51,126.14,125.85,125.68,124.24,120.27,120.06,118.70,70.18,63.01,60.15,25.23ppm.Anal.Calcd for C 52 H 46 Hf2N4:C,57.62;H,4.28;N,5.17.Found:C,57.59;H,4.31;N,5.22.

[0050] Example 3: Preparation of catalyst C3

[0051] Weigh 0.256 g (1.1 mmol) of zirconium tetrachloride (ZrCl4) and add 10 mL of dry toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), slowly add 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) and stir for 2 hours. Then add ligand C2-L (0.335 g / 0.5 mmol), and stir in the dark at -40 °C for 2 hours. After returning to room temperature, continue the reaction for 5 hours. After the reaction is complete, remove the solvent, extract with toluene, and filter to obtain product C3 0.327 g, yield 72%. 1H NMR (400MHz, C6D6): δ8.85 (s, 1H), 8.48 (d, J = 7.6Hz, 2H), 8.35 (s, 1H), 8.1 0(d,J=6.8Hz,2H),7.81–7.75(m,6H),7.60(d,J=6.7Hz,2H),7.39–7.30(m ,6H),7.08(d,J=8.0Hz,2H),6.21(d,J=7.7Hz,2H),6.07(t,J=7.8Hz,2H), 5.38(q,J=6.6Hz,2H),1.00(d,J=6.2Hz,6H),0.43(s,6H),0.30(s,6H)ppm. 13 C NMR (100MHz, C6D6): δ192.40,170.49,164.11,143.77,142.68,140.34,135.81,134.52,132.91,130.05,129.84,129.43,129.34 ,128.89,127.00,126.86,126.15,125.74,125.65,124.27,120.47,119.93,118.71,70.19,49.49,46.06,24.76ppm.Anal.Calcd forC 52 H 46 Zr2N4:C,68.68;H,5.10;N,6.16.Found:C,68.54;H,4.80;N,6.06.

[0052] Example 4: Preparation of Catalyst C4

[0053] Weigh out 0.638 g / 1 mmol of the corresponding C2-L ligand, purge with nitrogen three times under vacuum, add 20 mL of anhydrous diethyl ether, and slowly add a solution of 3 equivalents of 2-isopropylphenyl lithium salt (0.378 g / 3 mmol) in diethyl ether under a nitrogen atmosphere. Stir at room temperature for 2 h. Quench with 1 M NH4Cl aqueous solution, extract with ethyl acetate and water, collect the upper organic layer, dry, and remove the solvent under low pressure to obtain 0.668 g of yellow solid product C4-L, yield 76%. 1H NMR (4400MHz, CDCl3) δ8.32 (s, 1H), 8.24 (t, J = 2.2Hz, 1H), 8.06–7.95 (m, 6H), 7. 81–7.76(m,2H),7.75–7.68(m,4H),7.64–7.49(m,12H),7.36–7.15(m,8H),7.09 –7.04(m,2H),6.52–6.48(m,1H),6.41(dd,J=7.9,0.7Hz,1H),5.89(d,J=7.9Hz, 2H), 3.16 (hept, J=6.7, 0.6Hz, 2H), 1.28 (d, J=6.7Hz, 6H), 1.23 (d, J=6.7Hz, 6H). 13 C NMR (100MHz, CDCl3) δ162.62,156.95,147.30,143.52,137.95,137.03,134. 25,133.53,132.39,131.19,128.93,128.82,128.61,128.32,127.72,127.71 ,127.50,127.30,127.10,126.76,126.18,126.12,125.30,123.67,123.54, 122.70,122.14,118.66,113.40,61.73,61.72,29.58,23.51ppm.Anal.Calcd for C 64 H 54 N4:C,87.44;H,6.19;N,6.37.Found:C,87.44;H,6.18;N,6.26.

