Non-metallocene catalyst, polybutene-1 elastomer and preparation method thereof

Abstract

The present invention discloses a non-metallocene catalyst, a polybutene-1 elastomer, and a preparation method thereof. The bridged bipyridylamino hafnium compound has the structure shown in formula (I): #imgabs0#, wherein R1 is hydrogen or a methyl group; and R2 is a methyl group or a 2-isopropylphenyl group. The non-metallocene catalyst of the present invention can be used to prepare the polybutene-1 elastomer, thereby increasing the added value of the butene-1 product and reducing production costs.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin catalytic polymerization and olefin polymers, and more specifically to a bridged bipyridylamino hafnium compound, a non-metallocene catalyst, a polybutene-1 elastomer and a preparation method thereof. Background Art

[0002] Thermoplastic elastomers (TPEs) are polymer materials that exhibit the elasticity of rubber at room temperature but can be plasticized and molded at high temperatures, with properties intermediate between those of rubber and resin. Comprising both resin and rubber segments, they combine the physical and mechanical properties of rubber with the processing properties of plastic. Types include urethanes, olefins, and amides. Polyolefin elastomers, among others, are attracting significant attention due to their high added value.

[0003] Polyolefin elastomer (POE) refers to a random copolymer elastomer of ethylene and higher α-olefins (such as 1-butene, 1-hexene, 1-octene, etc.). Among them, ethylene-1-octene elastomer has a wide range of applications and strong market demand, becoming a key research direction at home and abroad. At present, POE is usually obtained by random copolymerization of ethylene and higher α-olefins catalyzed by catalysts such as metallocenes and nickel series. Among them, metallocene catalysts have unique properties and can control the polymer molecular weight (Mw), stereoregular structure and comonomer content to produce high-performance POE with a narrow molecular weight distribution (MWD) and long-chain branching. It also has good high-temperature tolerance and is more suitable for industrial production of POE. For example, in 1993, Dow Chemical Company of the United States used the high-temperature solution method Insite process to produce POE for the first time using a metallocene catalyst. Patent CN201810286354.5 discloses a catalytic system for the preparation of ethylene and / or α-olefin and cycloolefin copolymers, including a main catalyst and a cocatalyst, the main catalyst being a metallocene compound and the cocatalyst being an organic boron compound and an alkyl aluminum. Also disclosed is a method for preparing copolymers of ethylene and / or α-olefins and cycloolefins using the above-mentioned catalyst system: an inert organic solvent, ethylene / α-olefin, and cycloolefin are separately added to a reactor at a temperature of 40-100°C and a pressure of 130 bar; after the ethylene and / or α-olefin are dissolved to saturation in the inert organic solvent, a triisobutylaluminum solution, a metallocene catalyst solution, and an organoboron compound solution are sequentially added to initiate the reaction. Using the cocatalyst of the present invention enables more efficient polymerization of cycloolefin copolymers than MAO, MMAO, and dMAO, reduces the metal content in the polymerized product, and significantly reduces post-processing costs. The defects of this technology or the shortcomings relative to the present invention are: the patent uses a metallocene catalyst to catalyze the copolymerization of ethylene and / or α-olefins and cycloolefins. The metallocene catalyst has large steric hindrance, and the α-olefins and cycloolefin monomers with large steric hindrance are difficult to insert, resulting in poor copolymerization performance; secondly, the patent prepares vinyl elastomers, and the price of butene-1 (5,000 yuan / ton) is about 30 to 40% lower than the price of ethylene (8,000 yuan / ton), so the cost of vinyl elastomers is higher than that of butene-1-based elastomers.

[0004] Currently, numerous factors hinder the large-scale production and industrial development of high-end elastomers. Globally, there are no butene-1-based elastomer production technologies or products. Butene-1 is primarily used as a comonomer in polyethylene, with the remainder primarily used as a C4 fuel in mixed fuels. With the increasing trend of using higher-carbon alpha olefins such as hexene-1 and octene-1 as comonomers in polyethylene, butene-1 resources will become increasingly abundant in the future. Optimizing the industrial structure of butene-1 resources and maximizing their value-added utilization are pressing challenges for major chemical companies.

