Bridged pyridyl amido hafnium catalysts, methods of making and using the same

Abstract

The application provides a bridged pyridyl amido hafnium catalyst and a preparation method and application thereof, the catalyst is used for catalyzing the polymerization of butene-1, and the catalyst has the following formula I structure: wherein R1 is hydrogen or a hydrocarbon group with 1-10 carbon atoms, R2 is a hydrocarbon group with 1-10 carbon atoms, and R3 is a hydrocarbon group with 1-6 carbon atoms. The bridged pyridyl amido hafnium catalyst has excellent catalytic performance, and high-activity preparation can obtain high-stereoregularity, narrow distribution and high-molecular-weight polybutene-1.

Description

Technical Field

[0001] This invention relates to the field of olefin catalytic polymerization technology, specifically to bridged pyridine-amine hafnium catalysts, their preparation methods, and applications. Background Technology

[0002] High-isotropic polybutene-1 (PB) is a semi-crystalline polyolefin thermoplastic resin polymerized from butene-1 monomer, enjoying the reputation of "the gold standard among plastics." PB possesses excellent temperature resistance, durability, chemical stability, and plasticity. It is tasteless, non-toxic, and odorless, making it one of the most advanced chemical materials in the world. PB pipes are widely used in Europe, America, Australia, Southeast Asia, and other countries, with mature technology and well-developed supporting systems.

[0003] Currently, polybutene-1 is mainly prepared by Ziegler-Natta catalysts. Ziegler-Natta catalysts are widely used industrially for the production of polybutene-1 due to their high catalytic efficiency, the good overall performance of the produced polymers, and low cost. For example, European Patent 82111264.6 reports a method for synthesizing polybutene with an isotacticity of 70%-80%, a crystallinity of 25%-40%, and thermoplastic elastomer properties using a modified supported titanium catalytic system. Its properties are similar to those of EPDM / PP, SEBS thermoplastics, and plasticized PVC flexible materials, and it can replace them in many applications, thus expanding the uses and value of polybutene. In recent years, there have been increasing reports on polybutene-1 in China. For instance, Chinese Patent CN201510954491.8 reports the polymerization of butene-1 using a supported Ziegler-Natta catalyst, adjusting the isotacticity of polybutene-1 through a four-stage polymerization reaction and using alkoxysilane and ether composite external electron donors to prepare spherical polybutene-1 particles. Chinese patent CN200710013587.X reports the synthesis of powdered polybutene-1 polymers using butene-1 as a monomer and reaction medium, under reaction temperatures of 0-70℃, and with the catalysis of a supported titanium catalyst. The unpolymerized monomers are then removed by flash evaporation and repolymerized to obtain highly isomeric polybutene-1 powder particles. However, due to the multiple active sites of the Ziegler-Natta catalyst, the resulting polymer has a particularly wide molecular weight distribution, generally greater than 10. The poor mechanical properties of the low molecular weight fraction limit its application in high-end fields.

[0004] In addition, Resconi L, Camurati I, Malizia F. Metallocene Catalysts for 1-Butene Polymerization[J]. Macromolecular Chemistry & Physics, 2010, 208(4): 423-423. Dimethylsilyl-bridged zirconium dichloride catalysts with indene ligands containing different substituents were synthesized, and MAO was used as a co-catalyst. The effects of different ligand catalysts on the polymerization of 1-butene and the polymer were studied. It was found that the highest catalytic activity was 195.0 kgPB / g mc·h (mc = metallocene) during bulk polymerization at 70℃, Mw was higher than 4.0 × 105 g / mol, the molecular weight distribution was 2.1-2.7, and the isotacticity of the polymer was related to the indene complex, with the highest isotacticity reaching 98.5%. However, this technology uses a single-metal-center metallocene catalyst. The metallocene catalyst has large steric hindrance, and it is difficult for the sterically hindered 1-butene monomer to insert. The activity of the metallocene catalyst in catalyzing 1-butene is relatively low.

[0005] Meanwhile, butene-1 is currently mainly used as a comonomer for polyethylene, with the remainder primarily used as a mixed C4 fuel. With the successive commissioning of large-scale ethylene projects in China, butene-1 production capacity will exceed 850,000 tons per year by the end of 2021. Furthermore, as the trend of using high-carbon alpha-olefins such as hexene-1 and octene-1 as comonomers in polyethylene becomes increasingly apparent, butene-1 resources will become increasingly surplus in the future. How to optimize the industrial structure of butene-1 resources and utilize them for high added value is one of the urgent problems that major chemical companies in China need to solve. Summary of the Invention

[0006] The main objective of this invention is to provide a bridged pyridine-amine hafnium catalyst, its preparation method, and its application, in order to overcome the shortcomings and deficiencies of polybutene-1 prepared in the prior art, which has a wide molecular weight distribution and poor mechanical properties of the low molecular weight fraction.

[0007] To achieve the above objectives, the present invention provides a bridged pyridine-amine hafnium catalyst for catalyzing the polymerization of butene-1, the catalyst having the following structure:

[0008]

[0009] Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, R2 is a hydrocarbon group having 1-10 carbon atoms, and R3 is a hydrocarbon group having 1-6 carbon atoms.