[0054] Weigh 0.352 g (1.1 mmol) of hafnium tetrachloride (HfCl4) and add 10 mL of dry toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), slowly add 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) and stir for 2 hours. Then add ligand C4-L (0.440 g / 0.5 mmol), and stir in the dark at -40 °C for two hours. After returning to room temperature, continue the reaction for 5 hours. After the reaction is complete, remove the solvent, extract with toluene, filter, and give 0.413 g of product C4, yield 64%. 1H NMR(400MHz,C6D6)δ8.30(d,J=0.9Hz,1H),8.22–8.15(m,3H),8.10–8.04(m,2H),8 .02–7.94(m,4H),7.89–7.83(m,2H),7.68(d,J=9.3Hz,2H),7.55–7.39(m,10H),7. 33(dd,J=7.1,1.5Hz,2H),7.30–7.15(m,8H),6.63(s,2H),3.21(dd,J=13.3,6.7,0 .6Hz,2H),1.28(d,J=6.7Hz,6H),1.23(d,J=6.6Hz,6H),0.57(s,6H),0.34(s,6H). 13 C NMR(100MHz,C6D6)δ157.77,151.97,148.60,146.07,146.03,144.35,138.97,137.32 ,136.32,132.45,132.42,131.80,129.57,129.56,129.49,128.09,127.90,127.57,1 27.48,127.23,127.22,127.14,127.10,127.09,126.17,125.00,124.97,123.85,122 .16,121.86,119.22,60.69,29.36,23.51,17.36,17.34,17.32,17.29ppm.Anal.Calcd for C 68 H 62 Hf2N4:C,63.20;H,4.84;N,4.34.Found:C,62.24;H,4.80;N,4.33.

[0055] Example 5: Preparation of catalyst Me-Hf1

[0056] Weigh 0.885 g / 5 mmol of 2,6-diisopropylaniline, 1.29 g / 5.5 mmol of 6-naphthyl-2-pyridinaldehyde, and 2 mg of p-toluenesulfonic acid into a round-bottom flask. Add 100 mL of anhydrous ethanol and stir at room temperature for 6 hours to obtain a yellow suspension. Filter and wash with ice-cold ethanol to give 1.80 g of a bright yellow solid product, yield 92%. 1H NMR (400MHz, CDCl3) δ8.69(s,1H),8.06–7.98(m,2H),7.98–7.95(m,1H),7.83(dd,J=7.1,1.3Hz,1H),7.79(d,J=8.5Hz,1H),7.76–7 .71(m,1H),7.64–7.49(m,4H),7.26(dd,J=8.1,6.4Hz,1H),7.20(dd,J=7.3,0.9Hz,2H),3.16–3.02(m,2H),1.27(d,J=6.2Hz,12H). 13 C NMR (100MHz, CDCl3) δ160.12,158.16,156.27,146.83,138.51,138.15,134.00,133.40,132.37,128.93,128 .60,128.35,128.32,127.10,126.95,126.13,125.46,125.20,124.51,122.12,29.59,22.04ppm.Anal.Calcd for C 28 H 28 N2:C,85.67;H,7.19;N,7.14.Found:C,85.47;H,7.04;N,7.33.

[0057] Hafnium tetrachloride (HfCl4) (0.352 g, 1.1 mmol) was weighed and added to 10 mL of dry toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) was slowly added, and the mixture was stirred for 2 hours. Then, the aforementioned ligand (0.392 g / 1 mmol) was added, and the mixture was stirred in the dark at -40 °C for two hours. After returning to room temperature, the reaction was continued for 5 hours. After the reaction was complete, the solvent was removed under low pressure, and the mixture was extracted with toluene. The extract was filtered to obtain 0.455 g of product Me-Hf1, with a yield of 74%. 1H NMR (400MHz, C6D6): δ8.53(d,J=7.6Hz,1H),8.29(d,J=8.4Hz,1H),7.78(d,J=7.6Hz,1H),7.71(d,J=8.1 Hz,1H),7.52(d,J=8.0Hz,1H),7.35–7.19(m,5H),6.96(t,J=7.9Hz,1H),6.46(d,J=7.8Hz,1H),4.92(q,J =6.8Hz,1H),4.36(hept,J=6.8Hz,1H),3.12(hept,J=6.8Hz,1H),1.56(d,J=6.8Hz,3H),1.39(d,J=6.8H z,3H),1.34(d,J=6.7Hz,3H),1.22(d,J=6.8Hz,3H),1.13(d,J=6.8Hz,3H),0.79(s,3H),0.64(s,3H)ppm. 13 C NMR (100MHz, C6D6): δ206.23,171.17,164.97,147.29,146.75,145.47,143.82,140.74,135.72,134.29,130.70,130.00,129.77,126.90,126 .46,125.47,125.40,124.46,124.11,120.40,117.76,73.15,66.20,62.78,28.62,27.65,27.49,26.56,25.30,25.27,24.90ppm.Anal.Calcd for C 31 H 36 HfN2:C,60.53;H,5.90;N,4.55.Found:C,60.65;H,5.93;N,4.52.

