Polybutene-1 and a method for its production, a non-metallocene catalyst used therefor and a method for its production

Abstract

The application provides polybutene-1 and a preparation method thereof, a non-metallocene catalyst used in the preparation method and a preparation method of the non-metallocene catalyst, and the non-metallocene catalyst comprises the following formula I structure: wherein R1 and R2 are selected from hydrogen and a hydrocarbon group with 1-10 carbon atoms, R1 and R2 are the same or different, R3 is selected from hydrogen and a hydrocarbon group with 1-10 carbon atoms, R4 is selected from a methyl group, an ethyl group and a n-propyl group, and Ar is a phenyl group, a naphthyl group, a phenyl group substituted with an aliphatic hydrocarbon group or a naphthyl group substituted with an aliphatic hydrocarbon group. The non-metallocene catalyst of the application has a bridged pyridyl amine hafnium structure, is used for catalyzing synthesis of polybutene-1, has high catalytic activity, high monomer conversion rate, and the prepared polybutene-1 has high stereoregularity and narrow distribution.

Description

Technical Field

[0001] This invention relates to the field of olefin catalytic polymerization technology. More specifically, it relates to a non-metallocene catalyst and its preparation method, a method for catalytic synthesis of polybutene-1 using the non-metallocene catalyst, and the prepared polybutene-1. Background Technology

[0002] High-isobutylene-1 (PB) is a semi-crystalline polyolefin thermoplastic resin polymerized from butene-1 monomer, and enjoys the reputation of being "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. Therefore, this type of high-end thermoplastic resin has important applications in radiator connections, hot and cold water supply systems, underfloor heating, hot melt adhesives, and films and sheets.

[0003] Polybutene-1 (PP-1) is mainly prepared by bulk polymerization of PP-1 monomers catalyzed by a suitable catalyst. Currently, there are two main types of catalyst systems for catalyzing the polymerization of PP-1 monomers: Ziegler-Natta catalysts and metallocene catalysts. Early methods using magnesium chloride-supported Ziegler-Natta catalysts effectively catalyzed the polymerization of PP-1, yielding polymers with high isotactic crystallinity. Due to the high catalytic efficiency, good overall performance, and low cost of Ziegler-Natta catalysts, they are the primary catalysts used in the industrial production of PP-1. 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 titanium-supported catalyst 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. However, due to the multiple active sites of the Ziegler-Natta catalyst, the resulting polymers have 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] Metallocene catalysts can also catalyze the polymerization of 1-butene, but the structure of the metallocene catalyst has a significant impact on the isotacticity of the final product. Currently, it has been reported that metallocene catalysts can catalyze the polymerization of 1-butene, and the regularity of the product is as high as 90% or more. For example, Resconi (Resconi L, Camurati I, Malizia F. Metallocene Catalysts for 1-Butene Polymerization[J]. Macromolecular Chemistry & Physics, 2010, 208(4): 423-423.) synthesized dimethylsilyl-bridged zirconium dichloride catalysts with indene ligands containing different substituents, with MAO as a co-catalyst, and studied the effects of different ligand catalysts on the polymerization of 1-butene and the polymer. Studies have found that the highest catalytic activity during bulk polymerization at 70℃ is 195.0 kgPB / g mc·h (mc = metallocene), with a molecular weight (Mw) exceeding 4.0 × 10⁵ g / mol and a molecular weight distribution of 2.1–2.7. The isotacticity of the polymer is related to the indenyl complex, reaching a maximum of 98.5%. Due to the single metal center, the molecular weight distribution of polybutene-1 prepared by metallocene catalysts is relatively narrow, generally below 3. However, metallocene catalysts have large steric hindrance, making it difficult for sterically hindered butene-1 monomers to insert, resulting in lower catalytic activity for butene-1, more than 10 times lower than that of Ziegler-Natta catalysts.

[0005] Currently, polybutene-1 has been successfully commercialized by Basell and Mitsui Oil Company (now Mitsui Chemicals), but there is no domestic production of polybutene in China, and the product is entirely dependent on imports, resulting in high prices. At the same time, there is an overcapacity of butene-1 in China, with extremely low utilization rates, and more than 75% is sold as a fuel oil component. How to increase the added value of butene-1 products is a major problem that urgently needs to be solved. Summary of the Invention

[0006] The main objective of this invention is to provide a polybutene-1 and its preparation method, as well as the non-metallocene catalyst used and its preparation method, to overcome the shortcomings of the prior art in which polybutene-1 prepared by Ziegler-Natta catalyst has a wide molecular weight distribution, while polybutene-1 prepared by metallocene catalyst has a low molecular weight and low activity.

[0007] To achieve the above objectives, the present invention provides a non-metallocene catalyst for catalyzing the polymerization reaction of butene-1, the non-metallocene catalyst comprising the structure of Formula I:

[0008]

[0009] R1 and R2 are selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R1 and R2 may be the same or different. R3 is selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R4 is selected from methyl, ethyl, and n-propyl. Ar is phenyl, naphthyl, phenyl substituted with aliphatic hydrocarbon group, or naphthyl substituted with aliphatic hydrocarbon group.

