WO2025098181A1 - Tridentate coordinated aminoquinoline single-site complex, preparation method therefor and use thereof - Google Patents

Abstract

The present invention provides a tridentate coordinated aminoquinoline single-site complex, a preparation method therefor, and a use thereof. The tridentate coordinated aminoquinoline single-site complex has a structure as shown in formula (I). In formula (I), M is hafnium; R₁ is selected from hydrogen, a halogen, a C₁-C₆ hydrocarbon group and a derivative thereof, and a C₆-C₁₃ aryl group and a derivative thereof; and R₂ is selected from hydrogen, a C₁-C₆ hydrocarbon group and a derivative thereof, and a C₆-C₁₃ aryl group and a derivative thereof. The aminoquinoline single-site complex has a novel structure, is easy to synthesize, has a stable spatial configuration, and can maintain high catalytic activity and selectivity at high temperatures.

Description

A tridentate aminoquinoline single-center complex and its preparation method and application Technical Field

The invention belongs to the technical field of olefin catalytic polymerization, and specifically relates to a high-temperature resistant aminoquinoline complex and a preparation method and application thereof.

Background Art

Polyolefin elastomer (POE) is a type of polyolefin material formed by the copolymerization of ethylene and propylene or other α-olefins (such as 1-butene, 1-hexene, 1-octene, etc.). Compared with traditional polyolefin resins, its molecular weight distribution is narrower, the branching distribution is uniform, and the comonomer content is high. Since its molecular chain contains a large amount of comonomer, the polymer chain is composed of a crystalline resin phase and an amorphous rubber phase. Therefore, polyolefin elastomer materials have both the high elasticity of rubber and can be formed using the processing technology of thermoplastics. At the same time, polyolefin elastomers have excellent mechanical properties and low-temperature properties, good processability and reusability. They are mainly used as impact modifiers and toughening agents, and are widely used in automobiles, packaging, wires and cables, medical devices, and household appliances.

The production of polyolefin elastomers requires a high-temperature solution polymerization process. A higher polymerization temperature is conducive to reducing the viscosity of the reaction system and ensuring good heat and mass transfer in the reactor. The high-temperature solution polymerization used to prepare POE has high requirements for catalysts. Patent ZL 90107395.4 reports a cyclopentadienylsilylamine-based IVB family (constrained geometry catalyst, CGC), the prototype of which is Me ₂ Si(Me ₅ C ₅ )(t-BuN)TiCl ₂ . CGC catalysts have a high comonomer insertion rate and excellent heat resistance, so that they can be used in high-temperature solution polymerization processes without losing catalytic activity and reducing polymer molecular weight. Philip P. Fontaine (Organometallics 2012, 31, 6244-6251; Organometallics 2015, 34, 1354-1363) reported a bidentate aminoquinoline single-site catalyst that catalyzed the copolymerization of ethylene and octene at 140°C and still had good activity and copolymerization ability.

Compared with high temperature resistant polyethylene catalysts, there are fewer polypropylene catalysts that can maintain excellent activity and selectivity at high temperatures. "Ultrarigid Indenyl-based Hafnocene Complexes for the Highly Isoselective Polymerization of Propene: Tunable Polymerization Performance Adopting Various Sterically Demanding 4-Aryl Substituents, Organometallics 2017, 36, 399-408" and others reported highly isotactic and highly active polypropylene metallocene zirconium catalysts, but as the polymerization temperature increased to 110 degrees, the polymerization activity and the isotacticity of the product decreased significantly. In "ansa-Zirconocene Catalysts for Isotactic-Selective Propene Polymerization at High Temperature:A Long Story Finds a Happy Ending, J.Am.Chem.Soc.2021,143,7641-7647", highly rigid triptycene is introduced into the catalyst skeleton, so that the new metallocene compound can still produce highly isotactic polypropylene at 150 degrees, but the synthesis route is complicated and the catalyst cost is high.

“Development of Improved Amidoquinoline Polyolefin Catalysts with Ultrahigh Molecular Weight Capacity, Organometallics 2015, 34, 1354-1363” synthesized a two-dentate single-site catalyst based on a quinoline skeleton, which catalyzed the copolymerization of ethylene and octene at 140°C and still had good activity and copolymerization ability. However, it did not provide data on the high-temperature polymerization of propylene, nor did it provide data on polymerization at higher temperatures (≥140°C).

Summary of the invention

In order to solve the above problems, the purpose of the present invention is to provide a tridentate aminoquinoline single-center complex and its preparation method and application. The aminoquinoline single-center complex has a novel structure, is easy to synthesize, has a stable spatial configuration, and can maintain high catalytic activity and selectivity at high temperatures.

In order to achieve the above object, the present invention provides a tridentate aminoquinoline single-center complex having a structure shown in Formula I:

In formula I, M is hafnium; _R1 is selected from hydrogen, halogen, _C1 - _C6 hydrocarbon group and its derivatives, _C6 - _C13 aryl group and its derivatives; _R2 is selected from hydrogen, _C1 - _C6 hydrocarbon group and its derivatives, _C6 - _C13 aryl group and its derivatives.

According to a specific embodiment of the present invention, preferably, in Formula I, R ₁ is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, fluoro, trifluoromethyl; R ₂ is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl.

The present invention also provides a method for preparing the above-mentioned aminoquinoline single-center complex, which comprises the following steps:

(1) 2-phenyl-8-aminoquinoline and substituted bromobenzene are reacted with tri(dibenzylideneacetone)dipalladium, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl and sodium tert-butoxide and refluxed to obtain a ligand. The reaction process is as follows:

(2) The ligand is subjected to a deprotonation reaction with a strong base, and then hafnium tetrachloride is added to prepare an aminoquinoline hafnium chloride compound, which is further subjected to a methylation reaction with methylmagnesium bromide to obtain a complex shown in formula I. The reaction process is as follows;

The present invention also provides a catalyst system, which comprises a main catalyst and a co-catalyst, wherein the main catalyst comprises the above-mentioned aminoquinoline single-center complex.