[0010] In one embodiment of the bridged pyridineamine hafnium catalyst of the present invention, R1 is hydrogen, an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; R2 is an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; and R3 is an alkyl group having 1-6 carbon atoms.

[0011] To achieve the above objectives, the present invention also provides a method for preparing a bridged pyridine-amine hafnium catalyst, wherein the catalyst is used to catalyze the polymerization of butene-1, and the preparation method includes the following steps:

[0012] Step 1: The compound of formula II is subjected to a condensation reaction with 2,6-diisopropylaniline to obtain the compound of formula III;

[0013]

[0014] Step 2: The compound of formula III is reduced to obtain the compound of formula IV. The reducing agent is trialkylaluminum or alkyllithium.

[0015]

[0016] Step 3: The compound of formula IV undergoes a deprotonation reaction, and then reacts with hafnium tetrachloride to obtain the compound of formula V;

[0017]

[0018] Step 4: Compound V reacts with alkyl magnesium halide to generate catalyst I;

[0019]

[0020] Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, the hydrocarbon group R2 in the reducing agent has 1-10 carbon atoms, the alkyl group R3 in the alkyl magnesium halide has 1-6 carbon atoms, and X is a halogen.

[0021] In one embodiment of the method for preparing the bridged pyridine-amine hafnium catalyst of the present invention, the preparation method of the compound of formula II is as follows: the compound of formula VI and the compound of formula VII are coupled together to obtain the compound of formula II;

[0022]

[0023] In one embodiment of the preparation method of the bridged pyridine-amine hafnium catalyst of the present invention, the preparation method of compound VII is as follows: o-chlorophenol is reacted with dibromobutane to generate dichlorophenyl diether compound, and then the dichlorophenyl diether compound is reacted with alkyl lithium reagent and dialkyl borate ester to obtain compound VII;

[0024]

[0025] In one embodiment of the preparation method of the bridged pyridineamine hafnium catalyst of the present invention, the alkyl lithium reagent has the structure R4Li, wherein R4 is an alkyl group having 1-6 carbons; and the dialkyl borate ester has the structure R5OBOR5, wherein R5 is an alkyl group having 1-6 carbons.

[0026] To achieve the above objectives, the present invention further provides a method for polymerizing butene-1, using butene-1 as raw material, the above-mentioned bridged pyridine-amine hafnium catalyst as the main catalyst, and a boron compound as a co-catalyst to carry out the polymerization reaction.

[0027] In one embodiment of the butene-1 polymerization method of the present invention, the boron compound is [Ph3C][B(C6F5)4], and the molar ratio of the co-catalyst to the main catalyst is (0.5-5):1; alkyl aluminum is also added as an activator during polymerization, and the molar ratio of the activator to the main catalyst is (0.01-1100):1.

[0028] In one embodiment of the butene-1 polymerization method of the present invention, the molar ratio of the butene-1 monomer to the main catalyst is 8000 to 40000:1, and the polymerization reaction temperature is 25 to 90°C.

[0029] To achieve the above objectives, the present invention further provides polybutene-1 obtained by the above method, wherein the polybutene-1 has a weight-average molecular weight of not less than 3 million, a molecular weight distribution of not more than 3.0, an isotacticity of not less than 98%, and a melting temperature of not less than 220°C.

[0030] The beneficial effects of this invention are:

[0031] The bridged pyridine-amine hafnium catalyst of this invention exhibits excellent catalytic performance, enabling the highly active preparation of polybutene-1 with high isotacticity, narrow molecular weight distribution, and high molecular weight. Furthermore, when using the bridged pyridine-amine hafnium catalyst of this invention for the polymerization of butene-1, the polymerization conditions are mild, the polymerization activity is high, the monomer conversion rate is high, and the entire polymerization reaction is highly efficient and controllable. The polybutene-1 prepared by the catalyst of this invention has a weight-average molecular weight exceeding 3 million, a narrower molecular weight distribution (below 3.0), better mechanical properties, and a higher melting point. Attached Figure Description

[0032] Figure 1 The image shows the carbon NMR spectrum of polybutene-1 prepared in Example 2 of this invention.

[0033] Figure 2 This is a DSC curve of polybutene-1 prepared in Example 2 of the present invention.

[0034] Figure 3 This is a GPC curve of polybutene-1 prepared in Example 2 of the present invention. Detailed Implementation

[0035] The technical solution of the present invention will be described in detail below. The following embodiments are implemented under the premise of the technical solution of the present invention and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. The structures or experimental methods that are not specified in the following embodiments are generally carried out under conventional conditions. Unless otherwise specified, the raw materials and reagents used are all raw materials and reagents that can be obtained from conventional markets and other commercial channels.

[0036] This invention provides a bridged pyridine-amine hafnium catalyst for catalyzing the polymerization of butene-1, the catalyst having the following structure:

[0037]

[0038] Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, R2 is a hydrocarbon group having 1-10 carbon atoms, and R3 is a hydrocarbon group having 1-6 carbon atoms.