[0058] Example 6: Preparation of catalyst mono-Hf1

[0059] Weigh 0.386 g / 2 mmol of 1-aminoanthracene, 0.47 g / 2 mmol of 6-naphthyl-2-pyridinaldehyde, and 2 mg of p-toluenesulfonic acid into a round-bottom flask. Add 100 mL of anhydrous ethanol and stir at room temperature for 6 hours to obtain a yellow suspension. Filter and wash with ice-cold ethanol to obtain 0.68 g of yellow solid ligand, yield 84%. 1H NMR (400MHz, CDCl3): δ8.99(s,1H),8.93(s,1H),8.61(d,J=7.8Hz,1H),8.46(s,1H),8.16(d,J=7.3Hz,1H),8.09(dd,J=8.6,4.4Hz,2H),8.04(dd,J =9.0,5.1Hz,1H),7.98–7.91(m,3H),7.74(d,J=7.3Hz,1H),7.72(d,7.3Hz ,1H),7.61(t,J=7.6Hz,1H),7.57–7.43(m,5H),7.15(d,J=7.0Hz,1H)ppm. 13 CNMR (100MHz, CDCl3): δ161.29,159.52,154.86,148.69,138.10,137.34,134.17,132.27,132.15,131.79,131.30,129.35,128.88,128.59,128 .18,127.93,127.73,127.10,126.81,126.77,126.26,126.17,125.84,1 25.67,125.62,125.57,125.52,122.95,120.39,111.73ppm.Anal.Calcd for C 30 H 20 N2:C,87.55;H,5.03;N,6.77.Found:C,87.32;H,4.85;N,6.71.

[0060] Hafnium tetrachloride (HfCl4) (0.352 g, 1.1 mmol) was weighed and added to 10 mL of dry toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) was slowly added, and the mixture was stirred for 2 hours. Then, the aforementioned ligand (0.408 g / 1 mmol) was added, and the mixture was stirred in the dark at -40 °C for two hours. After returning to room temperature, the reaction was continued for 5 hours. After the reaction was complete, the solvent was removed under low pressure, and the mixture was extracted with toluene. The extract was filtered to obtain 0.485 g of the product mono-Hf1, with a yield of 77%. 1H NMR (400MHz, C6D6): δ8.83(s,1H),8.49(d,J=7.6Hz,1H),8.35(d,J=8.5Hz,1H),8.30(s,1 H),7.86–7.75(m,3H),7.72–7.65(m,3H),7.60(d,J=8.0Hz,1H),7.44–7.34(m,2H),7.32–7 .28(m,1H),7.27(dd,J=6.5,1.2Hz,1H),7.25–7.21(m,1H),6.99(t,J=7.9Hz,1H),6.45(d ,J=7.7Hz,1H),5.63(q,J=6.3Hz,1H),1.12(d,J=6.6Hz,3H),0.88(s,3H),0.36(s,3H)ppm. 13 C NMR (100MHz, C6D6): δ206.23,171.95,166.17,144.91,140.58,135.82,134.42,133.75,132.28,132.14,130.66,130.09,129 .89,129.01,126.97,126.85,125.98,125.72,125.61,125.50,124.16,123.65,120.46,118.59,63.58,24.77ppm.Anal.Calcd for C 33 H 28 HfN2:C,62.81;H,4.47;N,4.44.Found:C,62.75;H,4.51;N,4.52.

[0061] Example 7: C1-catalyzed propylene polymerization

[0062] A 350 mL glass reactor equipped with a magnetic induction valve was used for the polymerization reaction. 2 μmol of catalyst C1, 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization line. Once the temperature reached 80 °C, 50 mL of toluene was added. Propylene gas was continuously introduced during polymerization to maintain a reaction pressure of 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 to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 90200 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 2730 kg·mol -1Mw / Mn = 2.0, mmmm% = 16.9%, fracture stress is 3.4 MPa, elongation at break is 1830%, and elastic recovery rate is 91%.

[0063] Example 8: C1-catalyzed propylene polymerization

[0064] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 120°C. Polymerization activity: 62300 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 2610 kg·mol -1 Mw / Mn = 2.2, mmmm% = 15.9%, fracture stress is 3.8 MPa, elongation at break is 1900%, and elastic recovery rate is 89%.