According to a specific embodiment of the present invention, preferably, the co-catalyst comprises an alkyl aluminum and/or a boron-containing compound.

According to a specific embodiment of the present invention, preferably, the alkyl aluminum includes one or a combination of two or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, and triisobutylaluminum.

According to a specific embodiment of the present invention, preferably, the boron-containing compound includes one or a combination of two or more of tri(pentafluorophenyl)borane, triphenylcarbonium tetra(pentafluorophenyl)borane, triphenylcarbonium tetra(p-trifluoromethylphenyl)borane, N,N-dimethylaniline tetra(pentafluorophenyl)borane, triphenylcarbonium tetra(pentafluorophenyl)borate, and N,N-dimethylaniline tetra(pentafluorophenyl)borate.

According to a specific embodiment of the present invention, preferably, the co-catalyst includes one or a combination of two or more of tri(pentafluorophenyl)borane, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, or a combination of one or more of tri(pentafluorophenyl)borane, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylaniline tetrakis(pentafluorophenyl)borate and triisobutylaluminum.

According to a specific embodiment of the present invention, preferably, the molar ratio of elements in the main catalyst and the co-catalyst is M:B:Al=1:1.0-5.0:50-1000, wherein M is hafnium.

The present invention also provides an olefin polymerization method, which comprises the following steps:

The aminoquinoline single-center complex or the catalyst system is used to catalyze olefin polymerization. Under the action of a co-catalyst, the homopolymerization and copolymerization of ethylene and α-olefin can be catalyzed with high activity.

According to a specific embodiment of the present invention, preferably, the olefin polymerization method comprises the following steps: mixing the catalyst system with olefin, reacting at 90-180° C. for 5-30 min, terminating the reaction, filtering, washing and drying to obtain an olefin polymerization product.

According to a specific embodiment of the present invention, preferably, in the catalyst system, the molar ratio of elements is Hf:Al=1:50-1000 and/or Hf:B=1:1.0-5.0.

According to a specific embodiment of the present invention, preferably, the olefin polymerization includes homopolymerization or copolymerization of ethylene and α-olefin, such as copolymerization of ethylene and α-olefin, isotactic homopolymerization of propylene or propylene-ethylene copolymerization.

According to a specific embodiment of the present invention, preferably, when the olefin polymerization method is polymerization of propylene and α-olefin, the olefin polymerization method comprises the following steps:

In the absence of water and oxygen, the solvent and the co-catalyst are mixed and then heated to 90-180°C, the main catalyst is added, propylene and α-olefin are introduced, the olefin pressure is 0.5-1Mpa, the reaction is carried out at 90-180°C for 5-30min, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained through filtering, washing and drying; or, in the absence of water and oxygen, propylene The propylene, α-olefin and co-catalyst are mixed, heated to 90-180° C., the main catalyst is added, reacted at 90-180° C. for 5-30 minutes, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained through filtering, washing and drying; or, propylene, α-olefin and co-catalyst are added under anhydrous and oxygen-free conditions, the temperature is raised to above 91° C., the critical temperature of propylene, the main catalyst is added, the pressure is 5-20 MPa, the reaction is carried out at 100-180° C. for 5-30 minutes, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained through filtering, washing and drying.

According to a specific embodiment of the present invention, preferably, when the olefin polymerization method is propylene homopolymerization, the olefin polymerization method comprises the following steps:

Under the condition of anhydrous and oxygen-free, the solvent and the co-catalyst are mixed, the temperature is raised to 90-180° C., the main catalyst is added, propylene is introduced, the olefin pressure is 0.5-1Mpa, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the propylene homopolymer product is obtained through filtering, washing and drying; or, under the condition of anhydrous and oxygen-free, propylene and the co-catalyst are mixed, the temperature is raised to 90-180° C., the main catalyst is added, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the propylene homopolymer product is obtained through filtering, washing and drying; or, under the condition of anhydrous and oxygen-free, propylene and the co-catalyst are added, the temperature is raised to above 91° C., the critical temperature of propylene is mixed, the main catalyst is added, the pressure is 5-20Mpa, the reaction is carried out at 100-180° C. for 5-30 minutes, the reaction is terminated, and the propylene homopolymer product is obtained through filtering, washing and drying.

According to a specific embodiment of the present invention, preferably, the α-olefin includes one or a combination of two or more of propylene, hexene, octene, styrene, and 4-methyl-1-pentene.

According to a specific embodiment of the present invention, preferably, the olefin polymerization is a batch polymerization.

According to a specific embodiment of the present invention, preferably, the activity of olefin polymerization reaction is greater than 1×10 ⁶ g/(mol Hf·h).

The present invention also provides polyolefin prepared by the olefin polymerization method.

According to a specific embodiment of the present invention, preferably, the molecular weight distribution of the homopolymer obtained by olefin polymerization is ≥1.32.

The aminoquinoline single-site catalyst of the present invention has a novel structure, simple synthesis, and a stable 2-phenyl-aminoquinoline skeleton structure, which ensures the thermal stability of the catalyst. At the same time, it has high activity in catalyzing olefin polymerization, and the molecular weight of the polymer product is high. The catalyst of the present invention can catalyze the copolymerization of ethylene and α-olefins with high activity during high-temperature polymerization (≥150° C.), and can also catalyze the copolymerization of propylene and ethylene, thereby preparing a high-performance polyolefin elastomer. The present invention has the following beneficial effects:

1. The aminoquinoline single-center complex of the present invention has a simple synthesis route, and the ligand can be obtained in high yield in one-step reaction. The synthesis is simple and efficient, and the yield of synthesizing the ligand from 2-phenyl-8-aminoquinoline raw material exceeds 75%;

2. The present invention introduces sterically hindered aniline into the skeleton of highly rigid 2-phenylquinoline, which provides better protection for the active center of the catalyst system, enhances the high temperature resistance and activity of catalytic olefin polymerization, and the polymerization activity can exceed 1×10 ⁷ g/(mol·h) at 150°C.