[0039] The non-metallocene catalyst of this invention, compared with the traditional Ziegler-Natta catalyst, has a more open steric sphere, which is conducive to the coordination insertion of the sterically hindered butene-1 monomer, resulting in higher catalytic polymerization activity (10-40 kg polymer / (mmol Hf·h). In addition, the non-metallocene-bridged bipyridineamine hafnium catalyst of this invention is a single active site catalyst, which can prepare polymers with a narrower distribution.

[0040] In one embodiment, R1 is hydrogen, an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, propenyl, phenyl, etc. R2 is an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, propenyl, phenyl, 2-isopropylphenyl, etc. R3 is an alkyl group having 1-6 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.

[0041] In one embodiment, the present invention also provides a method for preparing the above-mentioned bridged pyridine-amine hafnium catalyst, comprising the following steps:

[0042] Step 1a: o-chlorophenol is reacted with dibromobutane to generate dichlorophenyl diether compound, and then the dichlorophenyl diether compound is reacted with alkyllithium reagent and dialkyl borate ester to obtain compound VII;

[0043]

[0044] Step 1b: The compound of formula VI is coupled with the compound of formula VII to obtain the compound of formula II.

[0045]

[0046] Step 1: The compound of formula II is subjected to a condensation reaction with 2,6-diisopropylaniline to obtain the compound of formula III;

[0047]

[0048] Step 2: The compound of formula III is reduced to obtain the compound of formula IV. The reducing agent is trialkylaluminum or alkyllithium.

[0049]

[0050] Step 3: The compound of formula IV undergoes a deprotonation reaction, and then reacts with hafnium tetrachloride to obtain the compound of formula V;

[0051]

[0052] Step 4: Compound V reacts with alkyl magnesium halide to generate catalyst I;

[0053]

[0054] Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, the hydrocarbon group R2 in the reducing agent has 1-10 carbon atoms, the alkyl group R3 in the alkyl magnesium halide has 1-6 carbon atoms, and X is a halogen.

[0055] The above reaction steps can be derived by those skilled in the art based on the principles of organic reactions, and are not particularly limited in this invention. The preparation process of the bridged pyridine-amine hafnium catalyst of this invention is carried out under inert gas protection. This invention does not particularly limit the type of inert gas, such as nitrogen or argon.

[0056] As a preferred technical solution, the reaction of o-chlorophenol with dibromobutane is carried out under alkaline catalysis, such as potassium carbonate catalysis, at a reaction temperature of -10 to 5°C. The reaction is carried out under an inert gas atmosphere; the type of inert gas is not particularly limited, but can be nitrogen, argon, etc. The resulting dichlorophenyl diether compound reacts with an alkyllithium reagent and a dialkyl borate ester to obtain compound VII. In one embodiment, the alkyllithium reagent has the structure R4Li, where R4 is an alkyl group having 1-6 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.; the dialkyl borate ester has the structure R5OBOR5, where R5 is an alkyl group having 1-6 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. The reaction of dichlorophenyl diether compounds with alkyl lithium reagents and dialkyl borate esters is also carried out under an inert gas atmosphere. In another embodiment, the reaction process is as follows: the dichlorophenyl diether compound is dissolved in an organic solvent, and alkyl lithium reagents and dialkyl borate esters are added dropwise at -40 to -55°C. After the addition is complete, the temperature is raised to 20-30°C to carry out the reaction, and then post-treatment is performed to obtain compound VII.

[0057] Then, the compound of formula VII is coupled with the compound of formula VI to give the compound of formula II. In one embodiment, the reaction is carried out under palladium catalysis, for example, under palladium dichloride catalysis; in another embodiment, the reaction is carried out under alkaline conditions, for example, in the presence of potassium carbonate. The reaction temperature is, for example, the reflux temperature of a mixture of solvents ethanol, toluene, and water.

[0058] Step 1 involves reacting compound II with 2,6-diisopropylaniline via a condensation reaction to yield compound III. This reaction can be carried out under acid catalysis, such as p-toluenesulfonic acid, at a temperature, for example, the reflux temperature of the organic solvent.

[0059] Step 2 involves reducing compound III to obtain compound IV, using trialkylaluminum or alkyllithium as the reducing agent. In one embodiment, the alkyl group in the reducing agent is R2, which is a alkyl group having 1-10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, propenyl, phenyl, 2-isopropylphenyl, etc.; further, trialkylaluminum is, for example, trimethylaluminum, triethylaluminum, etc., and alkyllithium is, for example, 2-isopropylphenyllithium, isobutyllithium, etc. In another embodiment, the reaction process involves dissolving compound III in an organic solvent, adding the reducing agent at -30°C to -50°C, stirring, then heating to 20-30°C with stirring, and finally heating to reflux.

[0060] Step 3 involves deprotonating compound IV and then reacting it with hafnium tetrachloride to obtain compound V. The reagent used for the deprotonation reaction is, for example, alkyllithium, such as n-butyllithium, and the deprotonation reaction temperature is, for example, reflux temperature.