[0005] Patent CN1140545C discloses a polybutene-1 homopolymer, or a copolymer containing up to 20 wt% of an α-olefin having 2 to 10 carbon atoms other than butene-1, characterized by the following properties: (i) an isotactic index greater than 93, as determined by NMR analysis as specified below; (ii) a molecular weight distribution (MWD), expressed as Mw / Mn, greater than 6, as determined by GPC (gel permeation chromatography) analysis as specified below; and (iii) a catalyst residue content, expressed as ppm titanium, less than 50. The polymer is well suited for preparing articles, particularly pipes, with improved creep and burst stress resistance. A drawback of this technology or a disadvantage relative to the present invention is that the multiple active sites of the Ziegler-Natta catalyst used in this patent result in a polymer with an exceptionally broad molecular weight distribution, resulting in poor mechanical properties in the low molecular weight fraction, making it difficult to achieve the performance requirements of elastomers, limiting its application.

[0006] my country currently has no polyolefin elastomer manufacturers, relying entirely on imports. These products remain expensive, despite the increasing annual demand for polyolefin elastomers in the domestic market. However, the primary constraint on my country's polyolefin production is the monopoly of most high-end vinyl elastomer production technologies abroad, creating a bottleneck. Furthermore, the high price of comonomers used in high-end vinyl elastomers, such as octene-1, contributes to high production costs. Furthermore, domestic butene-1 production capacity is oversupplied, with extremely low utilization rates, with over 75% sold as fuel oil components. Improving the added value of butene-1 products is an urgent challenge that needs to be addressed. Summary of the Invention

[0007] The object of the present invention is to provide a bridged bipyridylamine hafnium compound, a non-metallocene catalyst, a polybutene-1 elastomer and a preparation method thereof. The non-metallocene catalyst of the present invention can be used to prepare the polybutene-1 elastomer, thereby increasing the added value of the butene-1 product and reducing the production cost.

[0008] To achieve the above-mentioned object, the present invention provides a bridged bipyridylamine hafnium compound having a structure as shown in formula (I):

[0009]

[0010] Wherein, R1 may be hydrogen or methyl; R2 may be methyl or 2-isopropylphenyl.

[0011] The present invention also provides a method for preparing the above-mentioned bridged bipyridylamine hafnium compound (the reaction scheme is as follows Figure 4 ), comprising the following steps:

[0012] 1) A pyridone (aldehyde) compound is subjected to a coupling reaction with 1,3-phenylboronic acid to obtain a phenyl-disubstituted 1,3-phenyl-dipyridone (aldehyde) compound,

[0013]

[0014] 2) 1,3-phenyl-dipyridone (aldehyde) compound undergoes condensation reaction with 2,6-diisopropylaniline to obtain a pyridine diimine compound,

[0015]

[0016] 3) subjecting the pyridine diimine compound to a reduction reaction with a strong reducing agent such as trimethylaluminum or 2-isopropylphenyl lithium to obtain a pyridine amino compound ligand,

[0017]

[0018] 4) The pyridinylamino compound ligand reacts with n-butyl lithium to undergo a deprotonation reaction, and then a metal salt of hafnium tetrachloride is added to obtain a pyridinylamino hafnium chloride compound.

[0019]

[0020] 5) the pyridylamino hafnium chloride compound reacts with methylmagnesium bromide to obtain a bridged pyridylamino hafnium compound,

[0021]

[0022] The present invention further provides a non-metallocene catalyst comprising the bridged bipyridylamino hafnium compound, a co-catalyst and an activator.

[0023] The non-metallocene catalyst of the present invention comprises a co-catalyst which is a boron compound selected from at least one of [Ph3C][B(C6F5)4] and B(C6F5)3; an activator which is an alkyl aluminum selected from at least one of trimethylaluminum, triethylaluminum and triisobutylaluminum; and a molar ratio of the bridged bipyridylamino hafnium compound, the boron compound and the alkyl aluminum in the non-metallocene catalyst is Hf:B:Al=1:(1-3):(0-900).

[0024] Preferably, the co-catalyst is [Ph3C][B(C6F5)4].

[0025] Preferably, the activator is triisobutylaluminum.

[0026] Preferably, in the non-metallocene catalyst, the molar ratio of the bridged bipyridylamino hafnium compound, the boron compound and the alkyl aluminum is Hf:B:Al=1:(1.2-2):(100-600).

[0027] The present invention further provides a polybutene-1 elastomer, which is obtained by catalyzing the copolymerization of butene-1 and an α-olefin comonomer using the above-mentioned non-metallocene catalyst. The polybutene-1 elastomer has a structure represented by formula (II):

[0028]

[0029] Among them, the molar insertion rate of the comonomer is 5-40%, the isotacticity of the butene-1 chain segment is ≥98%, the melting temperature is 80-110°C, the weight-average molecular weight is 200,000-350,000, the molecular weight distribution PDI is ≤3, and it has good processing performance. At the same time, the insertion of long-chain α-olefins on the butene-1 main chain significantly improves the toughness and elasticity of the polymer, so that it has a very high nominal strain at break (650-1050%) and elastic modulus (13-50MPa).