3. The tridentate coordination environment can affect the stereoselectivity in the polymerization process of propylene and obtain highly isotactic polymerization The product has a homopolymer isotacticity of propylene of more than 90% at 150°C, and the propylene polymerization still maintains high isotacticity at high temperatures and has high activity, and the obtained polymer has a relatively high molecular weight.

DETAILED DESCRIPTION

In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of the present invention. The experimental methods in the following examples without specifying specific conditions are usually based on conventional conditions.

The catalyst synthesis routes involved are as follows:

(1) Synthesis route of ligand L:

(2) Synthesis route of catalyst a:

(3) Synthesis route of catalyst b:

Preparation Example 1 Synthesis of Ligand L1

This preparation example provides ligand L1, and its synthesis steps are as follows:

Take a 100ml flask, add 20mmol of 2-phenyl-8-aminoquinoline, 0.8mmol of tris(dibenzylideneacetone)dipalladium, 1.6mmol of 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl and 35mmol of sodium tert-butoxide, then take 20mmol of 2,6-diisopropylbromobenzene and add 50ml of toluene. The temperature rises to 110℃, after reflux for 12 hours, stop heating, load on silica gel, prepare eluent (petroleum ether: ethyl acetate = 9:1), elute the product 2-3 times. Obtain the target product: ligand L1. The detection parameters of the obtained product are:

¹ H-NMR: 8.33-8.36(s, 2H), 8.21-8.23(m, 4H), 7.75-7.76(m, 4H), 6.85(m, 1H), 6 .63-6.65(m, 2H), 4.12(s, 1H), 3.12(m, 2H), 1.33-1.35(m, 12H); Calcd.(%)for C ₂₇ H ₂₈ N ₂ : C: 85.22, H: 7.42, N: 7.36; found: C: 85.25, H: 7.44, N: 7.31.

Preparation Example 2 Synthesis of Ligand L2

This preparation example provides ligand L2, and the difference between its synthesis steps and those of preparation example 1 is that 2,6-diisopropylbromobenzene is replaced by 2,6-difluorobromobenzene. The detection parameters of the obtained product are:

¹ H-NMR: 7.99 (s, 2H), 7.68 (s, 1H), 7.28-7.39 (m, 6H), 6.55-6.73 (m, 4H), 4.16 (s, 1H); Calcd. (%) for C ₂₁ H ₁₄ F ₂ N ₂ : C: 75.89, H: 4.25, N: 8.43; found: C: 75.65, H: 4.34, N: 8.31.

Preparation Example 3 Synthesis of Ligand L3

This preparation example provides ligand L3, and the difference between its synthesis steps and those of preparation example 1 is that 2,6-diisopropyl bromobenzene is replaced by 2,6-diisopropyl-4-methyl-bromobenzene. The detection parameters of the obtained product are:

¹ H-NMR: 8.13-8.16(s, 2H), 8.01-8.03(m, 4H), 7.65-7.67(m, 4H), 6.63-6.65(m, 2H), 4.12(s, 1H), 3.12(m, 2H), 2.35(s, 3H), 1.33-1.35(m, 12H); Calcd.(%)for C ₂₈ H ₃₀ N ₂ : C: 85.24, H: 7.66, N: 7.10; found: C: 85.35, H: 7.74, N: 6.91.

Preparation Example 4 Synthesis of Ligand L4

This preparation example provides ligand L4, and the difference between its synthesis steps and those of Preparation Example 1 is that 2,6-diisopropyl bromobenzene is replaced by 2,6-dimethyl bromobenzene. The detection parameters of the obtained product are:

¹ H-NMR: 8.01 (s, 2H), 7.67 (s, 1H), 7.28-7.39 (m, 6H), 6.45-6.74 (m, 4H), 4.17 (s, 1H), 2.38 (s, 6H); Calcd. (%) for C ₂₃ H ₂₀ N ₂ : C: 85.15, H: 6.21, N: 8.63; found: C: 85.25, H: 6.23, N: 8.52.

In order to clearly describe the ligand L prepared in Preparation Example 1-4, its structure is described as follows, see Table 1 for details, and its yield is given:

Ligand L:

Table 1: Ligand L structure and yield information

From the data recorded in the above table, it can be concluded that this type of ligand is prepared by coupling reaction, is easy to synthesize and has a high yield.

The ligands L prepared in Preparation Examples 1-4 have a yield of not less than 79%. The use of the ligand L prepared in the present invention to prepare a bidentate aminoquinoline-based single-site catalyst can achieve higher economic benefits. In actual industrial production, the conversion rate of the reactants can be increased, thereby reducing the amount of reactants used and effectively reducing production costs.

Using the ligand L prepared in the above Preparation Example 1-4 as a raw material, a bidentate aminoquinoline single-site catalyst (cat-a) was further prepared, namely Example 1-4.

Example 1 Synthesis of Catalyst Cat-1a

This embodiment provides a catalyst cat-1a, which is prepared by the following steps:

Use a 50ml Schlenk bottle to weigh the ligand L1 (2mmol) prepared in Preparation Example 1, dissolve it in 10mL toluene, slowly drop 1.6M n-butyllithium solution (2.2mmol) under nitrogen protection and -20°C, and react for 6h. Drain the toluene with a vacuum pump, wash the unreacted n-butyllithium with n-hexane, pour out the supernatant, and obtain a yellow precipitate of lithium salt;

Take another 100ml flask, add the above lithium salt and toluene in turn, shake to dissolve, then add HfCl ₄ (2.5mmol) to the system, raise the temperature to 110℃ and reflux for 12 hours. After the solution cools to room temperature, filter, concentrate the filtrate to 1mL, add n-hexane to obtain a suspension, freeze overnight, filter, and filter to obtain brown-yellow crystals. The detection parameters of the obtained product are:

¹ H-NMR: 8.10-8.13 (s, 2H), 8.03-8.05 (m, 5H), 7.35-7.36 (m, 4H), 6.65-6.67 (m, 2H), 3.08 (m, 2H), 1.31-1.33 (m, 12H); Calcd. (%) for C ₂₇ H ₂₇ Cl ₃ HfN ₂ : C: 48.81, H: 4.10, N: 4.22; found: C: 48.91, H: 4.24, N: 4.21.