[0061] Step 4 involves reacting compound V with alkyl magnesium halide to generate catalyst of formula I. In one embodiment, the alkyl group R3 in the alkyl magnesium halide is a hydrocarbon group having 1-6 carbon atoms, such as ethylene, methyl, propyl, butyl, etc., and X is a halogen, such as chlorine, bromine, etc. The reaction is carried out, for example, at 20-30°C, and the target product can be purified by crystallization or other methods.

[0062] Therefore, this invention provides a method for preparing the above-mentioned bridged pyridine-amine hafnium catalyst. First, o-chlorophenol undergoes a substitution reaction with dibromobutane to obtain a dichlorophenyl diether compound. Then, the dichlorophenyl diether compound reacts with an alkyllithium reagent and a dialkyl borate ester to obtain a phenyl diboronic acid compound. A pyridone (aldehyde) compound undergoes a coupling reaction with the phenyl diboronic acid compound to obtain a phenyl-substituted diphenylpyridone (aldehyde) compound. The phenyl-substituted diphenylpyridinaldehyde or pyridone compound undergoes a condensation reaction with 2,6-diisopropylaniline to obtain a pyridine diimine compound. The obtained pyridine diimine compound is reduced with a strong reducing agent, trialkylaluminum or alkyllithium, to prepare a pyridine-amine compound. The pyridine-amine compound undergoes a deprotonation reaction with n-butyllithium, followed by the addition of a hafnium tetrachloride metal salt to prepare the corresponding bridged pyridine-amine hafnium chloride compound. Finally, the bridged pyridine-amine hafnium chloride compound reacts with alkyl magnesium halide to prepare the corresponding bridged pyridine-amine hafnium catalyst.

[0063] The bridged pyridine-amine hafnium catalyst of the present invention can be used in the butene-1 polymerization reaction. In one embodiment, butene-1 is used as raw material in the butene-1 polymerization reaction, the above-mentioned bridged pyridine-amine hafnium catalyst is used as the main catalyst, and a boron compound is used as a co-catalyst.

[0064] In one embodiment, the boron compound is [Ph3C][B(C6F5)4], and the molar ratio of the co-catalyst to the main catalyst is (0.5-5):1. In another embodiment, alkyl aluminum is added as an activator during polymerization, and the molar ratio of the activator to the main catalyst is (0.01-1100):1. The alkyl aluminum can be trimethylaluminum, triethylaluminum, or triisobutylaluminum; preferably, the alkyl aluminum is triisobutylaluminum. In yet another embodiment, the molar ratio of the main catalyst, co-catalyst, and activator, expressed as Hf:B:Al, is 1:(1.5-1.8):(180-400).

[0065] In one embodiment, the butene-1 polymerization reaction is a bulk polymerization, the molar ratio of butene-1 monomer to bridged pyridine-amine hafnium catalyst is 8000 to 40000:1, and the polymerization temperature is 25 to 90°C.

[0066] The polybutene-1 obtained by the method of this invention has a molecular weight ≥3 million, a molecular weight distribution ≤3, a melting point ≥220℃, and better mechanical properties, with a tensile strength ≥25MPa and an impact strength ≥130kJ / m. 2 Furthermore, the polymerization reaction conditions are mild, the polymerization activity is high, the monomer conversion rate is high, and the entire polymerization reaction is highly efficient and controllable.

[0067] In one embodiment, the polybutene-1 of the present invention has a weight-average molecular weight of 3.8 million to 6.5 million, a molecular weight distribution of 2.0 to 3.0, an isotacticity greater than 98%, a melting temperature of 245 to 300°C, a tensile strength of 34 to 57 MPa, and an impact strength of 50 to 175 kJ / m. 2 .

[0068] Therefore, this invention can not only solve the problem of overcapacity of butene-1, but also prepare high-performance polybutene-1 resin, which has a positive effect on optimizing the industrial structure of butene-1 resources.

[0069] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0070] The structural formulas of the bridged pyridineamine hafnium complexes in each embodiment are as follows:

[0071]

[0072] In the bridged pyridineamine hafnium complex Hf1, R1 represents hydrogen, R2 represents 2-isopropylphenyl, and R3 represents methyl.

[0073] The pyridineamine hafnium complex Hf2, where R1 represents methyl, R2 represents methyl, and R3 represents methyl;

[0074] The pyridineamine hafnium complex Hf3, where R1 represents hydrogen, R2 represents 2-isopropylphenyl, and R3 represents ethyl;

[0075] The pyridineamine hafnium complex Hf4, where R1 represents methyl, R2 represents methyl, and R3 represents ethyl;

[0076] The pyridineamine hafnium complex Hf5, where R1 represents methyl, R2 represents methyl, and R3 represents n-propyl;

[0077] The pyridineamine hafnium complex Hf6, where R1 represents methyl, R2 represents methyl, and R3 represents isopropyl;

[0078] The pyridineamine hafnium complex Hf7, where R1 represents hydrogen, R2 represents ethyl, and R3 represents methyl;

[0079] The pyridine-amino-hafnium complex Hf8, where R1 represents ethyl, R2 represents 2-isopropylphenyl, and R3 represents methyl.