[0030] Preferably, the comonomer molar insertion rate of the polybutene-1 elastomer is 25-30%.

[0031] Preferably, the molecular weight distribution PDI of the polybutene-1 elastomer is ≤2.

[0032] Preferably, the melting temperature of the polybutene-1 elastomer is 85-95°C.

[0033] Preferably, the polybutene-1 elastomer has a nominal strain at break of 850-1000% and an elastic modulus of 30-35 MPa.

[0034] The present invention further provides a method for preparing a polybutene-1 elastomer, comprising the following steps: reacting a certain amount of butene-1 and an appropriate amount of α-olefin comonomer, using the above-mentioned non-metallocene catalyst as a catalyst, adding an appropriate amount of molecular weight regulator, and adopting a bulk polymerization process to obtain the polybutene-1 elastomer.

[0035] When the copolymerization product is a binary copolymer, the α-olefin comonomer is selected from butene-1 and one of hexene-1, octene-1 or decene-1.

[0036] When the copolymerization product is a terpolymer, the α-olefin comonomer is selected from ethylene, butene-1 and two of hexene-1, octene-1 or decene-1.

[0037] Preferably, the molar ratio of butene-1 and non-metallocene catalyst is 2000-31800:1, the mass ratio of butene-1 and α-olefin comonomer is 100:10-60; the molecular weight regulator is H2, the polymerization pressure of H2 is 0-0.1 MPa; the temperature of the polymerization reaction is 25-100°C.

[0038] Preferably, the mass ratio of the butene-1 to the α-olefin comonomer is 100:10-60.

[0039] Preferably, the molar ratio of butene-1 to the non-metallocene catalyst is 10,000 to 30,000:1.

[0040] Preferably, the polymerization reaction temperature is 60-80°C.

[0041] The present invention has the following beneficial effects:

[0042] (1) The non-metallocene catalyst of the present invention can catalyze the copolymerization of butene-1 with α-olefins to produce polybutene-1 elastomers. The introduction of flexible side chains into the butene-1 chain segments creates an island-in-the-sea structure, resulting in high nominal strain at break (650-1050%) and elastic modulus (13-50 MPa).

[0043] (2) The bridged bipyridylamine hafnium compound and non-metallocene catalyst of the present invention have a broader space due to the unique monomer activation mechanism compared to metallocene catalysts, which is conducive to the insertion of long-chain α-olefins with large steric hindrance, thereby improving polymerization activity and achieving the preparation of polybutene-1 elastomers with a high monomer insertion rate and a butene-1 segment isotacticity of ≥98%. Compared with traditional Ziegler-Natta catalysts or metallocene catalysts, the non-metallocene catalyst has higher polymerization activity (10-60 kg polymer / (mmol Hf·h)).

[0044] (3) The butene-1 monomer used in the present invention is cheaper than the ethylene monomer used in polyolefin elastomer (POE). At the same time, the production capacity of butene-1 monomer is in excess. The high value-added utilization of butene-1 resources has a positive effect on optimizing the industrial structure of butene-1 resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the C-NMR spectrum of the polybutene-1 elastomer prepared in Example 2 of the present invention.

[0046] Figure 2 This is a DSC curve of the polybutene-1 elastomer prepared in Example 2 of the present invention.

[0047] Figure 3 This is a GPC curve of the polybutene-1 elastomer prepared in Example 2 of the present invention.

[0048] Figure 4 The present invention is a reaction scheme for preparing the bridged bipyridylamino hafnium compound.

[0049] Figure 5 This is a structural diagram of the zirconocene catalyst of Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0050] The present invention is further described below with reference to the examples. These examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. Experimental methods in the following examples where specific conditions are not specified are generally performed in accordance with conventional conditions in the art or the conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from conventional markets. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention fall within the scope of protection claimed in the present invention.