Example 2 Synthesis of Catalyst Cat-2a

This example provides a catalyst cat-2a, and the difference between its preparation method and that of Example 1 is that the ligand L2 in Preparation Example 2 is used to replace the ligand L1 in Preparation Example 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.75-7.88 (m, 3H), 7.29-7.39 (m, 6H), 6.51-6.75 (m, 4H); Calcd. (%) for C ₂₁ H ₁₃ Cl ₃ F ₂ HfN ₂ : C: 40.93, H: 2.13, N: 4.55; found: C: 40.91, H: 2.24, N: 4.61.

Example 3 Synthesis of Catalyst Cat-3a

This example provides a catalyst cat-3a, and the difference between its preparation method and that of Example 1 is that the ligand L3 in Preparation Example 3 is used to replace the ligand L1 in Preparation Example 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.73-7.86 (m, 3H), 7.27-7.32 (m, 6H), 6.62-6.70 (m, 3H), 3.13 (m, 2H), 2.42 (s, 3H), 1.33-1.34 (m, 12H); Calcd. (%) for C ₂₈ H ₂₉ Cl ₃ HfN ₂ : C: 49.57, H: 4.31, N: 4.13; found: C: 49.61, H: 4.27, N: 4.11.

Example 4 Synthesis of Catalyst Cat-4a

This example provides a catalyst cat-4a, and the difference between its preparation method and that of Example 1 is that the ligand L4 in Preparation Example 4 is used to replace the ligand L1 in Preparation Example 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.78-7.88 (m, 3H), 7.32-7.38 (m, 6H), 6.41-6.68 (m, 4H), 2.41 (s, 6H); Calcd. (%) for C ₂₃ H ₁₉ Cl ₃ HfN ₂ : C: 45.42, H: 3.15, N: 4.61; found: C: 45.55, H: 3.21, N: 4.68.

In order to clearly describe the bidentate aminoquinoline-based single-site catalyst (cat-a) prepared in Examples 1-4, its structure is described as follows, as shown in Table 2, and its yield is given:

Catalyst cat-a:

Table 2: Catalyst structure information and yield table

According to the experimental data recorded in the above table, the synthesis route of this type of catalyst is simple and has a high yield, which can effectively reduce the production cost of the catalyst.

The bidentate aminoquinoline-based single-site catalyst (cat-a) prepared in the above Examples 1-4 was used as a raw material to further prepare the tridentate aminoquinoline-based single-site catalyst (cat-b) of the present invention, namely Examples 5-8.

Example 5: Synthesis of catalyst cat-1b

This embodiment provides a catalyst cat-1b, and the preparation method thereof is as follows:

The catalyst cat-1a prepared in Example 1 was dissolved in 5 mL of toluene. When the solution temperature dropped to -20°C, MeMgBr solution (4 mmol) was added dropwise. The addition time was controlled to be 5 min and stirred for 3 h. The solution after the reaction was filtered with filter paper, and the filtrate was collected after filtration. The filtrate was concentrated to about 3 ml and crystallized at -35°C for about 18 h. The crystals were then filtered, washed with frozen n-hexane, and vacuum filtered to obtain orange-yellow crystals. The measured parameters are:

¹ H-NMR: 8.10-8.13 (s, 2H), 8.03-8.05 (m, 5H), 7.35-7.36 (m, 4H), 6.65-6.67 (m, 2H), 3.08 (m, 2H), 1.31-1.33 (m, 12H); Calcd. (%) for C ₂₇ H ₂₇ Cl ₃ HfN ₂ : C: 48.81, H: 4.10, N: 4.22; found: C: 48.91, H: 4.24, N: 4.21.

Example 6 Synthesis of Catalyst cat-2b

This embodiment provides a catalyst cat-2b, and the difference between its preparation method and that of embodiment 5 is that cat-2a prepared in embodiment 2 is used to replace cat-1a prepared in embodiment 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.75-7.88 (m, 2H), 7.28-7.35 (m, 6H), 6.53-6.72 (m, 4H), 0.97 (s, 6H); Calcd. (%) for C ₂₃ H ₁₈ F ₂ HfN ₂ : C: 51.26, H: 3.37, N: 5.20; found: C: 51.31, H: 3.31, N: 5.27.

Example 7 Synthesis of Catalyst Cat-3b

This embodiment provides a catalyst cat-3b, and the difference between its preparation method and that of embodiment 5 is that cat-3a prepared in embodiment 3 is used to replace cat-1a prepared in embodiment 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.78-7.86 (m, 2H), 7.29-7.37 (m, 6H), 6.51-6.69 (m, 3H), 3.13 (m, 2H), 2.40 (s, 3H), 1.31-1.33 (m, 12H), 0.95 (s, 6H); Calcd. (%) for C ₃₀ H ₃₄ HfN ₂ : C: 59.94, H: 5.70, N: 4.66; found: C: 60.01, H: 5.67, N: 4.71.

Example 8 Synthesis of Catalyst Cat-4b

This embodiment provides a catalyst cat-4b, and the difference between its preparation method and that of embodiment 5 is that cat-4a prepared in embodiment 4 is used to replace cat-1a prepared in embodiment 1. The detection parameters of the obtained product are:

¹ H-NMR: 7.77-7.86 (m, 2H), 7.27-7.38 (m, 6H), 6.49-6.71 (m, 4H), 2.43 (s, 6H), 0.95 (s, 6H); Calcd. (%) for C ₂₅ H ₂₄ HfN ₂ : C: 56.55, H: 4.56, N: 5.28; found: C: 56.51, H: 4.61, N: 5.23.