[0080] Example 1

[0081] This embodiment provides a method for synthesizing a pyridine-amine hafnium complex, the reaction route of which is shown below. Under a nitrogen atmosphere, 10 mmol of dibromobutane, 25 mmol of o-chlorophenol, and 3 g of potassium carbonate are placed in a reaction flask and reacted at 0°C for 12 h. The dichlorophenyl diether compound is obtained by vacuum distillation.

[0082] Under a nitrogen atmosphere, 11 mmol of dichlorophenyl diether was dissolved in tetrahydrofuran, and 20 mmol of n-butyllithium and 40 mmol of dimethyl borate were added dropwise at -50°C. After the addition was completed, the temperature was raised to room temperature and the reaction was continued for 12 h. The reaction was quenched with ammonium chloride in an ice-water bath, separated, extracted with ethyl acetate, and dried under vacuum to obtain phenyl diboronic acid compound.

[0083] Under a nitrogen atmosphere, 25 mmol of 6-bromopyridin-2-carboxaldehyde / 2-acetyl-6-bromopyridinium, 10 mmol of phenyl diboronic acid, 15 mg of palladium dichloride (triphenylphosphine) chloride, and 3 g of potassium carbonate were added sequentially to a side-necked flask. Then, 30 mL of ethanol, 20 mL of toluene, and 10 mL of water were added using a syringe, and the mixture was refluxed for 24 h. After separation, the mixture was extracted with ethyl acetate, washed with NaHCO3 solution, dried over anhydrous Na2SO4, and evaporated to dryness to obtain the diphenylpyridinone (aldehyde) compound.

[0084] Under a nitrogen atmosphere, 10 mmol of diphenylpyridone (aldehyde), 25 mmol of 2,6-di-tert-butylaniline, and 10 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene, and the mixture was refluxed for 48 h after separation of water. The solvent was evaporated, the mixture was washed with ethanol, and dried to obtain the pyridine diimide compound.

[0085] The pyridine diimine compound was dissolved in dry tetrahydrofuran. 2-Isopropylbenzenelithium / trimethylaluminum was slowly added dropwise to the solution at -40°C, stirred for 1 h, then slowly restored to room temperature, and heated to 90°C under reflux overnight. The solution was quenched with aqueous NH₄Cl solution in an ice-water bath, separated, extracted with ethyl acetate, washed with brine, dried over anhydrous Na₂SO₄, and then evaporated to dryness to obtain the pyridine amino compound ligand.

[0086] In a nitrogen-filled reaction flask, 1.7 mmol of pyridineamine ligand was weighed and dissolved in 20 mL of dry toluene. 1.14 mL of n-butyllithium solution was added dropwise at 0 °C, and the mixture was heated under reflux for 3 h. The toluene was dried under vacuum, and the solid was washed with n-hexane. The supernatant was discarded to obtain a yellow lithium salt. The lithium salt was redissolved in toluene, and 0.61 g of HfCl4 was transferred into the reaction system. The mixture was heated to 90 °C and refluxed overnight. The solution temperature was then lowered to room temperature, and 2.13 mL of MeMgBr / EtMgBr / PrMgBr / i-PrMgBr solution was added dropwise. The mixture was stirred at room temperature for 3 h. The solvent was dried under vacuum, and the solid was washed three times with n-hexane. The n-hexane filtrate was collected after filtration. The solvent was concentrated to approximately 3 mL, and the solid was crystallized overnight at -35 °C. The crystals were filtered, washed with frozen n-hexane, and dried to obtain the pyridineamine hafnium complex.

[0087]

[0088] Example 2

[0089] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf1 catalyst. The steps are as follows:

[0090] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 1500g of butene-1 monomer (monomer to pyridine-amine hafnium catalyst molar ratio 26000:1) was added, followed by 0.1mol of triisobutylaluminum (Al:Hf = 200). The temperature was maintained at 60℃ and stirred for half an hour. Subsequently, a toluene solution prepared by 0.001mol of bridged pyridine-amine hafnium catalyst Hf1 and 0.0015mol of [Ph3C][B(C6F5)4] was added to the system to initiate polymerization. After 60 minutes of polymerization, a 10wt% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, washed three times with ethanol, and vacuum dried to constant weight.

[0091] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 21.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 5.1 million, a molecular weight distribution index of 2.2, a melting temperature of 237℃, an isotacticity of >99%, a tensile strength of 42 MPa, and an impact strength of 168 KJ / m. 2 The carbon NMR spectrum of the prepared polybutene-1 is shown below. Figure 1 As shown, the DSC curve of polybutene-1 is as follows: Figure 2 As shown, the GPC curve of polybutene-1 is as follows: Figure 3 As shown. By Figure 1 As shown, the isotacticity of polybutene-1 is ≥99%; from Figure 2As shown, the melting temperature of polybutene-1 is 241.5℃; from Figure 3 As shown, polybutene-1 has a weight-average molecular weight of 5.1 million and a molecular weight distribution index of 2.2.

[0092] Example 3

[0093] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf2.