[0051] The structural formula of the bridged bipyridylamine hafnium compound in each embodiment is as follows:

[0052]

[0053] Wherein, R1 can be hydrogen or methyl; R2 can be methyl or 2-isopropylphenyl. Specifically:

[0054] Bridged pyridylamino hafnium compound 1: Ar represents a benzene ring, R1 represents hydrogen, and R2 represents 2-isopropylphenyl;

[0055] Bridged bipyridylamino hafnium compound 2: Ar represents a benzene ring, R1 represents a methyl group, and R2 represents a methyl group;

[0056] The compositions of the co-catalyst and activator in each embodiment are as follows:

[0057] Composition A1: a composition of [Ph3C][B(C6F5)4] and trimethylaluminum, in a molar ratio of 1:67;

[0058] Composition A2: a composition of [Ph3C][B(C6F5)4] and triethylaluminum, in a molar ratio of 1:67;

[0059] Composition A3: a composition of [Ph3C][B(C6F5)4] and triisobutylaluminum, in a molar ratio of 1:67;

[0060] Composition A4: a composition of [Ph3C][B(C6F5)4] and triisobutylaluminum, in a molar ratio of 1:50;

[0061] Composition A5: a composition of [Ph3C][B(C6F5)4] and triisobutylaluminum, in a molar ratio of 1:150;

[0062] Composition A6: a composition of [Ph3C][B(C6F5)4] and triisobutylaluminum, in a molar ratio of 1:300;

[0063] Composition A7: a composition of B(C6F5)3 and triisobutylaluminum, in a molar ratio of 1:50;

[0064] Composition A8: a composition of B(C6F5)3 and triisobutylaluminum, in a molar ratio of 1:150;

[0065] Composition A9: a composition of B(C6F5)3 and triisobutylaluminum, with a molar ratio of 1:300.

[0066] The composition of the non-metallocene catalyst in each embodiment is as follows:

[0067] Non-metallocene catalyst C1-1: a composition of composition A1 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0068] Non-metallocene catalyst C1-2: a composition of composition A2 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0069] Non-metallocene catalyst C1-3: a composition of composition A3 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0070] Non-metallocene catalyst C1-4: a composition of composition A4 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0071] Non-metallocene catalyst C1-5: a composition of composition A5 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0072] Non-metallocene catalyst C1-6: a composition of composition A6 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0073] Non-metallocene catalyst C1-7: a composition of composition A7 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0074] Non-metallocene catalyst C1-8: a composition of composition A8 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0075] Non-metallocene catalyst C1-9: a composition of composition A9 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.5:1;

[0076] Non-metallocene catalyst C1-10: a composition of composition A3 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 1.0:1;

[0077] Non-metallocene catalyst C1-11: a composition of composition A3 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 3.0:1;

[0078] Non-metallocene catalyst C1-12: a composition of composition A3 and bridged bipyridylamine hafnium compound 1, in a molar ratio of 5.0:1;

[0079] Non-metallocene catalyst C2-1: a composition of composition A1 and bridged bipyridylamine hafnium compound 2, in a molar ratio of 1.5:1;

[0080] Non-metallocene catalyst C2-2: a composition of composition A2 and bridged bipyridylamine hafnium compound 2, in a molar ratio of 1.5:1;

[0081] Non-metallocene catalyst C2-3: a composition of composition A3 and bridged bipyridylamino hafnium compound 2, in a molar ratio of 1.5:1.

[0082] Example 1

[0083] This embodiment provides a method for preparing a bridged bipyridylamine hafnium compound, which is as follows: Figure 4 The reaction scheme shown is prepared. Under nitrogen atmosphere, first, 6-bromopyridine-2-carboxaldehyde / 2-acetyl-6-bromopyridine 10mmol, 1,3-phenylenediboronic acid 10mmol, bis(triphenylphosphine)palladium dichloride 15mg, and potassium carbonate 3g are added sequentially in a flask, and then 30mL of ethanol, 20mL of toluene, and 10mL of water are added with a syringe, and the reaction is refluxed for 24h. After separation, the mixture is extracted with ethyl acetate, washed with NaHCO3 solution, dried over anhydrous Na2SO4, and spin-dried to obtain 1,3-phenyl-dipyridone (aldehyde) compound.

[0084] Under nitrogen atmosphere, 10 mmol of 1,3-phenyl-dipyridone (aldehyde), 10.5 mmol of 2,6-di-tert-butylaniline, and 10 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene, separated by water and refluxed for 48 hours. The solvent was dried, rinsed with ethanol, and dried to obtain a pyridine diimine compound.

[0085] Dissolve the pyridine diimine compound in dry tetrahydrofuran. Slowly add 2-isopropylphenyl lithium / trimethylaluminum dropwise to the solution at -40°C. Stir for 1 hour, then slowly return to room temperature. Heat to 90°C and reflux overnight. Quench with aqueous NH4Cl solution in an ice-water bath. Separate the layers and extract with ethyl acetate. Wash with brine, dry over anhydrous Na2SO4, and spin-dry to obtain the pyridine amino compound ligand.