In order to clearly describe the tridentate aminoquinoline-based single-site catalyst cat-b prepared in Examples 5-8, its structure is described as follows, as shown in Table 3, and its yield is given:

Catalyst cat-b:

Table 3: Catalyst structure information and yield table

According to the experimental data recorded in the above table, the tridentate aminoquinoline-based single-site catalysts prepared in Examples 5-8 have a yield higher than 60%. The catalyst is easy to synthesize and can obtain a higher yield.

The catalysts prepared in the above Examples 5-8 were applied to catalyze olefin polymerization reactions, and the following Application Examples 1-22 were obtained.

Application Example 1

This application example provides a method for catalyzing the copolymerization of ethylene and octene at a high temperature of 150° C. using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-1b is 4.4×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 353 kg/mol, the molecular weight distribution index is 1.9, the glass transition temperature is -52°C, and the melting temperature is 63°C.

Application Example 2

This application example provides a method for catalyzing the copolymerization of ethylene and octene at a high temperature of 150° C. using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-2b is 2.9×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared ethylene-octene copolymer is 251 kg/mol, the molecular weight distribution index is 2.2, the glass transition temperature is -45°C, and the melting temperature is 75°C.

Application Example 3

This application example provides a method for catalyzing the copolymerization of ethylene and octene at a high temperature of 150° C. using the catalyst cat-3b prepared in Example 7, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-3b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-3b is 4.2×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 331 kg/mol, the molecular weight distribution index is 2.1, the glass transition temperature is -50°C, and the melting temperature is 65°C.

Application Example 4

This application example provides a method for catalyzing the copolymerization of ethylene and octene at a high temperature of 150° C. using the catalyst cat-4b prepared in Example 8, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-4b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-4b is 2.9×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 257 kg/mol, the molecular weight distribution index is 2.2, the glass transition temperature is -47°C, and the melting temperature is 73°C.

Application Example 5

This application example provides a method for catalyzing the copolymerization of ethylene and octene using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:50) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-1b is 2.9×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 342 kg/mol, the molecular weight distribution index is 2.1, the glass transition temperature is -51°C, and the melting temperature is 68°C.

Application Example 6

This application example provides a method for catalyzing the copolymerization of ethylene and octene using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and methylaluminoxane (Hf:Al=1:1000) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene, the ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-1b is 3.3×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 307 kg/mol, the molecular weight distribution index is 2.3, the glass transition temperature is -53°C, and the melting temperature is 67°C.

Application Example 7

This application example provides a method for catalyzing the copolymerization of ethylene and octene using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, triisobutylaluminum (Hf:Al=1:50) and tri(pentafluorophenyl)borane (Hf:B=1:1) were added into the reactor and the temperature was raised to 150°C. 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene. The ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The filtered product was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain ethylene-octene copolymer.

In this application example, the catalytic activity of cat-1b is 3.1×10 ⁷ g/(mol Hf·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 291 kg/mol, the molecular weight distribution index is 2.2, the glass transition temperature is -48°C, and the melting temperature is 72°C.

Application Example 8

This application example provides a method for catalyzing the copolymerization of ethylene and octene using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, triisobutylaluminum (Hf:Al=1:1000) and tri(pentafluorophenyl)borane (Hf:B=1:5) were added into the reactor and the temperature was raised to 150°C. 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then pressed into the reactor with ethylene. The ethylene pressure was adjusted to 2 MPa, and the copolymerization of ethylene and 1-octene was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The filtrate was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain ethylene-octene copolymer.

The catalytic activity of cat-1b in this application example is 1.1×10 ⁷ g/(mol Hf·h), and the prepared ethylene-octene copolymer The weight average molecular weight is 181 kg/mol, the molecular weight distribution index is 2.6, the glass transition temperature is -41°C, and the melting temperature is 82°C.

Application Example 9

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 3.3×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 255 kg/mol, the molecular weight distribution index is 2.3, and the isotacticity is 95%.

Application Example 10

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 1.9×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 201 kg/mol, the molecular weight distribution index is 2.6, and the isotacticity is 90%.

Application Example 11

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-3b prepared in Example 7, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-3b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-3b in this application example is 3.1×10 ⁷ g PP/(mol Hf·h), and the polypropylene prepared is The weight average molecular weight is 241 kg/mol, the molecular weight distribution index is 2.4, and the isotacticity is 93%.

Application Example 12

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-4b prepared in Example 8, which specifically includes the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-4b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

In this application example, the catalytic activity of the catalyst cat-4b is 3.1×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 331 kg/mol, the molecular weight distribution index is 2.5, and the isotacticity is 91%.

Application Example 13

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 90°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtered. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

In this application example, the catalytic activity of the catalyst cat-1b is 3.8×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 322 kg/mol, the molecular weight distribution index is 2.5, and the isotacticity is 98%.

Application Example 14

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 120°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 3.6×10 ⁷ g PP/(mol Hf·h), and the polypropylene prepared is The weight average molecular weight is 289 kg/mol, the molecular weight distribution index is 2.1, and the isotacticity is 96%.

Application Example 15

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:1000) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 2.8×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 178 kg/mol, the molecular weight distribution index is 2.4, and the isotacticity is 92%.

Application Example 16

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 4.1×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 293 kg/mol, the molecular weight distribution index is 2.1, the ethylene content (mass) is 16%, the copolymer has a glass transition temperature of -30°C and a melting point of 95°C.

Application Example 17

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. After stirring for 0.5 hour, the mixture was filtered, washed three times with ethanol, and vacuum dried at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 2.0×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 211 kg/mol, the molecular weight distribution index is 2.1, the ethylene content (mass) is 14%, the copolymer has a glass transition temperature of -25°C and a melting point of 110°C.