[0094] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 25.8 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 3.86 million, a molecular weight distribution index of 2.4, a melting temperature of 233°C, an isotacticity of >99%, a tensile strength of 31 MPa, and an impact strength of 148 KJ / m². 2 .

[0095] Example 4

[0096] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the alkyl aluminum is trimethylaluminum.

[0097] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 19.9 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 3.02 million, a molecular weight distribution index of 2.7, a melting temperature of 310°C, an isotacticity of >99%, a tensile strength of 29 MPa, and an impact strength of 135 KJ / m². 2 .

[0098] Example 5

[0099] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the alkyl aluminum is triethylaluminum.

[0100] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 24.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 3.89 million, a molecular weight distribution index of 2.1, a melting temperature of 325°C, an isotacticity of >99%, a tensile strength of 32 MPa, and an impact strength of 138 KJ / m². 2 .

[0101] Example 6

[0102] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of [Ph3C][B(C6F5)4] to the hafnium complex Hf2 is 1:1.

[0103] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 18.7 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 3.06 million, a molecular weight distribution index of 2.4, a melting temperature of 321℃, an isotacticity of >99%, a tensile strength of 30 MPa, and an impact strength of 131 KJ / m. 2 .

[0104] Example 7

[0105] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of [Ph3C][B(C6F5)4] to the hafnium complex Hf2 is 3:1.

[0106] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 30.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 4.08 million, a molecular weight distribution index of 2.8, a melting temperature of 354 °C, an isotacticity of >99%, a tensile strength of 33 MPa, and an impact strength of 145 KJ / m². 2 .

[0107] Example 8

[0108] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of triisobutylaluminum to the hafnium complex Hf2 is 0:1, i.e., no triisobutylaluminum is added.

[0109] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 8.1 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 2.46 million, a molecular weight distribution index of 2.2, a melting temperature of 154 °C, an isotacticity of >99%, a tensile strength of 27 MPa, and an impact strength of 131 KJ / m². 2 .

[0110] Example 9

[0111] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of triisobutylaluminum to the hafnium complex Hf2 is 300:1.

[0112] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 48.0 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 4.65 million, a molecular weight distribution index of 2.5, a melting temperature of 280℃, an isotacticity of >99%, a tensile strength of 39 MPa, and an impact strength of 142 KJ / m. 2 .

[0113] Example 10

[0114] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the polymerization reaction temperature was 20°C.

[0115] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 13.1 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 1.75 million, a molecular weight distribution index of 2.2, a melting temperature of 140°C, an isotacticity of >99%, a tensile strength of 21 MPa, and an impact strength of 112 KJ / m. 2 .

[0116] Example 11

[0117] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the polymerization reaction temperature was 80°C.

[0118] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 18.3 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 2.64 million, a molecular weight distribution index of 2.3, a melting temperature of 165℃, an isotacticity of >99%, a tensile strength of 24 MPa, and an impact strength of 129 KJ / m. 2 .

[0119] Example 12

[0120] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the polymerization reaction temperature was 100°C.

[0121] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 2.1 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 960,000, a molecular weight distribution index of 2.5, a melting temperature of 148℃, an isotacticity of >99%, a tensile strength of 18 MPa, and an impact strength of 94 KJ / m. 2 .

[0122] Example 13

[0123] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of butene-1 monomer to Hf2 is 4000.

[0124] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 0.95 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 740,000, a molecular weight distribution index of 2.6, a melting temperature of 114℃, an isotacticity of >99%, a tensile strength of 15 MPa, and an impact strength of 89 KJ / m. 2 .

[0125] Example 14

[0126] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of butene-1 monomer to Hf2 is 15000.

[0127] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 6.9 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 1.31 million, a molecular weight distribution index of 2.7, a melting temperature of 145°C, an isotacticity of >99%, a tensile strength of 23 MPa, and an impact strength of 119 KJ / m. 2 .

[0128] Example 15

[0129] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of butene-1 monomer to Hf2 is 40000.

[0130] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 32.2 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 3.8 million, a molecular weight distribution index of 2.7, a melting temperature of 264 °C, an isotacticity of >99%, a tensile strength of 29 MPa, and an impact strength of 135 KJ / m². 2 .

[0131] Example 16

[0132] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf2 catalyst. Following the experimental method in Example 2, the molar ratio of butene-1 monomer to Hf2 is 60000.

[0133] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 50.1 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 5.52 million, a molecular weight distribution index of 2.9, a melting temperature of 280℃, an isotacticity of >99%, a tensile strength of 49 MPa, and an impact strength of 154 KJ / m. 2 .

[0134] Example 17

[0135] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf3 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf3.

[0136] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 16.7 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 3.04 million, a molecular weight distribution index of 2.4, a melting temperature of 229 °C, an isotacticity of >99%, a tensile strength of 22 MPa, and an impact strength of 111 KJ / m. 2 .

[0137] Example 18

[0138] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf4 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf4.

[0139] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 17.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 2.99 million, a molecular weight distribution index of 2.3, a melting temperature of 231℃, an isotacticity of >97%, a tensile strength of 24 MPa, and an impact strength of 137 KJ / m. 2 .