[0086] In a nitrogen-filled reaction flask, 1.7 mmol of the pyridylamino 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 heated under reflux for 3 hours. The toluene was drained, the mixture was washed with n-hexane, and the supernatant was decanted to yield a yellow lithium salt. The lithium salt was redissolved in toluene, and 0.61 g of HfCl₄ was transferred to the reaction system. The temperature was then raised to 90°C and refluxed overnight. The solution was then cooled to room temperature, and 2.13 mL of MeMgBr solution was added dropwise. The mixture was stirred at room temperature for 3 hours. The solvent was drained, and the solid was washed three times with n-hexane. The n-hexane filtrate was filtered and collected. The solvent was concentrated to approximately 3 mL and allowed to crystallize at -35°C overnight. The crystals were filtered, washed with chilled n-hexane, and dried. This yielded a bridged pyridylamino hafnium compound.

[0087] Example 2

[0088] This embodiment provides a polybutene-1 elastomer, which is prepared by copolymerizing butene-1 and hexene-1 catalyzed by a non-metallocene catalyst C1-3, in the following steps:

[0089] The 10L reactor was continuously purged with nitrogen for 30 minutes to ensure the removal of water and oxygen. Then, 240g of butene-1 monomer and 80g of hexene-1 monomer (the molar ratio of monomer to hafnium pyridylamine catalyst was 23900:1) were added, the temperature maintained at 60°C, and stirring was continued for half an hour. Subsequently, 180μmol of the non-metallocene catalyst C1-3 was injected into the autoclave, and the hydrogen pressure was raised to 0.05MPa to initiate the copolymerization reaction. After 30 minutes of polymerization, a hydrochloric acid-treated ethanol solution was added to terminate the polymerization reaction. The polymer was filtered, washed three times with ethanol, and vacuum-dried to constant weight.

[0090] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 14.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 237,000, a molecular weight distribution index of 1.9, a melting temperature of 78°C, an isotacticity of 98%, an elongation at break of 1020%, and an elastic modulus of 39 MPa.

[0091] The polybutene-1 elastomer prepared in this example was subjected to NMR carbon spectroscopy, DSC and GPC analysis, and the results are as follows: Figure 1 、 Figure 2 、 Figure 3 As shown. Figure 1 It can be seen that the isotacticity of polybutene elastomer is 98%; Figure 2 It can be seen that the melting temperature of polybutene-1 elastomer is 78°C; Figure 3 It can be seen that the weight average molecular weight of the polybutene-1 elastomer is 237,000 and the molecular weight distribution index is 1.6.

[0092] Example 3

[0093] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-3. According to the experimental method in Example 2, the polymerization temperature was 25°C.

[0094] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 5.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 173,000, a molecular weight distribution index of 2.4, a melting temperature of 74°C, an isotacticity of >99%, an elongation at break of 980%, and an elastic modulus of 40 MPa.

[0095] Example 4

[0096] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-3. According to the experimental method in Example 2, the polymerization temperature is 100°C.

[0097] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 4.9 kg polymer / (mmol Hf·h). The prepared poly(4-methyl-1-pentene) has a weight-average molecular weight of 21.3 kg / mol, a molecular weight distribution index of 2.1, a melting temperature of 68°C, an isotacticity of 97%, an elongation at break of 780%, and an elastic modulus of 32 MPa.

[0098] Example 5

[0099] This embodiment provides a polybutene-1 elastomer, which is prepared by copolymerizing butene-1 and hexene-1 catalyzed by a pyrrolidine metallocene catalyst C2-3. The experimental method in Example 2 is used.

[0100] The catalytic activity of the non-metallocene catalyst C2-3 in this example is 1.9 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 295,000, a molecular weight distribution index of 2.2, a melting temperature of 81°C, an isotacticity of 96%, an elongation at break of 720%, and an elastic modulus of 23 MPa.

[0101] Example 6

[0102] This embodiment provides a polybutene-1 elastomer, which is prepared by copolymerizing butene-1 and octene-1 catalyzed by a non-metallocene catalyst C1-3. The experimental method in Example 2 is used.

[0103] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 21.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 230,000, a molecular weight distribution index of 2.5, a melting temperature of 76°C, an isotacticity of 98%, an elongation at break of 850%, and an elastic modulus of 42 MPa.