[0010] The non-metallocene catalyst of the present invention, wherein R1 and R2 are selected from hydrogen, alkyl groups having 1-6 carbon atoms, olefinic groups having 1-6 carbon atoms, or aromatic hydrocarbon groups having 6-10 carbon atoms; the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted phenyl group has 1-6 carbon atoms, and the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted naphthyl group has 1-6 carbon atoms.

[0011] The non-metallocene catalyst of the present invention, wherein R1 and R2 are selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, and 2-isopropylphenyl; the aliphatic hydrocarbon group in the phenyl group substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms, and the aliphatic hydrocarbon group in the naphthyl group substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms; R3 is selected from methyl, ethyl, n-propyl, and isopropyl; and R4 is selected from methyl.

[0012] In the non-metallocene catalyst of the present invention, when Ar is phenyl or naphthyl, R1 is hydrogen and R2 is 2-isopropylphenyl, or R1 is methyl and R2 is methyl.

[0013] To achieve the above objectives, the present invention also provides a method for preparing a non-metallocene catalyst for catalyzing the polymerization reaction of butene-1. The preparation method includes the following steps:

[0014] Step 1: The pyridone (aldehyde) compound undergoes a coupling reaction with arylboronic acid to obtain an aryl-substituted 2-aryl-pyridone (aldehyde) compound.

[0015]

[0016] Step 2: The 2-aryl-pyridone (aldehyde) compound undergoes a condensation reaction with 3,3-disubstituted-4,4-biphenyldiamine to give the pyridinediimide compound;

[0017]

[0018] Step 3: The pyridine diimine compound undergoes a reduction reaction with a reducing agent to obtain a bridged substituted pyridine amino compound ligand;

[0019]

[0020] Step 4: The bridged substituted pyridine amino compound ligand undergoes a deprotonation reaction, and then reacts with hafnium tetrachloride to obtain the bridged substituted pyridine amino hafnium chloride compound;

[0021]

[0022] Step 5: The bridged substituted pyridine-amine hafnium chloride compound reacts with alkyl magnesium bromide to give the bridged pyridine-amine hafnium alkyl compound;

[0023]

[0024] In this context, R1 and R2 are selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R1 and R2 may be the same or different. R3 is selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R4 is selected from methyl, ethyl, and n-propyl. Ar is phenyl, naphthyl, phenyl substituted with aliphatic hydrocarbon group, or naphthyl substituted with aliphatic hydrocarbon group. n is 1, 2, or 3. M is a metal.

[0025] The method for preparing the non-metallocene catalyst of the present invention, wherein the reducing agent is trialkylaluminum or aryllithium.

[0026] To achieve the above objectives, the present invention further provides a method for preparing polybutene-1, wherein butene-1 is used as a monomer and the above-mentioned non-metallocene catalyst is used as a catalyst to carry out a polymerization reaction to obtain polybutene-1.

[0027] The method for preparing polybutene-1 according to the present invention includes the addition of an activator in the polymerization reaction, wherein the molar ratio of the catalyst to the activator is 1:1 to 10; the activator is a composition of triphenylcarbazide tetra(pentafluorobenzene)borate and alkylaluminum, wherein the molar ratio of triphenylcarbazide tetra(pentafluorobenzene)borate to alkylaluminum is 1:50 to 300.

[0028] The method for preparing polybutene-1 according to the present invention, wherein the molar ratio of the butene-1 monomer to the sum of the amounts of the catalyst and the activator is 100 to 60000:1; and the polymerization reaction temperature is 25 to 100°C.

[0029] To achieve the above objectives, the present invention further provides polybutene-1 prepared by the above preparation method.

[0030] The beneficial effects of this invention are:

[0031] This invention provides a non-metallocene catalyst with a bridged pyridineamine hafnium structure for the catalytic synthesis of polybutene-1. This catalyst exhibits high catalytic activity and high monomer conversion, producing polybutene-1 with high isotacticity and a narrow molecular weight distribution. Furthermore, the polybutene-1 prepared by this non-metallocene catalyst has a weight-average molecular weight exceeding 300,000, a narrower molecular weight distribution (below 3.0), and better mechanical properties and thermal stability. The isotacticity can reach >99%, and the melting temperature can reach 170°C. In addition, the catalyst of this invention provides mild reaction conditions and highly efficient and controllable polymerization for the catalytic synthesis of polybutene-1. Attached Figure Description

[0032] Figure 1 This is the carbon NMR spectrum of polybutene-1 prepared in Example 1 of the present invention.

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

[0034] Figure 3 This is a reaction route diagram for the pyridineamine hafnium complex of the present invention.

[0035] Figure 4 The structural formula of the zirconium cyclone catalyst of Comparative Example 20 of this invention is shown.

[0036] Figure 5 The pyridineamine hafnium complex Hf4 of this invention 1 H NMR spectrum.

[0037] Figure 6 This is the mass spectrum of the pyridineamine hafnium complex Hf4 of the present invention.

[0038] Figure 7 The pyridineamine hafnium complex Hf1 of this invention 1 H NMR spectrum.