[0065] Example 9: C1-catalyzed propylene polymerization

[0066] A 100 mL steel reactor equipped with a magnetic inductor was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 160 °C. The reactor was saturated with propylene gas at 1 MPa. In a glove box, 2 μmol of catalyst C1, 100 μmol of methylaluminoxane, and 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube using a syringe. Nitrogen gas (above 1 MPa) was introduced into the reactor, and the reaction pressure was maintained at 1 MPa by continuously introducing propylene gas during polymerization. After the set reaction time of 2 minutes, 2 mL of ethanol was introduced into the reactor under nitrogen gas (above 1 MPa). The reactor was cooled and vented. The contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 50-200 kg·mol⁻¹ 1 (Hf)·h -1 Polymer Mw = 3380 kg·mol -1 , Mw / Mn=2.2, mmmm%=18.9%, T g = -8℃, fracture stress is 3.65MPa, fracture elongation is 2100%, elastic recovery rate is 87%.

[0067] Example 10: C1-catalyzed propylene polymerization

[0068] The polymerization process and conditions were the same as in Example 9, with a polymerization temperature of 180°C. Polymerization activity: 31090 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 3350 kg·mol -1 , Mw / Mn=2.0, mmmm%=17%, T g= -8℃, fracture stress is 3.92MPa, fracture elongation is 1940%, elastic recovery rate is 89%.

[0069] Example 11: C1-catalyzed propylene polymerization

[0070] A 350 mL glass reactor equipped with a magnetic induction chamber was used for the polymerization reaction. 2 μmol of catalyst C1, 2.2 μmol of trifluorophenylborate, and methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization pipeline. Once the temperature reached 80 °C, 50 mL of toluene was added. Propylene gas was continuously introduced during polymerization to maintain a reaction pressure of 5 atm. After reacting for 10 min, 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 to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 700 × 10⁻⁶ kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 3750 kg·mol -1 , Mw / Mn=2.0, mmmm%=18.8%, T g At -10℃, the fracture stress is 3.75MPa, the elongation at break is 1850%, and the elastic recovery rate is 92%.

[0071] Example 12: C1-catalyzed propylene polymerization

[0072] A 350 mL glass reactor equipped with a magnetic stir bar 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 pipeline. Once the temperature reached 120 °C, 50 mL of toluene was added. Propylene gas was continuously introduced during polymerization to maintain a reaction pressure of 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 to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 203 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 1300 kg·mol -1 , Mw / Mn=2.2, mmmm%=8.9%, T g At -10℃, the fracture stress is 1.95MPa, the elongation at break is 1160%, and the elastic recovery rate is 74.5%.

[0073] Example 13: C2-catalyzed propylene polymerization

[0074] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was C2. Polymerization activity: 72500 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 2800 kg·mol-1 , Mw / Mn=2.0, mmmm%=14.9%, T g = -9℃, fracture stress is 3.25MPa, fracture elongation is 1690%, elastic recovery rate is 83%.

[0075] Example 14: C3-catalyzed propylene polymerization

[0076] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was C3. Polymerization activity: 85100 kg·mol⁻¹ -1 (Zr)·h -1 Polymer Mw = 10¹⁰ kg·mol⁻¹ -1 , Mw / Mn=2.1, mmmm%=10.9%, T g = -9℃, fracture stress is 2.65MPa, fracture elongation is 1290%, elastic recovery rate is 75%.

[0077] Example 15: C4-catalyzed propylene polymerization

[0078] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was C4. Polymerization activity: 10520 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 4650 kg·mol -1 , Mw / Mn=2.1, mmmm%=9.8%, T g = -8℃, fracture stress is 4.77MPa, fracture elongation is 290%, elastic recovery rate is 92%.

[0079] Example 16: Ar-Hf1 catalyzed propylene copolymerization

[0080] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was Ar-Hf1. Polymerization activity: 35750 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 360 kg·mol -1 , Mw / Mn=1.9, mmmm%=94%, T m =153℃, fracture stress is 36.5MPa, fracture elongation is 120%, elastic recovery rate is 5%.

[0081] Example 17: Me-Hf1-catalyzed propylene copolymerization

[0082] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was Me-Hf1. Polymerization activity: 22450 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 320 kg·mol -1,Mw / Mn=17,,mmmm%=79%,T g = -9℃, T m =132℃, fracture stress is 28.5MPa, fracture elongation is 1100%, elastic recoverability is 14.5%.