[0104] Example 7

[0105] This embodiment provides a polybutene-1 elastomer, which is prepared by copolymerizing butene-1 and decene-1 catalyzed by a non-metallocene catalyst C1-3. The experimental method in Example 2 is used.

[0106] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 18.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 199,000, a molecular weight distribution index of 2.7, a melting temperature of 72°C, an isotacticity of 98%, an elongation at break of 790%, and an elastic modulus of 27 MPa.

[0107] Example 8

[0108] This embodiment provides a polybutene-1 elastomer, which is prepared by terpolymerization of butene-1, hexene-1, and ethylene catalyzed by a non-metallocene catalyst C1-3, in the following steps:

[0109] A 10L reactor was continuously N2-purged for 30 minutes to ensure the removal of water and oxygen from the reactor. Then, 240g of butene-1 monomer and 45g of hexene-1 monomer (the molar ratio of monomer to non-metallocene catalyst was 23900:1) were added, the temperature maintained at 60°C, and stirring was continued for half an hour. Subsequently, the non-metallocene catalyst C1-3 was injected into the autoclave, and the ethylene pressure was adjusted to 0.15 MPa to initiate the copolymerization reaction. After 30 minutes of polymerization, a hydrochloric acid-treated ethanol solution was added to terminate the polymerization reaction. The polymer was filtered, washed three times with ethanol, and vacuum-dried to constant weight.

[0110] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 26.7 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 176,000, a molecular weight distribution index of 1.7, a melting temperature of 94°C, an isotacticity of 96%, an elongation at break of 1030%, and an elastic modulus of 47 MPa.

[0111] Example 9

[0112] This embodiment provides a polybutene-1 elastomer, which is prepared by terpolymerization of butene-1, octene-1, and ethylene catalyzed by a non-metallocene catalyst C1-3. The experimental method in Example 8 is used.

[0113] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 25.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 172,000, a molecular weight distribution index of 1.7, a melting temperature of 91°C, an isotacticity of 95%, an elongation at break of 810%, and an elastic modulus of 24 MPa.

[0114] Example 10

[0115] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-3. According to the experimental method in Example 2, the amount of hexene-1 monomer added was 25 g.

[0116] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 22.3 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 352,000, a molecular weight distribution index of 2.8, a melting temperature of 72°C, an isotacticity of 99%, an elongation at break of 980%, and an elastic modulus of 30 MPa.

[0117] Example 11

[0118] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-3. According to the experimental method in Example 2, the amount of hexene-1 monomer added was 55 g.

[0119] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 19.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 295,000, a molecular weight distribution index of 2.4, a melting temperature of 75°C, an isotacticity of 98%, an elongation at break of 650%, and an elastic modulus of 32 MPa.

[0120] Example 12

[0121] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-3. According to the experimental method in Example 2, the amount of hexene-1 monomer added was 110 g.

[0122] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 14.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 125,000, a molecular weight distribution index of 1.8, a melting temperature of 71°C, an isotacticity of 99%, an elongation at break of 1000%, and an elastic modulus of 36 MPa.

[0123] Example 13

[0124] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-3. Following the experimental method of Example 2, 42,800 μmol of the non-metallocene catalyst C1-3 was added (the molar ratio of monomer to non-metallocene catalyst was 100:1).

[0125] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 39.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 112,000, a molecular weight distribution index of 2.0, a melting temperature of 77°C, an isotacticity of 99%, an elongation at break of 970%, and an elastic modulus of 39 MPa.

[0126] Example 14

[0127] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-3. Following the experimental method of Example 2, 4280 μmol of the non-metallocene catalyst C1-3 was added (the molar ratio of monomer to non-metallocene catalyst was 1000:1).

[0128] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 30.8 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 143,000, a molecular weight distribution index of 2.2, a melting temperature of 74°C, an isotacticity of 98%, an elongation at break of 850%, and an elastic modulus of 40 MPa.

[0129] Example 15

[0130] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-3. Following the experimental method of Example 2, 540 μmol of the non-metallocene catalyst C1-3 was added (the molar ratio of monomer to non-metallocene catalyst was 8000:1).

[0131] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 24.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 176,000, a molecular weight distribution index of 2.3, a melting temperature of 75°C, an isotacticity of 96%, an elongation at break of 890%, and an elastic modulus of 42 MPa.

[0132] Example 16

[0133] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-3. Following the experimental method of Example 2, 110 μmol of the non-metallocene catalyst C1-3 was added (the molar ratio of monomer to non-metallocene catalyst was 40,000:1).