[0140] Example 19

[0141] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf5 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf5.

[0142] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 9.9 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 2.47 million, a molecular weight distribution index of 2.5, a melting temperature of 231 °C, an isotacticity of >99%, a tensile strength of 17 MPa, and an impact strength of 97 KJ / m². 2 .

[0143] Example 20

[0144] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf6 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf6.

[0145] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 14.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 3.17 million, a molecular weight distribution index of 2.4, a melting temperature of 233℃, an isotacticity of >98%, a tensile strength of 28 MPa, and an impact strength of 122 KJ / m. 2 .

[0146] Example 21

[0147] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf7 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf7.

[0148] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 10.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 2.46 million, a molecular weight distribution index of 2.2, a melting temperature of 221℃, an isotacticity of >99%, a tensile strength of 19 MPa, and an impact strength of 98 KJ / m.2 .

[0149] Example 22

[0150] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf8 catalyst. Following the experimental method in Example 2, the hafnium complex is Hf8.

[0151] In this embodiment, the bridged pyridine-amine hafnium catalyst exhibited a catalytic activity of 9.7 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 1.97 million, a molecular weight distribution index of 2.4, a melting temperature of 219 °C, an isotacticity of >98%, a tensile strength of 11 MPa, and an impact strength of 87 KJ / m². 2 .

[0152] Example 23

[0153] This embodiment provides a method for preparing ultra-high molecular weight polybutene-1, which involves bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium Hf1 catalyst. Following the experimental method in Example 2, the co-catalyst is B(C6F5)3.

[0154] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst is 19.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 has a weight-average molecular weight of 5.07 million, a molecular weight distribution index of 2.2, a melting temperature of 237℃, an isotacticity of >99%, a tensile strength of 39 MPa, and an impact strength of 147 KJ / m. 2 .

[0155] To better illustrate the beneficial effects of the present invention, polybutene-1 was prepared by bulk polymerization of butene-1 monomer using Ziegler-Natta catalyst and zirconium monoxide catalyst as a comparative example.

[0156] Comparative Example 1

[0157] This comparative example provides a method for preparing polybutene-1, which involves homopolymerization of butene-1 catalyzed by a Ziegler-Natta catalyst, and the steps are as follows:

[0158] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 1500g of 1-Butene monomer and 6ml of triethylaluminum were added, and the mixture was stirred at 60℃ for half an hour. Subsequently, 400mg of Ziegler-Natta catalyst (prepared according to the literature "Isospecific olymerizations of 1-Butene Catalyzed by MgCl2 / TiCl4 / Internal Donor-AlR3 / External Donor System") was added to the reaction system, and the time was set. After 60 minutes of polymerization, a 10wt% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, washed three times with ethanol, and vacuum dried to constant weight.

[0159] In this embodiment, the Ziegler-Natta catalyst exhibited a catalytic activity of 9.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 had a weight-average molecular weight of 580,000, a molecular weight distribution index of 6.2, a melting temperature of 126 °C, an isotacticity of 97%, a tensile strength of 7.4 MPa, and an impact strength of 39 KJ / m². 2 .

[0160] Comparative Example 2

[0161] This comparative example provides a method for preparing polybutene-1, which involves homopolymerization of butene-1 catalyzed by a zirconium-based catalyst. The structural formula of the zirconium-based catalyst is shown below, and the preparation method steps are as follows:

[0162] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 1500g of butene-1 monomer and 7ml of methylaluminoxane (MAO) were added, and the mixture was stirred at 60℃ for half an hour. Subsequently, 0.015mol of zirconium monoxide catalyst was added to the reaction system and the time was set. After polymerization reached 60 minutes, a 10wt% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, washed three times with ethanol, and vacuum dried to constant weight.

[0163] In this comparative example, the catalytic activity of the zirconium cadmium catalyst was 4.9 kg polymer / (mmol Zr·h). The prepared polybutene-1 had a weight-average molecular weight of 380,000, a molecular weight distribution index of 1.9, a melting temperature of 102℃, an isotacticity of 90%, a tensile strength of 6.9 MPa, and an impact strength of 29 KJ / m. 2 .

[0164]

[0165] The results from the examples and comparative examples show that the non-metallocene catalyst of this invention exhibits a high polymerization activity of 50.1 kg polymer / (mmol Hf·h) for butene-1 polymerization. Furthermore, the prepared polybutene-1 has a high weight-average molecular weight of 5.52 million, a molecular weight distribution index of 2.2, a melting temperature of 280°C, and an isotacticity of >99%. It also possesses excellent temperature resistance and mechanical properties, with a tensile strength of 49 MPa and an impact strength of 154 KJ / m². 2 The polymerization of butene-1 using a Ziegler-Natta catalyst resulted in decreased catalytic activity, only 9.6 kg polymer / (mmol Ti·h). Furthermore, due to the multiple active sites, the polymer distribution was significantly broadened, with a molecular weight distribution index of 6.2, and the resulting polymer melt temperature was significantly lower, only 126 °C. Simultaneously, the polymerization of butene-1 using a metallocene catalyst showed further decreased activity, only 4.9 kg polymer / (mmol Zr·h), due to the large steric hindrance making it difficult for butene-1 monomers to insert.