[0039] Figure 8 This is the mass spectrum of the pyridineamine hafnium complex Hf1 of the present invention. Detailed Implementation

[0040] The present invention is further illustrated below with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of protection claimed by the present invention.

[0041] This invention discloses a non-metallocene catalyst for catalyzing the polymerization of butene-1, the non-metallocene catalyst comprising the structure of Formula I:

[0042]

[0043] R1 and R2 are selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R1 and R2 may be the same or different. R3 is selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R4 is selected from methyl, ethyl, and n-propyl. Ar is phenyl, naphthyl, phenyl substituted with aliphatic hydrocarbon group, or naphthyl substituted with aliphatic hydrocarbon group.

[0044] In this invention, Ar and Hf (hafnium) are bonded by single bonds, and Ar is bonded by a single bond to the carbon at position 2 of the pyridine group. In addition, Hf and the carbon at position 2 of the pyridine group are respectively connected to two adjacent carbons on the same benzene ring of Ar. When Ar is a phenyl or an aliphatic hydrocarbon-substituted phenyl, the non-metallocene catalyst of this invention can be represented by the following formula, where R is an aliphatic hydrocarbon substituent. This invention does not particularly limit the position and number of aliphatic hydrocarbon substituents. For example, each benzene ring may have 1, 2, 3 or 4 substituents.

[0045]

[0046] When Ar is a naphthyl or an aliphatic hydrocarbon-substituted naphthyl group, the non-metallocene catalyst of the present invention can be represented by the following formula, wherein R is an aliphatic hydrocarbon substituent. The present invention does not particularly limit the number and position of the aliphatic hydrocarbon substituent, which can be located on any benzene ring of the naphthyl group. Each naphthyl ring can have 1, 2, 3, 4, 5 or 6 substituents.

[0047]

[0048] The non-bridged bipyridinamide hafnium catalyst provided by this invention has a more open steric sphere compared to metallocene catalysts, which is beneficial for the coordination insertion of sterically hindered butene-1 monomers, thus improving the polymerization activity and increasing the molecular weight of the product. Furthermore, as a single-active-center catalyst system, this non-bridged bipyridinamide hafnium catalyst can produce polymers with narrower distributions compared to Ziegler-Natta catalysts. Additionally, this non-bridged bipyridinamide hafnium catalyst controls the polymerization of butene-1 through a chiral metal center, enabling the production of highly isotactic polymers. Therefore, the catalyst of this invention can produce highly active, high-molecular-weight, narrow-distribution, highly isotactic polybutene-1, and the resulting polymers exhibit better mechanical properties and thermal stability.

[0049] In one embodiment, the aliphatic hydrocarbon group (R) in the aliphatic hydrocarbon-substituted phenyl group has 1-6 carbon atoms, and the aliphatic hydrocarbon group (R) in the aliphatic hydrocarbon-substituted naphthyl group has 1-6 carbon atoms; in another embodiment, the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted phenyl group is an alkyl group having 1-6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc., and the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted naphthyl group is an alkyl group having 1-6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc.

[0050] In one embodiment, R1 and R2 of the present invention are selected from hydrogen, alkyl groups having 1-6 carbon atoms, olefinic groups having 1-6 carbon atoms, or aromatic hydrocarbon groups having 6-10 carbon atoms; in another embodiment, R1 and R2 of the present invention are selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl; R3 is selected from methyl, ethyl, n-propyl, isopropyl; R4 is selected from methyl; in yet another embodiment, Ar of the present invention is phenyl or naphthyl, R1 is hydrogen, and R2 is 2-isopropylphenyl; or Ar is phenyl or naphthyl, R1 is methyl, and R2 is methyl.

[0051] In the catalyst of the present invention, when the steric hindrance of the R4 group connected to the active center is small, the catalyst has high catalytic activity. When used to catalyze olefin polymerization, the olefin can be introduced into the main chain more quickly. Therefore, the R4 group of the present invention is more preferably methyl.

[0052] This invention also provides a method for preparing the above-mentioned non-metallocene catalyst. First, a pyridone (aldehyde) compound is coupled with arylboronic acid to obtain an aryl-substituted 2-aryl-pyridone (aldehyde) compound. Then, the 2-aryl-pyridone (aldehyde) compound is condensed with 3,3-disubstituted-4,4-biphenyldiamine to obtain a pyridinediimine compound. The obtained pyridinediimine compound is reduced with a strong reducing agent to prepare a bridged substituted pyridineamine ligand. The bridged substituted pyridineamine ligand undergoes a deprotonation reaction. Then, hafnium tetrachloride is added to prepare the corresponding bridged substituted pyridineamine hafnium chloride compound. Finally, the bridged substituted pyridineamine hafnium chloride compound reacts with alkyl magnesium bromide to prepare the corresponding bridged pyridineamine hafnium alkyl compound, which is the non-metallocene catalyst of this invention.

[0053] In one embodiment, the method for preparing the non-metallocene catalyst of the present invention includes the following steps:

[0054] Step 1: The pyridone (aldehyde) compound undergoes a coupling reaction with arylboronic acid to obtain an aryl-substituted 2-aryl-pyridone (aldehyde) compound.