[0134] The catalytic activity of the non-metallocene catalyst C1-3 in this example is 9.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 154,000, a molecular weight distribution index of 2.7, a melting temperature of 78°C, an isotacticity of 98%, an elongation at break of 880%, and an elastic modulus of 37 MPa.

[0135] Example 17

[0136] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 catalyzed by a non-metallocene catalyst C1-10. Following the experimental method described in Example 2, the amount of [Ph3C][B(C6F5)4] used was 180 μmol (the molar ratio of activator to bridged bipyridylamino hafnium compound 1 was 1:1).

[0137] The catalytic activity of the non-metallocene catalyst C1-10 in this example is 7.6 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 199,000, a molecular weight distribution index of 2.5, a melting temperature of 82°C, an isotacticity of 98%, an elongation at break of 850%, and an elastic modulus of 42 MPa.

[0138] Example 18

[0139] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-11. Following the experimental method described in Example 2, the amount of [Ph3C][B(C6F5)4] used was 540 μmol (the molar ratio of activator to bridged bipyridylamino hafnium compound 1 was 3:1).

[0140] The catalytic activity of the non-metallocene catalyst C1-11 in this example is 8.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 276,000, a molecular weight distribution index of 2.6, a melting temperature of 81°C, an isotacticity of 98%, an elongation at break of 750%, and an elastic modulus of 45 MPa.

[0141] Example 19

[0142] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-12. Following the experimental method described in Example 2, the amount of [Ph3C][B(C6F5)4] used was 900 μmol (the molar ratio of activator to bridged bipyridylamino hafnium compound 1 was 5:1).

[0143] The catalytic activity of the non-metallocene catalyst C1-12 in this example is 10.2 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 246,000, a molecular weight distribution index of 2.7, a melting temperature of 81°C, an isotacticity of 98%, an elongation at break of 840%, and an elastic modulus of 29 MPa.

[0144] Example 20

[0145] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-4. Following the experimental method described in Example 2, the amount of triisobutylaluminum used was 13,500 μmol (the molar ratio of [Ph3C][B(C6F5)4] to triisobutylaluminum was 1:50).

[0146] The catalytic activity of the non-metallocene catalyst C1-4 in this example is 10.4 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 243,000, a molecular weight distribution index of 2.8, a melting temperature of 81°C, an isotacticity of 98%, an elongation at break of 950%, and an elastic modulus of 32 MPa.

[0147] Example 21

[0148] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-5. Following the experimental method described in Example 2, the amount of triisobutylaluminum used was 27,000 μmol (the molar ratio of [Ph3C][B(C6F5)4] to triisobutylaluminum was 1:150).

[0149] The catalytic activity of the non-metallocene catalyst C1-5 in this example is 11.2 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 228,000, a molecular weight distribution index of 3.0, a melting temperature of 81°C, an isotacticity of 98%, an elongation at break of 690%, and an elastic modulus of 43 MPa.

[0150] Example 22

[0151] This example provides a polybutene-1 elastomer prepared by copolymerizing butene-1 with hexene-1 using a non-metallocene catalyst C1-6. Following the experimental method described in Example 2, the amount of triisobutylaluminum used was 54,000 μmol (the molar ratio of [Ph3C][B(C6F5)4] to triisobutylaluminum was 1:300).

[0152] The catalytic activity of the non-metallocene catalyst C1-6 in this example is 18.3 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 273,000, a molecular weight distribution index of 2.9, a melting temperature of 80°C, an isotacticity of 98%, an elongation at break of 960%, and an elastic modulus of 39 MPa.

[0153] Example 23

[0154] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-1. According to the experimental method of Example 2, the alkyl aluminum added was trimethyl aluminum.

[0155] The catalytic activity of the non-metallocene catalyst C1-1 in this example is 8.9 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 199,000, a molecular weight distribution index of 2.7, a melting temperature of 78°C, an isotacticity of 98%, an elongation at break of 860%, and an elastic modulus of 29 MPa.

[0156] Example 24

[0157] This embodiment provides a polybutene-1 elastomer prepared by copolymerizing butene-1 and hexene-1 using a non-metallocene catalyst C1-2. According to the experimental method of Example 2, the alkyl aluminum added was triethylaluminum.

[0158] The catalytic activity of the non-metallocene catalyst C1-2 in this example is 17.5 kg polymer / (mmol Hf·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 261,000, a molecular weight distribution index of 2.8, a melting temperature of 76°C, an isotacticity of 98%, an elongation at break of 790%, and an elastic modulus of 35 MPa.