Application Example 18

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-3b prepared in Example 7, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-3b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, ethanol was acidified with 5% hydrochloric acid to terminate the polymerization. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-3b in this application example is 3.6×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 252 kg/mol, the molecular weight distribution index is 2.3, the ethylene content (mass) is 15%, the copolymer has a glass transition temperature of -28°C and a melting point of 101°C.

Application Example 19

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-4b prepared in Example 8, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-4b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-4b in this application example is 3.2×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 342 kg/mol, the molecular weight distribution index is 2.2, the ethylene content (mass) is 14%, the copolymer has a glass transition temperature of -26°C and a melting point of 110°C.

Application Example 20

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added to the reactor, the temperature was raised to 120°C, 2 μmol of the catalyst cat-1b was dissolved in 10 mL of toluene, and the propylene-ethylene mixed gas (propylene The mixture was heated to 30 ℃ and then cooled to 40 ℃ and then cooled to 80 ℃. The mixture was cooled to 80 ℃ and then cooled to 10 ℃. The mixture was cooled to 80 ℃ and then cooled to 10 ℃. The mixture was cooled to 80 ℃ and then cooled to 10 ℃. The mixture was cooled to 80 ℃ and then cooled to 10 ℃. The mixture was cooled to 80 ℃ and then cooled to 10 ℃.

The catalytic activity of the catalyst cat-1b in this application example is 4.5×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 352 kg/mol, the molecular weight distribution index is 2.2, the ethylene content (mass) is 15%, the copolymer has a glass transition temperature of -31°C and a melting point of 98°C.

Application Example 21

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, triisobutylaluminum (Hf:Al=1:50) and tri(pentafluorophenyl)borane (Hf:B=1:1.5) were added into the reactor and the temperature was raised to 150°C. After 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene, a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% mass fraction of hydrochloric acid. After stirring for 0.5 hour, the mixture was filtered, washed three times with ethanol, and vacuum dried at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 2.9×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 292 kg/mol, the molecular weight distribution index is 2.4, the ethylene content (mass) is 14%, the copolymer has a glass transition temperature of -24°C and a melting point of 106°C.

Application Example 22

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-1b prepared in Example 5, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-1b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 95%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, ethanol was acidified with 5% hydrochloric acid to terminate the polymerization. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 4.2×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 334 kg/mol, the molecular weight distribution index is 2.1, the ethylene content (mass) is 11%, the copolymer has a glass transition temperature of -24°C and a melting point of 112°C.

The above-mentioned application examples 1-22 use a tridentate aminoquinoline-based single-site catalyst to catalyze olefin polymerization Effect:

Combined with Application Examples 1-22, it can be found that: the tridentate catalytic system can prepare high-performance polyolefin elastomers through high-temperature polymerization;

Combining Application Examples 1-4, Application Examples 9-12 and Application Examples 16-19, it can be found that: at high temperature, the tridentate catalyst system can not only catalyze the copolymerization of ethylene and α-olefins with high activity, but also catalyze the polymerization of propylene to obtain highly isotactic polypropylene, and then obtain propylene-based elastomers through copolymerization of propylene and ethylene;

Combining Application Example 9 with Application Examples 13-14, Application Example 16 with Application Example 20, it can be found that the tridentate catalytic system still has excellent catalytic performance at 150°C, indicating that the tridentate coordinated aminoquinoline-based single-center catalyst prepared by the present invention has good high temperature resistance;

Combining Application Example 1 with Application Examples 5-8, Application Example 9 with Application Example 15, and Application Example 16 with Application Examples 21-22, it can be found that when different co-catalysts are selected to assist in the catalytic polymerization of olefins and propylene homopolymerization, the catalytic effects are also different. By comparing the catalytic effects of the above application examples, it is more preferred to use methylaluminoxane when selecting a co-catalyst.

The following are comparative application examples of the present invention. The catalysts used in the comparative application examples are all preferred objects for catalyzing olefin polymerization reactions in the prior art.

Under the same polymerization conditions as those of the present invention, the type of catalyst was changed, the catalytic effect was tested, and the following application comparative examples 1-2 were given.

Application Comparative Example 1:

The catalyst used in this comparative example is: dimethylsilyl tert-butylamine tetramethylcyclopentadiene titanium dichloride; it is used to catalyze the copolymerization of ethylene-octene, and the polymerization conditions are the same as those in Application Example 1.

The catalytic activity of the catalyst used in this comparative example is 2.6×10 ⁷ g/(mol Ti·h), and the weight average molecular weight of the prepared ethylene-octene copolymer is 103 kg/mol, the molecular weight distribution index is 2.2, the glass transition temperature is -50°C, and the melting temperature is 71°C.

Application Comparative Example 2:

The catalyst used in this comparative example is: vinyl bisindenyl zirconium dichloride; it is used to catalyze the homopolymerization of propylene, and the polymerization conditions are the same as those in Application Example 14.

The catalytic activity of the catalyst used in the comparative example of this application is 4×10 ⁶ g PP/(mol Zr·h), and the weight average molecular weight of the prepared polypropylene is 4 kg/mol, the molecular weight distribution index is 2.9, and the isotacticity is 77%.

By comparing Application Example 1 and Comparative Application Example 1, it can be seen that the catalyst cat-1b of the present invention has higher activity in catalyzing ethylene-octene polymerization, and the obtained ethylene-octene copolymer has higher molecular weight.

By comparing Application Example 14 with Comparative Example 2, it can also be seen that the catalyst cat-1b of the present invention is used to catalyze Propylene polymerization has higher activity, and the resulting polypropylene has higher isotacticity and molecular weight.

In summary, the tridentate aminoquinoline single-site catalyst prepared by the present invention has excellent high temperature resistance and activity, and the polymerization activity can exceed 1×10 ⁷ g/(mol·h) at 150°C. When catalyzing the homopolymerization of olefin monomers, the homopolymer distribution is below 2.6, and the regularity of the α-olefin polymerization product can be improved; when catalyzing the copolymerization of ethylene and other α-olefin monomers, the distribution is narrow, showing the characteristics of a single active center.