[0055]

[0056] In one embodiment, R1 is selected from hydrogen, a hydrocarbon group having 1-10 carbon atoms; in another embodiment, R1 is selected from hydrogen, an alkyl group having 1-6 carbon atoms, an olefin group having 1-6 carbon atoms, or an aromatic hydrocarbon group having 6-10 carbon atoms; in yet another embodiment, R1 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl.

[0057] Wherein, Ar is phenyl, naphthyl, phenyl substituted with an aliphatic hydrocarbon group, or naphthyl substituted with an aliphatic hydrocarbon group. In another embodiment, the aliphatic hydrocarbon group in the phenyl substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms, and the aliphatic hydrocarbon group in the naphthyl substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms.

[0058] This invention does not impose particular limitations on the conditions for the coupling reaction of pyridone (aldehyde) compounds with arylboronic acids, as long as the two react to generate an aryl-substituted 2-aryl-pyridone (aldehyde) compound. In one embodiment, the catalyst in the reaction is palladium dichloride bis(triphenylphosphine) chloride, and the reaction temperature is the temperature at which toluene is refluxed.

[0059] Step 2: The 2-aryl-pyridone (aldehyde) compound undergoes a condensation reaction with 3,3-disubstituted-4,4-biphenyldiamine to give the pyridinediimide compound;

[0060]

[0061] R3 is selected from hydrogen and a hydrocarbon group having 1-10 carbon atoms; in one embodiment, R3 is selected from methyl, ethyl, n-propyl, and isopropyl. The present invention does not particularly limit the conditions for the condensation reaction of the 2-aryl-pyridone (aldehyde) compound with 3,3-disubstituted-4,4-biphenyldiamine, as long as the reaction can occur to generate a pyridinediimide compound. In one embodiment, the reaction temperature is the temperature at which toluene is refluxed.

[0062] Step 3: The pyridine diimine compound undergoes a reduction reaction with a reducing agent to obtain a bridged substituted pyridine amino compound ligand;

[0063]

[0064] In this embodiment, R2 is selected from hydrogen, a hydrocarbon group having 1-10 carbon atoms, R1 and R2 may be the same or different, M is a metal, and n is 1, 2, or 3. In another embodiment, R2 is selected from hydrogen, an alkyl group having 1-6 carbon atoms, an olefin group having 1-6 carbon atoms, or an aromatic hydrocarbon group having 6-10 carbon atoms. In yet another embodiment, R2 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, or 2-isopropylphenyl. In yet another embodiment, the reducing agent (R2) is used. n M is a strong reducing agent, such as trialkylaluminum or aryllithium.

[0065] This invention does not impose particular limitations on the conditions for the reduction reaction of the pyridine diimide compound with the reducing agent, as long as the two react to generate the pyridine diimide compound. In one embodiment, the mixing temperature of the pyridine diimide compound and the reducing agent is -40°C to 25°C, and the reaction temperature is the temperature at which toluene is refluxed.

[0066] Step 4: The bridged substituted pyridine amino compound ligand undergoes a deprotonation reaction, and then reacts with hafnium tetrachloride to obtain the bridged substituted pyridine amino hafnium chloride compound;

[0067]

[0068] In one embodiment, the bridged-substituted pyridineamine compound ligand undergoes a deprotonation reaction in the presence of n-butyllithium, followed by a reaction with hafnium tetrachloride to yield a bridged-substituted pyridineamine hafnium chloride compound. The present invention does not particularly limit the deprotonation reaction conditions or the conditions for the reaction with hafnium tetrachloride; in one embodiment, the reaction temperature is the temperature at which toluene is refluxed.

[0069] Step 5: The bridged substituted pyridine-amine hafnium chloride compound reacts with alkyl magnesium bromide to give the bridged pyridine-amine hafnium alkyl compound;

[0070]

[0071] R4 is selected from methyl, ethyl, and n-propyl. This invention does not impose particular limitations on the reaction conditions between the bridged substituted pyridine-amine hafnium chloride compound and alkyl magnesium bromide, as long as the reaction can occur to obtain the bridged pyridine-amine hafnium alkyl compound. In one embodiment, the reaction temperature is room temperature, such as 20-30°C. In one embodiment, the preparation of the bridged pyridine-amine hafnium alkyl compound of this invention is carried out under an inert gas atmosphere. This invention does not impose particular limitations on the type of inert gas, such as nitrogen or argon.

[0072] The bridged pyridine-amino hafnium alkyl compound prepared by this invention can be used as a catalyst for butene-1 polymerization. It exhibits high polymerization activity, high monomer conversion rate (up to 100%), mild reaction conditions, and efficient and controllable reaction.

[0073] In one embodiment, butene-1 is used as a monomer and the non-metallocene catalyst of the present invention is used as a catalyst to carry out a polymerization reaction to obtain polybutene-1. The polymerization reaction temperature is 25–100°C. In another embodiment, the polymerization reaction is a bulk polymerization.