[0166] This invention provides a bridged pyridine-amine hafnium catalyst, which mainly synthesizes the bridged pyridine-amine hafnium compound through Suzuki coupling reaction, Schiff base reaction, and reduction reaction. This non-metallocene catalyst has a wider steric fossa, which is conducive to the coordination insertion of sterically hindered butene-1 monomers, thus improving the polymerization activity and the molecular weight of the product. Furthermore, this non-metallocene bridged pyridine-amine hafnium complex is a single-active-center catalyst system. By controlling the polymerization of butene-1 through the chiral metal center, polymers with narrower molecular weight distribution and higher isotacticity can be prepared. Therefore, the bridged pyridine-amine hafnium catalyst of this invention overcomes the defects or shortcomings of Ziegler-Natta catalysts in producing polybutene-1 with a wide molecular weight distribution, while polybutene-1 produced by metallocene catalysts has low molecular weight and low activity. Simultaneously, this invention also provides a method for the preparation of polybutene-1 catalyzed by a non-metallocene catalyst. This polymerization reaction is characterized by mild reaction conditions, high polymerization activity, high monomer conversion rate, and efficient and controllable polymerization. Furthermore, this technology can effectively break the foreign monopoly on polybutene-1 products and optimize the industrial structure of butene-1 resources for high-end utilization.

[0167] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A bridged pyridineamine-based hafnium catalyst, characterized in that, The catalyst is used to catalyze the polymerization of butene-1, and the catalyst has the following structure: Formula I: Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, R2 is a hydrocarbon group having 1-10 carbon atoms, and R3 is a hydrocarbon group having 1-6 carbon atoms.

2. The bridged pyridineamine hafnium catalyst according to claim 1, characterized in that, R1 is hydrogen, an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; R2 is an alkyl group having 1-6 carbon atoms, an olefinic group having 2-6 carbon atoms, or an aromatic group having 6-10 carbon atoms; and R3 is an alkyl group having 1-6 carbon atoms.

3. A method for preparing a bridged pyridine-amine hafnium catalyst, characterized in that, The catalyst is used to catalyze the polymerization of butene-1, and the preparation method includes the following steps: Step 1: The compound of formula II is subjected to a condensation reaction with 2,6-diisopropylaniline to obtain the compound of formula III; Step 2: The compound of formula III is reduced to obtain the compound of formula IV. The reducing agent is trialkylaluminum or alkyllithium. Step 3: The compound of formula IV undergoes a deprotonation reaction, and then reacts with hafnium tetrachloride to obtain the compound of formula V; Step 4: Compound V reacts with alkyl magnesium halide to generate catalyst I; Wherein, R1 is hydrogen, a hydrocarbon group having 1-10 carbon atoms, the hydrocarbon group R2 in the reducing agent has 1-10 carbon atoms, the alkyl group R3 in the alkyl magnesium halide has 1-6 carbon atoms, and X is a halogen.

4. The method for preparing the bridged pyridine-amine hafnium catalyst according to claim 3, characterized in that, The preparation method of the compound of formula II is as follows: the compound of formula VI and the compound of formula VII are coupled together to obtain the compound of formula II; 5. The method for preparing the bridged pyridine-amine hafnium catalyst according to claim 4, characterized in that, The preparation method of the compound of formula VII is as follows: o-chlorophenol is reacted with dibromobutane to generate dichlorophenyl diether compound, and then the dichlorophenyl diether compound is reacted with alkyllithium reagent and dialkyl borate ester to obtain compound of formula VII; 6. The method for preparing the bridged pyridine-amine hafnium catalyst according to claim 5, characterized in that, The alkyl lithium reagent has the structure R4Li, wherein R4 is an alkyl group having 1-6 carbons; the dialkyl borate ester has the structure R5OBOR5, wherein R5 is an alkyl group having 1-6 carbons.

7. A method for butene-1 polymerization, characterized in that, The polymerization reaction is carried out using butene-1 as raw material, the bridged pyridine-amine hafnium catalyst as described in claim 1 or 2 as the main catalyst, and a boron compound as a co-catalyst.

8. The method for butene-1 polymerization according to claim 7, characterized in that, The boron compound has the structure [Ph3C][B(C6F5)4], and the molar ratio of the co-catalyst to the main catalyst is (0.5-5):1; alkyl aluminum is also added as an activator during polymerization, and the molar ratio of the activator to the main catalyst is (0.01-1100):

1.

9. The method for butene-1 polymerization according to claim 7, characterized in that, The molar ratio of butene-1 monomer to the main catalyst is 8000–40000:1, and the polymerization temperature is 25–90°C.

10. The polybutene-1 obtained by the method according to any one of claims 7-9, characterized in that, The polybutene-1 has a weight-average molecular weight of not less than 3 million, a molecular weight distribution of not more than 3.0, an isotacticity of not less than 98%, and a melting temperature of not less than 220°C.

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