The above are only preferred feasible embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Various modifications or applications made according to the above embodiments are within the protection scope of this technical solution.

Although the specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art. According to all the teachings disclosed, various modifications and replacements can be made to those details, and these changes are all within the protection scope of the present invention. The full scope of the present invention is given by the attached claims and any equivalents thereof.

Application Example 23

This application example provides a method for catalyzing propylene homopolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:1000) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene and then gaseous propylene was pressed into the reactor, the propylene pressure was adjusted to 1 MPa, and propylene homopolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, and then filtering. The filtrate was washed three times with ethanol and vacuum dried at 70°C for 12 h to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 2.7×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 238 kg/mol, the molecular weight distribution index is 2.5, and the isotacticity is 92%.

Application Example 24

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:1000) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, ethanol was acidified with 5% hydrochloric acid to terminate the polymerization. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 2.7×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 231 kg/mol, the molecular weight distribution index is 2.0, the ethylene content (mass) is 15%, and the copolymer Glass transition temperature -26℃, melting point 108℃.

Application Example 25

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene, triisobutylaluminum (Hf:Al=1:50) and tri(pentafluorophenyl)borane (Hf:B=1:1.5) were added into the reactor and the temperature was raised to 150°C. After 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene, a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% mass fraction of hydrochloric acid. After stirring for 0.5 hour, the mixture was filtered, washed three times with ethanol, and vacuum dried at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-1b in this application example is 3.1×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 299 kg/mol, the molecular weight distribution index is 2.3, the ethylene content (mass) is 15%, the copolymer has a glass transition temperature of -27°C and a melting point of 102°C.

Application Example 26

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 95%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 3.2×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 238 kg/mol, the molecular weight distribution index is 2.1, the ethylene content (mass) is 12%, the copolymer has a glass transition temperature of -21°C and a melting point of 112°C.

Application Example 27

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:500) were added to the reactor, and the temperature was raised to 150°C. After 2 μmol of the catalyst cat-2b was dissolved in 10 mL of toluene, a propylene-ethylene mixture (97% by mass of propylene) was pressed into the reactor, and the pressure of the mixed gas was adjusted to 1 MPa. Propylene-ethylene copolymerization was carried out at 150°C. The polymerization was carried out for 30 minutes. After the reaction stopped, ethanol was acidified with 5% hydrochloric acid to terminate the polymerization. After stirring for 0.5 hours, it was filtered, washed three times with ethanol, and vacuum dried at 70° C. for 12 hours to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 3.1×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 231 kg/mol, the molecular weight distribution index is 2.2, the ethylene content (mass) is 8%, the copolymer has a glass transition temperature of -15°C and a melting point of 121°C.

Application Example 28

This application example provides a method for catalyzing propylene-ethylene copolymerization using the catalyst cat-2b prepared in Example 6, which specifically comprises the following steps:

Under anhydrous and oxygen-free conditions, 1000 mL of toluene and methylaluminoxane (Hf:Al=1:100) were added into the reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 10 mL of toluene, and a propylene-ethylene mixture (propylene mass content 93%) was pressed into the reactor. The pressure of the mixed gas was adjusted to 1 MPa, and propylene-ethylene copolymerization was carried out at 150°C for 30 min. After the reaction stopped, ethanol was acidified with 5% hydrochloric acid to terminate the polymerization. The mixture was stirred for 0.5 hour and then filtered. The mixture was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 1.7×10 ⁷ g/(mol Hf·h), the weight average molecular weight of the prepared propylene-ethylene polymer is 161 kg/mol, the molecular weight distribution index is 2.5, the ethylene content (mass) is 14%, the glass transition temperature of the copolymer is -23°C, and the melting point is 110°C.

Application Example 29

This application example provides a method for catalyzing homopolymerization of propylene under supercritical conditions using the catalyst cat-2b prepared in Example 6, which specifically includes the following steps:

Under anhydrous and oxygen-free conditions, 500 g of propylene and 1000 μmol of methylaluminoxane (Hf:Al=1:500) were added into a 2L reactor, the temperature was raised to 150°C, 2 μmol of catalyst cat-2b was dissolved in 5 mL of toluene and then pressed into the reactor through a catalyst adding tank with high-pressure nitrogen, and propylene homopolymerization was carried out at 150°C and 10 MPa for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid, stirring for 0.5 hour, filtering, washing the filtrate three times with ethanol, and vacuum drying at 70°C for 12 hours to obtain a polypropylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 3.9×10 ⁷ g PP/(mol Hf·h), and the weight average molecular weight of the prepared polypropylene is 245 kg/mol, the molecular weight distribution index is 2.4, and the isotacticity is 95%.

Application Example 30

This application example provides a method for copolymerizing propylene and ethylene under supercritical conditions using the catalyst cat-2b prepared in Example 6, which specifically includes the following steps:

Under anhydrous and oxygen-free conditions, 500 g of propylene, 16.7 g of ethylene, and 1000 μmol of methylaluminoxane (Hf:Al=1:500) were added into a 2L reactor, and the temperature was raised to 150°C. 0.5 μmol of catalyst cat-1 was dissolved in 3 mL of toluene and then pressed into the reactor through a catalyst adding tank with high-pressure nitrogen. The polymerization reaction was carried out at 150°C and 10 MPa for 30 min. After the reaction stopped, the polymerization was terminated by acidifying ethanol with 5% hydrochloric acid. The mixture was stirred for 0.5 hour and then filtered. The filtrate was washed three times with ethanol and dried in vacuo at 70°C for 12 h to obtain a propylene-ethylene polymer.