[0074] In another embodiment, an activator is also added to the polymerization reaction. The molar ratio of the non-metallocene catalyst to the activator is 1:1 to 10. The activator is a composition of triphenylcarbamate tetra(pentafluorobenzene)borate and alkylaluminum, with a molar ratio of triphenylcarbamate tetra(pentafluorobenzene)borate to alkylaluminum of 1:50 to 300. The molar ratio of butene-1 monomer to the sum of the amounts of the non-metallocene catalyst and the activator is 100 to 60000:1. Further, the alkylaluminum can be trimethylaluminum, triethylaluminum, triisobutylaluminum, etc.

[0075] The polybutene-1 obtained by the above method has a weight-average molecular weight of not less than 300,000, 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 150℃, thus giving polybutene-1 better mechanical properties and thermal stability.

[0076] In one embodiment, the polybutene-1 prepared by the method of the present invention has a weight-average molecular weight of 300,000 to 700,000, a dispersion coefficient of 2.0 to 3.0, an isotacticity greater than or equal to 98%, and a melting temperature of 155 to 170°C.

[0077] This invention provides a non-metallocene catalyst for the synthesis of polybutene-1 from butene-1. This catalyst can address the problem of domestic overcapacity of butene-1, extremely low utilization rate, and the fact that over 75% of it is sold as a fuel oil component, thereby increasing the added value of butene-1 products. In addition, the polybutene-1 obtained by the method of this invention has excellent mechanical properties and thermal stability, which can meet the production needs of radiator connections, hot and cold water supply, floor heating, hot melt adhesives, and thin film and sheet applications, thus breaking the monopoly.

[0078] The technical solution of the present invention will be further described below through specific embodiments. The activators used in the following embodiments are as follows:

[0079] Activator A1: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and trimethylaluminum in a molar ratio of 1:67;

[0080] Activator A2: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and triethylaluminum in a molar ratio of 1:67;

[0081] Activator A3: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and triisobutylaluminum in a molar ratio of 1:67;

[0082] Activator A4: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and triisobutylaluminum in a molar ratio of 1:50;

[0083] Activator A5: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and triisobutylaluminum in a molar ratio of 1:150;

[0084] Activator A6: A composition of triphenylcarbazide tetra(pentafluorobenzene)borate and triisobutylaluminum in a molar ratio of 1:300.

[0085] The following provides a specific synthetic method for pyridineamine hafnium complexes, the reaction route is as follows: Figure 3 No.

[0086] Under a nitrogen atmosphere, 10 mmol of 6-bromopyridine-2-carboxaldehyde / 2-acetyl-6-bromopyridine, 10 mmol of naphthaleneboronic acid / phenylboronic acid, 15 mg of palladium di(triphenylphosphine) dichloride, 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 2-aryl-pyridinone (aldehyde) compound.

[0087] Under a nitrogen atmosphere, 10 mmol of 2-aryl-pyridone (aldehyde), 5.5 mmol of 2,2′-di-tert-butyl-1,1′-diaminobiphenyl, and 10 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene, and the mixture was refluxed with water for 48 h. The solvent was evaporated, the mixture was washed with ethanol, and dried to obtain the pyridine diimine compound.

[0088] 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.

[0089] In a nitrogen-filled reaction flask, 1.7 mmol of a pyridine-amino compound 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 refluxed for 3 h. The toluene was dried under vacuum, and the solid was washed with n-hexane. The supernatant was discarded to give 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 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 give a pyridine-amino hafnium methyl compound.

[0090] The structural formula of the bridged pyridine amino hafnium compound obtained by the above method is as follows:

[0091]

[0092] In the pyridineamine hafnium complex Hf1: Ar represents a naphthalene ring, R1 represents hydrogen, and R2 represents 2-isopropylphenyl;

[0093] Pyridineamine hafnium complex Hf2: Ar represents the naphthalene ring, R1 represents methyl, and R2 represents methyl;

[0094] Pyridineamine hafnium complex Hf3: Ar represents a benzene ring, R1 represents hydrogen, and R2 represents 2-isopropylphenyl;

[0095] Pyridineamine hafnium complex Hf4: Ar represents benzene ring, R1 represents methyl, and R2 represents methyl.

[0096] Figure 5 The pyridineamine hafnium complex Hf4 of this invention 1 H NMR spectrum Figure 6 This is the mass spectrum of the pyridineamine hafnium complex Hf4 of this invention. Figure 7 The pyridineamine hafnium complex Hfl of this invention 1 H NMR spectrum Figure 8 This is the mass spectrum of the pyridine-amine hafnium complex Hfl of this invention. Figures 5-8 As shown, the method of the present invention for synthesizing pyridineamine hafnium complexes can yield the target compound.