[0083] Example 18: Mono-Hf1 Catalyzed Propylene Copolymerization

[0084] The polymerization process and reaction conditions were the same as in Example 8, and the catalyst used was mono-Hf1. Polymerization activity: 3450 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 190 kg·mol -1 , Mw / Mn=2.0, mmmm%=8.9%, T g = -9℃, fracture stress is 1.8MPa, elongation at break is 650%, elastic recovery rate is 75%.

[0085] Example 19: C2-catalyzed ethylene polymerization

[0086] A 350 mL glass reactor equipped with a magnetic induction chamber was used for the polymerization reaction. 2 μmol of catalyst C2, 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization pipeline. Once the temperature reached 80 °C, 50 mL of toluene was added. Ethylene gas was continuously introduced during polymerization to maintain a reaction pressure of 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 to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 8500 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 503 kg·mol -1 Mw / Mn = 2.0.

[0087] Example 20: C2-catalyzed ethylene polymerization

[0088] The polymerization process and conditions were the same as in Example 19, with a polymerization temperature of 120°C. Polymerization activity: 6230 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 361 kg·mol -1 Mw / Mn = 2.2.

[0089] Implementing 21, C2 catalytic ethylene polymerization

[0090] A 100 mL steel reactor equipped with a magnetic induction device was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 160 °C. The reactor was saturated with 1 MPa of ethylene. In a glove box, 2 μmol of catalyst C2, 100 μmol of methylaluminoxane, and 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube using a syringe. Nitrogen gas (above 1 MPa) was introduced into the reactor, and the reaction pressure was maintained at 1 MPa by continuously introducing ethylene gas during polymerization. After the set reaction time of 2 minutes, 2 mL of ethanol was injected into the reactor under nitrogen (above 1 MPa). The reactor was cooled and vented. The contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 16200 kg·mol⁻¹ 1 (Hf)·h -1 Polymer Mw = 338 kg·mol -1 Mw / Mn = 2.2.

[0091] Example 22: C2-catalyzed ethylene polymerization

[0092] The polymerization process and conditions were the same as in Example 21, with a polymerization temperature of 180°C. Polymerization activity: 10390 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 235 kg·mol -1 Mw / Mn = 2.3.

[0093] Example 23: C2-catalyzed ethylene polymerization

[0094] A 350 mL glass reactor equipped with a magnetic induction chamber was used for the polymerization reaction. 2 μmol of catalyst C2, 2.2 μmol of trifluorophenylborate, and methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization pipeline. Once the temperature reached 120 °C, 50 mL of toluene was added. Ethylene gas was continuously introduced during polymerization to maintain a reaction pressure of 5 atm. After reacting for 10 min, 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 to settle. The mixture was then filtered and dried to obtain the final polymer. Polymerization activity: 9881 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 632 kg·mol -1 Mw / Mn = 2.2.

[0095] Example 24: C2-catalyzed ethylene polymerization

[0096] A 350 mL glass reactor equipped with a magnetic induction chamber was used for the polymerization reaction. 2 μmol of catalyst C2 and 1000 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was connected to the polymerization pipeline. Once the temperature reached 120 °C, 50 mL of toluene was added. Ethylene gas was continuously introduced during polymerization to maintain a reaction pressure of 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 to settle. The final polymer was obtained after filtration and drying. Polymerization activity: 3250 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 230 kg·mol -1 Mw / Mn = 2.4.

[0097] Example 25: C1-catalyzed ethylene polymerization

[0098] The polymerization process and reaction conditions were the same as in Example 24, and the catalyst used was C1. Polymerization activity: 7250 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 280 kg·mol -1 Mw / Mn = 2.0.

[0099] Example 26: C3-catalyzed ethylene polymerization

[0100] The polymerization process and reaction conditions were the same as in Example 24, and the catalyst used was C3. Polymerization activity: 8510 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 485 kg·mol -1 Mw / Mn = 2.1.

[0101] Example 27: C4-catalyzed ethylene polymerization

[0102] The polymerization process and reaction conditions were the same as in Example 24, and the catalyst used was C4. Polymerization activity: 10520 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 561 kg·mol -1 Mw / Mn = 2.1.

[0103] Example 28: C3-catalyzed copolymerization of ethylene / 1-octene

[0104] A 350 mL glass reactor equipped with a magnetic induction chamber was used for the polymerization reaction. 2 μmol of catalyst C3, 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was then connected to the polymerization line. Once the temperature reached 120 °C, 26.6 mL of toluene and 23.4 mL of 1-octene were added. Ethylene gas was continuously introduced during polymerization to maintain a reaction pressure of 5 atm. After 2 minutes of reaction, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large volume of ethanol to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 59700 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 668 kg·mol -1 Mw / Mn = 2.0, and the copolymer contains 32.6 mol% 1-octene.