The catalytic activity of the catalyst cat-2b in this application example is 3.6×10 ⁷ g PP/(mol Hf·h), the prepared propylene-ethylene polymer has a weight average molecular weight of 253 kg/mol, a molecular weight distribution index of 2.2, an ethylene content (mass) of 8.1%, and a copolymer melting point of 110°C.

Claims (19)

A tridentate aminoquinoline single-center complex having a structure shown in Formula I:
In formula I, M is hafnium; _R1 is selected from hydrogen, halogen, _C1 - _C6 hydrocarbon group and its derivatives, _C6 - _C13 aryl group and its derivatives; _R2 is selected from hydrogen, _C1 - _C6 hydrocarbon group and its derivatives, _C6 - _C13 aryl group and its derivatives. The aminoquinoline single-center complex according to claim 1, wherein, in formula I, _R1 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, fluoro, trifluoromethyl; _R2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl. The method for preparing the aminoquinoline single-center complex according to claim 1 or 2, comprising the following steps: (1) 2-phenyl-8-aminoquinoline and substituted bromobenzene are reacted with tri(dibenzylideneacetone)dipalladium, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl and sodium tert-butoxide and refluxed to obtain a ligand. The reaction process is as follows:
(2) The ligand is subjected to a deprotonation reaction with a strong base, and then hafnium tetrachloride is added to prepare an aminoquinoline hafnium chloride compound, which is further subjected to a methylation reaction with methylmagnesium bromide to obtain a complex shown in formula I. The reaction process is as follows;
A catalyst system comprises a main catalyst and a co-catalyst, wherein the main catalyst comprises the aminoquinoline single-center complex according to claim 1 or 2. The catalyst system according to claim 4, wherein the co-catalyst comprises an alkyl aluminum and/or a boron-containing compound. The catalyst system according to claim 5, wherein the alkyl aluminum comprises one or a combination of two or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, and triisobutylaluminum. The catalyst system according to claim 5, wherein the boron-containing compound comprises tri(pentafluorophenyl)borane, One or a combination of two or more of triphenylcarbonium tetrakis(pentafluorophenyl)boron, triphenylcarbonium tetrakis(p-trifluoromethylphenyl)boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. The catalyst system according to claim 5, wherein the co-catalyst comprises one or more of tri(pentafluorophenyl)borane, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, or a combination of tri(pentafluorophenyl)borane, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylaniline tetrakis(pentafluorophenyl)borate and triisobutylaluminum. The catalyst system according to claim 8, wherein the molar ratio of the elements in the main catalyst and the co-catalyst is M:B:Al=1:1.0-5.0:50-1000, wherein M is hafnium. An olefin polymerization method comprising the following steps: The aminoquinoline single-center complex according to claim 1 or 2 or the catalyst system according to any one of claims 4 to 9 is used to catalyze olefin polymerization. The olefin polymerization method according to claim 10, wherein the olefin polymerization method comprises the following steps: The catalyst system is mixed with olefins, reacted at 90-180° C. for 5-30 minutes, the reaction is terminated, and the olefin polymerization product is obtained through filtering, washing and drying. The olefin polymerization method according to claim 11, wherein in the catalyst system, the element molar ratio is Hf:Al=1:50-1000 and/or Hf:B=1:1.0-5.0. The olefin polymerization method according to claim 10, wherein the olefin polymerization comprises homopolymerization or copolymerization of ethylene and α-olefin. The olefin polymerization method according to claim 11 or 12, wherein when the olefin polymerization method is polymerization of propylene and α-olefin, the olefin polymerization method comprises the following steps: In the absence of water and oxygen, the solvent and the co-catalyst are mixed and then heated to 90-180° C., the main catalyst is added, propylene and α-olefin are introduced, the olefin pressure is 0.5-1Mpa, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained through filtering, washing and drying; Alternatively, in the absence of water and oxygen, propylene, α-olefin and co-catalyst are mixed, the temperature is raised to 90-180° C., the main catalyst is added, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained by filtering, washing and drying; Alternatively, under the condition of anhydrous and oxygen-free, propylene, α-olefin and co-catalyst are added, the temperature is raised to above 91° C., the critical temperature of propylene, and the main catalyst is added at a pressure of 5-20 MPa. The reaction is carried out at 100-180° C. for 5-30 minutes, the reaction is terminated, and the polymerization product of propylene and α-olefin is obtained through filtering, washing and drying. The olefin polymerization method according to claim 11 or 12, wherein when the olefin polymerization method is propylene homopolymerization, the olefin polymerization method comprises the following steps: In the absence of water and oxygen, the solvent and the co-catalyst are mixed and then heated to 90-180° C., the main catalyst is added, propylene is introduced, the olefin pressure is 0.5-1Mpa, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the propylene homopolymer product is obtained by filtering, washing and drying; Alternatively, in the absence of water and oxygen, propylene and a co-catalyst are mixed, the temperature is raised to 90-180° C., the main catalyst is added, the reaction is carried out at 90-180° C. for 5-30 minutes, the reaction is terminated, and the product is filtered, washed and dried to obtain a propylene homopolymer product; Alternatively, under the condition of anhydrous and oxygen-free, propylene and a co-catalyst are added, the temperature is raised to above the critical temperature of propylene at 91° C. after mixing, the main catalyst is added, the pressure is 5-20 MPa, the reaction is carried out at 100-180° C. for 5-30 minutes, the reaction is terminated, and the propylene homopolymer product is obtained through filtering, washing and drying. The olefin polymerization method according to claim 11, wherein the α-olefin comprises one or a combination of two or more of propylene, hexene, octene, styrene, and 4-methyl-1-pentene. The olefin polymerization method according to claim 10, wherein the activity of the olefin polymerization reaction is greater than 1×10 ⁶ g/(mol Hf·h). The polyolefin prepared by the olefin polymerization method according to any one of claims 10 to 17. The polyolefin according to claim 18, wherein the molecular weight distribution of the homopolymer obtained by olefin polymerization is ≥1.32.