[0097] The compositional ratios of the pyridine-amine hafnium catalyst and activator in each embodiment are as follows:

[0098] Pyridine-amine hafnium catalyst C1-1: A composition of activator A1 and pyridine-amine hafnium complex Hf1 (the activator is calculated as triphenylcarbazium tetra(pentafluorobenzene)borate), with a molar ratio of 1.5:1;

[0099] Pyridine-amine hafnium catalyst C1-2: a composition of activator A2 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.5:1;

[0100] Pyridine-amine hafnium catalyst C1-3: a composition of activator A3 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.5:1;

[0101] Pyridine-amine hafnium catalyst C1-4: a composition of activator A4 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.5:1;

[0102] Pyridine-amine hafnium catalyst C1-5: a composition of activator A5 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.5:1;

[0103] Pyridine-amine hafnium catalyst C1-6: a composition of activator A6 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.5:1;

[0104] Pyridine-amine hafnium catalyst C1-7: a composition of activator A3 and pyridine-amine hafnium complex Hf1 in a molar ratio of 1.0:1;

[0105] Pyridine-amine hafnium catalyst C1-8: a composition of activator A3 and pyridine-amine hafnium complex Hf1 in a molar ratio of 3.0:1;

[0106] Pyridine-amine hafnium catalyst C1-9: a composition of activator A3 and pyridine-amine hafnium complex Hf1 in a molar ratio of 5.0:1;

[0107] Pyridine-amine hafnium catalyst C2-1: a composition of activator A1 and pyridine-amine hafnium complex Hf2 in a molar ratio of 1.5:1;

[0108] Pyridine-amine hafnium catalyst C2-2: a composition of activator A2 and pyridine-amine hafnium complex Hf2 in a molar ratio of 1.5:1;

[0109] Pyridine-amine hafnium catalyst C2-3: a composition of activator A3 and pyridine-amine hafnium complex Hf2 in a molar ratio of 1.5:1;

[0110] Pyridine-amine hafnium catalyst C3-3: a composition of activator A3 and pyridine-amine hafnium complex Hf3 in a molar ratio of 1.5:1;

[0111] Pyridine-amine hafnium catalyst C4-3: a composition of activator A3 and pyridine-amine hafnium complex Hf4 in a molar ratio of 1.5:1;

[0112] Example 1

[0113] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. The steps are as follows:

[0114] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 400g of butene-1 monomer (monomer to catalyst C1-3 molar ratio of 24000:1) was added, and the polymerization temperature was maintained at 60℃ with stirring for half an hour. Subsequently, 292μmol of bridged pyridine-amine hafnium catalyst C1-3 containing a pyridine-amine hafnium complex (Hf1 in this example) was added to the system to initiate polymerization. After 60 minutes of polymerization, the polymerization was terminated by adding a 10 vol% hydrochloric acid-acidified ethanol solution. The polymer was filtered, washed three times with ethanol, and vacuum dried to constant weight.

[0115] Figure 1 This is the carbon NMR spectrum of polybutene-1 prepared in Example 1 of the present invention. Figure 2 This is a GPC curve of polybutene-1 prepared in Example 1 of the present invention. Figure 1 As shown, the absorption peak at δ 39.4 ppm is the methylene group of the main chain of polybutene-1, the absorption peak at δ 36.9 ppm is the methine group of the main chain of polybutene-1, the absorption peak at δ 27.8 ppm is the methylene group of the branched chain of polybutene-1, and the absorption peak at δ 11.7 ppm is the methyl group of the branched chain of polybutene-1. Figure 2 As shown, polybutene-1 has a weight-average molecular weight of 580,000 and a molecular weight distribution index of 2.2.

[0116] Therefore, in this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 19.6 kg polymer / (mmol Hf·h), and the prepared polybutene-1 has a weight-average molecular weight of 580,000, a molecular weight distribution index of 2.2, a melting temperature of 166℃, and an isotacticity of >99%.

[0117] Example 2

[0118] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. The experimental method in Example 1 is followed, but the polymerization temperature is changed to 25°C.

[0119] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 5.8 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 310,000, a molecular weight distribution index of 3.0, a melting temperature of 161℃, and an isotacticity of 97%.

[0120] Example 3

[0121] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. The polymerization temperature is 80°C, following the experimental method in Example 1.

[0122] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 12.9 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 490,000, a molecular weight distribution index of 1.6, a melting temperature of 162℃, and an isotacticity of 97%.

[0123] Example 4

[0124] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C2-3. The experimental method in Example 1 was followed.

[0125] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C2-3 is 11.6 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 450,000, a molecular weight distribution index of 3.0, a melting temperature of 167℃, and an isotacticity of 95%.

[0126] Example 5

[0127] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C3-3. The experimental method in Example 1 was followed.

[0128] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C3-3 is 28.3 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 340,000, a molecular weight distribution index of 2.0, a melting temperature of 166℃, and an isotacticity of 97%.

[0129] Example 6

[0130] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C4-3. The experimental method in Example 1 was followed.

[0131] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C4-3 is 4.6 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 610,000, a molecular weight distribution index of 2.8, a melting temperature of 170℃, and an isotacticity of 98%.

[0132] Example 7

[0133] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. Following the experimental method in Example 1, 2g of butene-1 monomer was added (the molar ratio of monomer to catalyst C1-3 was 100:1).

[0134] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 9.5 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 360,000, a molecular weight distribution index of 1.0, a melting temperature of 169℃, and an isotacticity of 99%.

[0135] Example 8

[0136] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. Following the experimental method in Example 1, 20g of butene-1 monomer was added (the molar ratio of monomer to catalyst C1-3 was 1000:1).

[0137] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 34.3 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 330,000, a molecular weight distribution index of 1.2, a melting temperature of 169℃, and an isotacticity of 99%.

[0138] Example 9

[0139] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. Following the experimental method in Example 1, 160 g of butene-1 monomer was added (the molar ratio of monomer to catalyst C1-3 was 8000:1).