[0105] Example 29: C3-catalyzed copolymerization of ethylene / 1-octene

[0106] The polymerization process and conditions were the same as in Example 28, using 34.4 mL of toluene and 15.6 mL of 1-octene. Polymerization activity: 54250 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 455 kg·mol -1 Mw / Mn = 2.1, and the content of 1-octene in the copolymer is 23.7 mol%.

[0107] Example 30: C3-catalyzed copolymerization of ethylene / 1-octene

[0108] The polymerization process and reaction conditions were the same as in Example 28, using 42.2 mL of toluene and 7.8 mL of 1-octene. Polymerization activity: 52500 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 345 kg·mol -1 Mw / Mn = 2.2, and the copolymer contains 16.6 mol% 1-octene.

[0109] Example 31: C3-catalyzed copolymerization of ethylene / 1-octene

[0110] A 100 mL steel reactor equipped with a magnetic inductor was used for the polymerization reaction. A mixture of 26.6 mL toluene and 23.4 mL 1-octene (total 50 mL) was injected using a syringe. The reactor contents were heated to 120 °C, and the reactor was saturated with ethylene at 1 MPa. In a glove box, 2 μmol of catalyst C3, 100 μmol of methylaluminoxane, and 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube via a syringe. Nitrogen gas (above 1 MPa) was then pressurized into the reactor. During polymerization, the reaction pressure was maintained at 1 MPa by continuously introducing ethylene gas. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 1 MPa). After the reactor cooled and the atmosphere was vented, the contents were poured into a large volume of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 74920 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 630 kg·mol -1 Mw / Mn = 2.1, and the copolymer contains 21.5 mol% 1-octene.

[0111] Example 32: C3-catalyzed copolymerization of ethylene / 1-octene

[0112] The polymerization process and conditions were the same as in Example 31, with a polymerization pressure of 2 MPa. Polymerization activity: 82600 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 690 kg·mol -1 Mw / Mn = 2.1, and the copolymer contains 15.0 mol% 1-octene.

[0113] Example 33: C3-catalyzed copolymerization of ethylene / 1-octene

[0114] The polymerization process and conditions were the same as in Example 31, with a polymerization pressure of 3 MPa. Polymerization activity: 85600 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 708 kg·mol -1 Mw / Mn = 2.0, and the copolymer contains 12.7 mol% 1-octene.

[0115] Example 34: C3-catalyzed copolymerization of ethylene / 1-octene

[0116] The polymerization process and reaction conditions were the same as in Example 31, with the selected temperature being 140℃. Polymerization activity: 26550 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 600 kg·mol-1 Mw / Mn = 2.2, and the content of 1-octene in the copolymer is 22.0 mol%.

[0117] Example 35: C3-catalyzed copolymerization of ethylene / 1-octene

[0118] The polymerization process and reaction conditions were the same as in Example 31, with the selected temperature being 160℃. Polymerization activity: 22450 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 550 kg·mol -1 Mw / Mn = 2.3, and the copolymer contains 21.3 mol% 1-octene.

[0119] Example 36: C1-catalyzed copolymerization of ethylene / 1-octene

[0120] The polymerization process and reaction conditions were the same as in Example 31, and the catalyst used was C1. Polymerization activity: 81400 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 608 kg·mol -1 Mw / Mn = 2.1, and the content of 1-octene in the copolymer is 22.6 mol%.

[0121] Example 37: C2-catalyzed copolymerization of ethylene / 1-octene

[0122] The polymerization process and reaction conditions were the same as in Example 31, and the catalyst used was C2. Polymerization activity: 76400 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 485 kg·mol -1 Mw / Mn = 2.4, and the copolymer contains 21.4 mol% 1-octene.

[0123] Example 38: C4-catalyzed copolymerization of ethylene / 1-octene

[0124] The polymerization process and reaction conditions were the same as in Example 31, and the catalyst used was C4. Polymerization activity: 15050 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 652 kg·mol -1 Mw / Mn = 2.3, and the copolymer contains 15.5 mol% 1-octene.