[0140] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 23.4 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 410,000, a molecular weight distribution index of 1.3, a melting temperature of 158℃, and an isotacticity of 98%.

[0141] Example 10

[0142] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-3. Following the experimental method in Example 1, 800g of butene-1 monomer was added (the molar ratio of monomer to catalyst C1-3 was 40000:1).

[0143] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-3 is 57.3 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 640,000, a molecular weight distribution index of 1.7, a melting temperature of 168℃, and an isotacticity of 98%.

[0144] Example 11

[0145] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-7. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, and the amount of triphenylcarbium tetra(pentafluorobenzene)borate was changed to 292 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to the bridged pyridine-amine hafnium complex in the activator was 1:1).

[0146] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-7 is 12.4 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 490,000, a molecular weight distribution index of 1.5, a melting temperature of 168℃, and an isotacticity of 98%.

[0147] Example 12

[0148] This embodiment provides a preparation process for polybutene-1, which is prepared by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-8. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, and the amount of triphenylcarbium tetra(pentafluorobenzene)borate was changed to 876 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to bridged pyridine-amine hafnium complex 1 in the activator was 3:1).

[0149] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-8 is 14.6 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 590,000, a molecular weight distribution index of 1.6, a melting temperature of 168℃, and an isotacticity of 98%.

[0150] Example 13

[0151] This embodiment provides a preparation process for polybutene-1, which is prepared by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-9. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, and the amount of triphenylcarbium tetra(pentafluorobenzene)borate was changed to 1160 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to bridged pyridine-amine hafnium complex 1 in the activator was 5:1).

[0152] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-9 is 19.3 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 620,000, a molecular weight distribution index of 1.7, a melting temperature of 168℃, and an isotacticity of 98%.

[0153] Example 14

[0154] This embodiment provides a preparation process for polybutene-1, which is prepared by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-4. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, the amount of triphenylcarbium tetra(pentafluorobenzene)borate was 438 μmol, and the amount of triisobutylaluminum was changed to 21900 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to triisobutylaluminum was 1:50).

[0155] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-4 is 15.1 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 390,000, a molecular weight distribution index of 1.8, a melting temperature of 162℃, and an isotacticity of 98%.

[0156] Example 15

[0157] This embodiment provides a preparation process for polybutene-1, which is prepared by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-5. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, the amount of triphenylcarbium tetra(pentafluorobenzene)borate was 438 μmol, and the amount of triisobutylaluminum was changed to 65700 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to triisobutylaluminum was 1:150).

[0158] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-5 is 19.1 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 500,000, a molecular weight distribution index of 2.0, a melting temperature of 159℃, and an isotacticity of 98%.

[0159] Example 16

[0160] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-6. Following the experimental method in Example 1, the amount of bridged pyridine-amine hafnium complex added was 292 μmol, the amount of triphenylcarbium tetra(pentafluorobenzene)borate was 438 μmol, and the amount of triisobutylaluminum was changed to 131400 μmol (the molar ratio of triphenylcarbium tetra(pentafluorobenzene)borate to triisobutylaluminum was 1:300).

[0161] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-6 is 15.6 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 380,000, a molecular weight distribution index of 2.5, a melting temperature of 160℃, and an isotacticity of 98%.

[0162] Example 17

[0163] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-1. Following the experimental method in Example 1, the added alkyl aluminum is trimethylaluminum.

[0164] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-1 is 11.5 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 370,000, a molecular weight distribution index of 2.0, a melting temperature of 168℃, and an isotacticity of 98%.

[0165] Example 18

[0166] This embodiment provides a process for preparing polybutene-1, which is obtained by bulk polymerization of butene-1 catalyzed by a bridged pyridine-amine hafnium catalyst C1-2. Following the experimental method in Example 1, the added alkyl aluminum is triethylaluminum.

[0167] In this embodiment, the catalytic activity of the bridged pyridine-amine hafnium catalyst C1-2 is 19.9 kg polymer / (mmolHf·h), and the prepared polybutene-1 has a weight-average molecular weight of 460,000, a molecular weight distribution index of 1.8, a melting temperature of 164℃, and an isotacticity of 98%.

[0168] To better illustrate the beneficial effects of this invention, Ziegler-Natta catalyst and zirconium monoxide catalyst were used as comparative examples to catalyze the polymerization of butene-1.

[0169] Comparative Example 19

[0170] This comparative example provides a process for preparing polybutene-1, which is obtained by homopolymerization of butene-1 catalyzed by a Ziegler-Natta catalyst, and the steps are as follows:

[0171] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 400g of butene-1 monomer and 2ml of triethylaluminum were added, and the mixture was stirred at 60℃ for half an hour. Subsequently, 200mg of Ziegler-Natta catalyst was added to the reaction system and the time was set. After 60 minutes of polymerization, the polymerization was terminated by adding a 10% hydrochloric acid-acidified ethanol solution. The polymer was filtered, washed three times with ethanol, and vacuum dried to constant weight. The Ziegler-Natta catalyst used in this comparative example is the catalyst disclosed in Chinese Patent CN201510954492.2.

[0172] In this comparative example, the catalytic activity of the Ziegler-Natta catalyst was 2.2 kg polymer / (mmol Ti·h), and the prepared polybutene-1 had a weight-average molecular weight of 160,000, a molecular weight distribution index of 13.7, a melting temperature of 127℃, and an isotacticity of 96%.

[0173] Comparative Example 20

[0174] This comparative example provides a process for preparing polybutene-1, which is obtained by homopolymerization of butene-1 catalyzed by a metallocene catalyst. The steps are as follows:

[0175] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 400g of butene-1 monomer and 2ml of methylaluminoxane (MAO) were added, and the mixture was stirred at 60℃ for half an hour. Subsequently, 300μmol of zirconium-1 catalyst (the structure of which is shown in the image) was added. Figure 4 (As shown) was added to the reaction system and the time was started. After polymerization reached 60 min, a 10% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, washed three times with ethanol, and then vacuum dried to constant weight.

[0176] In this comparative example, the catalytic activity of the zirconium cadmium catalyst was 0.9 kg polymer / (mmol Zr·h), and 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 149℃, and an isotacticity of 90%.

[0177] The results of the examples and comparative examples show that the non-metallocene catalyst of the present invention exhibits a high catalytic activity of 19.6 kg polymer / (mmol Hf·h) for the polymerization of butene-1, and the prepared polybutene-1 has a weight-average molecular weight of 580,000, a molecular weight distribution index of 2.2, a melting temperature of 166 °C, and an isotacticity of >99%, demonstrating excellent temperature resistance. When using a Ziegler-Natta catalyst to catalyze the polymerization of butene-1, the catalytic activity decreases to only 2.2 kg polymer / (mmol Ti·h), and due to the multiple active sites, the polymer distribution is significantly broadened, with a molecular weight distribution index of 13.7. The resulting polymer melt temperature is significantly lower, at only 127 °C. Furthermore, when using a metallocene catalyst to catalyze the polymerization of butene-1, the steric hindrance makes it difficult for butene-1 monomers to insert, thus further reducing the polymerization activity to only 0.9 kg polymer / (mmol Zr·h).

[0178] Therefore, this invention provides a bridged pyridine-amine hafnium catalyst, which mainly synthesizes bridged pyridine-amine hafnium alkyl compounds 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. This 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 non-metallocene catalyst polybutene-1 preparation technology. This technology features mild polymerization reaction conditions, high polymerization activity, high monomer conversion rate, and highly efficient and controllable polymerization reaction. Moreover, 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.

[0179] 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. The application of a non-metallocene catalyst in the catalytic polymerization of butene-1, characterized in that, The non-metallocene catalyst comprises the following structure: Formula I R1 and R2 are selected from hydrogen and hydrocarbon groups having 1-10 carbon atoms. R1 and R2 may be the same or different. R3 is isopropyl. R4 is selected from methyl, ethyl, and n-propyl. Ar is phenyl, naphthyl, phenyl substituted with aliphatic hydrocarbon group, or naphthyl substituted with aliphatic hydrocarbon group.

2. The application of the non-metallocene catalyst according to claim 1 in the catalytic polymerization of butene-1, characterized in that, R1 and R2 are selected from hydrogen, alkyl groups having 1-6 carbon atoms, olefinic groups having 1-6 carbon atoms, or aromatic hydrocarbon groups having 6-10 carbon atoms; the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted phenyl group has 1-6 carbon atoms, and the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted naphthyl group has 1-6 carbon atoms.

3. The application of the non-metallocene catalyst according to claim 2 in the catalytic polymerization of butene-1, characterized in that, R1 and R2 are selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, and 2-isopropylphenyl; the aliphatic hydrocarbon group in the phenyl group substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms, and the aliphatic hydrocarbon group in the naphthyl group substituted with an aliphatic hydrocarbon group is an alkyl group having 1-6 carbon atoms; R4 is selected from methyl.

4. The application of the non-metallocene catalyst according to claim 3 in the catalytic polymerization of butene-1, characterized in that, When Ar is phenyl or naphthyl, R1 is hydrogen and R2 is 2-isopropylphenyl, or R1 is methyl and R2 is methyl.

5. The application of the non-metallocene catalyst according to any one of claims 1-4 in the catalytic polymerization of butene-1, characterized in that, Polybutene-1 was obtained by using butene-1 as a monomer and the aforementioned non-metallocene catalyst as a catalyst for polymerization.

6. The application of the non-metallocene catalyst according to claim 5 in the catalytic polymerization of butene-1, characterized in that, An activator is also added to the polymerization reaction, and the molar ratio of the catalyst to the activator is 1:1 to 10; the activator is a composition of triphenylcarbazide tetra(pentafluorobenzene)borate and alkylaluminum, and the molar ratio of triphenylcarbazide tetra(pentafluorobenzene)borate to alkylaluminum is 1:50 to 300.

7. The application of the non-metallocene catalyst according to claim 6 in the catalytic polymerization of butene-1, characterized in that, The molar ratio of the butene-1 monomer to the sum of the amounts of the catalyst and the activator is 100~60000:1; the polymerization temperature is 25~100°C.

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