[0125] Example 39: C3-catalyzed copolymerization of ethylene / 1-hexene

[0126] A 350 mL glass reactor equipped with a magnetic induction valve was used for the polymerization reaction. 2 μmol of catalyst C3, 2.2 μmol of triphenylcarbontetra(pentafluorophenyl)borate, and 100 μmol of methylaluminoxane were weighed in a glove box. The glass reactor was then connected to the polymerization line. Once the temperature reached 120 °C, 31.6 mL of toluene and 18.4 mL of 1-hexene were added. Ethylene gas was continuously introduced during polymerization to maintain a reaction pressure of 5 atm. After 2 minutes of reaction, 30 mL of ethanol was added to the reactor under a nitrogen atmosphere. After cooling, the reaction solution was poured into a large volume of ethanol to settle, filtered, and dried to obtain the final polymer. Polymerization activity: 40510 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 490 kg·mol -1 Mw / Mn = 1.8, the copolymer contains 28.0 mol% 1-hexene.

[0127] Example 40: Ar-Hf1-catalyzed copolymerization of ethylene / 1-hexene

[0128] The polymerization process and reaction conditions were the same as in Example 39, and the catalyst used was Ar-Hf1. Polymerization activity: 54520 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 380 kg·mol -1 Mw / Mn = 2.2, and the content of 1-hexene in the copolymer is 27.6 mol%.

[0129] Example 41: Me-Hf1-catalyzed copolymerization of ethylene / 1-hexene

[0130] The polymerization process and reaction conditions were the same as in Example 39, and the catalyst used was Me-Hf1. Polymerization activity: 42130 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 290 kg·mol -1 Mw / Mn = 2.7, and the content of 1-hexene in the copolymer is 25.3 mol%.

[0131] Example 42: Mono-Hf1-catalyzed copolymerization of ethylene / 1-hexene

[0132] The polymerization process and reaction conditions were the same as in Example 39, and the catalyst used was mono-Hf1. Polymerization activity: 3250 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 230 kg·mol -1 Mw / Mn = 2.7, and the content of 1-hexene in the copolymer is 4.9 mol%.

Claims

1. A class of anthracene-skeletal pyridine-amine binuclear metallic titanium-zirconium-hafnium catalysts, the structure of which is shown in formula (I): in, M is selected from titanium, zirconium, and hafnium; R 1 -R 4 R 1’ -R 4’ Each is independently selected from hydrogen, C1-C 20 Alkyl, C1-C 20 Alkoxy; R 1’ -R 4’ respectively with R 1 -R 4 Same or different; R 5 R 5’ Selected from C1-C6 straight-chain alkyl or tert-butyl groups.

2. A class of anthracene-skeletal pyridine-amine binuclear metallic titanium-zirconium-hafnium catalysts, the structure of which is shown in formula (II):

3. The preparation method of the anthracene skeleton pyridineamine-based binuclear metallic titanium zirconium hafnium catalyst according to claims 1 and 2 comprises the following steps: under a nitrogen atmosphere, dissolving the metal salt in 20-80 mL of anhydrous solvent, adding 4.0-5.0 molar equivalents of methyl magnesium bromide, reacting at low temperature for 2 hours under nitrogen protection, and then adding 0.5 molar equivalents of pyridineamine ligand and reacting for 5 hours; after the reaction is completed, removing the solvent under reduced pressure, extracting with a good solvent, and obtaining the anthracene skeleton pyridineamine-based binuclear metallic titanium zirconium hafnium catalyst according to claims 1 and 2.

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

5. The preparation method according to claim 3, characterized in that: The metal salt MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

6. A method for olefin polymerization, characterized in that: The catalyst used is the anthracene skeleton pyridineamine-based binuclear metal titanium zirconium hafnium catalyst as described in claims 1 and 2.

7. The method according to claim 6, characterized in that: The olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene, 4-methyl-1-pentene, and 1-octene.

8. The method according to claim 6, characterized in that: The anthracene skeleton pyridineamine-based binuclear metal titanium zirconium hafnium catalyst requires the use of a co-catalyst for catalysis. The co-catalyst is one or more of tripentafluorophenylboron, triphenylcarbium tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum, and alkylaluminum chloride.

9. The method according to claim 8, characterized in that: The aluminum oxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum chloride, sesqui-diethylaluminum chloride, or ethylaluminum dichloride.

10. The method according to claim 6, characterized in that: The polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5.0MPa, and the solvent used for polymerization is one or more of n-hexane, n-heptane, n-pentane, and toluene.

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