[0159] In order to better illustrate the beneficial effects of the present invention, a comparative example was used to prepare a polyethylene elastomer by copolymerizing ethylene and octene catalyzed by C1-3.

[0160] Comparative Example 1

[0161] This comparative example provides a polyethylene elastomer, which is prepared by copolymerizing ethylene and octene catalyzed by a C1-3 catalyst system, according to the following steps:

[0162] A 10L reactor was continuously purged with nitrogen for 30 minutes to ensure the removal of water and oxygen. Then, 100g of octene-1 monomer (the molar ratio of monomer to non-metallocene catalyst was 23900:1) was added, the temperature maintained at 60°C, and stirring was continued for half an hour. Subsequently, 180μmol of non-metallocene catalyst C1-3 was injected into the autoclave, the hydrogen pressure was raised to 0.05MPa, and the ethylene pressure was raised to 0.2MPa to initiate the copolymerization reaction. After 30 minutes of polymerization, a hydrochloric acid-treated ethanol solution was added to terminate the polymerization reaction. The polymer was filtered, washed three times with ethanol, and vacuum-dried to constant weight.

[0163] The catalytic activity of the non-metallocene catalyst C1-3 in this comparative example is 16.2 kg polymer / (mmol Hf·h). The prepared polyethylene elastomer has a weight-average molecular weight of 169,000, a molecular weight distribution index of 2.4, a melting temperature of 92°C, an elongation at break of 1010%, and an elastic modulus of 27 MPa.

[0164] Comparative Example 2

[0165] This comparative example provides a polybutene-1 elastomer, which is prepared by copolymerizing butene-1 and hexene-1 catalyzed by a metallocene catalyst, and the steps are as follows:

[0166] The 10L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 240g of butene-1 monomer, 80g of hexene-1 monomer, and 2ml of methylaluminoxane (MAO) were added, stirred, and the temperature maintained at 60°C for half an hour. Subsequently, 300μmol of zirconocene catalyst was injected into the autoclave, and the H2 pressure was raised to 0.05MPa to initiate the copolymerization reaction. After 60 minutes of polymerization, a 10% hydrochloric acid-containing ethanol solution was added to terminate the polymerization. The polymer was filtered, washed three times with ethanol, and vacuum-dried to constant weight.

[0167] The catalytic activity of the metallocene catalyst in this comparative example is 3.9 kg polymer / (mmol Zr·h). The prepared polybutene-1 elastomer has a weight-average molecular weight of 142,000, a molecular weight distribution index of 2.1, a melting temperature of 72°C, an isotacticity of 90%, an elongation at break of 680%, and an elastic modulus of 19 MPa.

[0168] The properties of the polybutene-1 elastomer obtained in Example 2 were compared with those obtained in the comparative example. The results are shown in Table 1 below:

[0169] Table 1 Comparison of polymerization results between Example 2 polybutene-1 elastomer and comparative example elastomer

[0170]

[0171] The polymerization results in Table 1 demonstrate that the non-metallocene catalyst prepared by the present invention can be used to copolymerize butene-1 with a series of α-olefins to produce elastomers. Compared to polyethylene elastomers, the elastomers exhibit a narrower molecular weight distribution, comparable polymerization activity, and an isotacticity of ≥98%. Furthermore, the non-metallocene catalyst exhibits significantly higher catalytic activity than metallocene catalysts, and the resulting elastomers exhibit higher molecular weights and narrower molecular weight distributions, resulting in superior mechanical properties compared to metallocene-catalyzed polybutene-1 elastomers.

[0172] The non-metallocene catalyst prepared by the present invention exhibits excellent copolymerization performance and product characteristics, and can use butene-1 monomer to prepare elastomers. Compared with the ethylene monomer used in polyolefin elastomers (POE), the price of the present invention is low. At the same time, the excess butene-1 monomer resources are utilized with high added value, which has a positive effect on optimizing the industrial structure of butene-1 resources.

[0173] The above embodiments are typical examples listed to illustrate the technical solutions of the present invention in detail. The present invention is subject to the scope of protection of the claims and the content of the invention and is not limited to the implementation scheme. Simple replacement or modification of the present invention is still within the scope of protection of the invention.

Claims

1. A bridged bipyridylamino hafnium compound, characterized in that: Having the structure shown in formula (I): Wherein, R1 is hydrogen or methyl; R2 is methyl or 2-isopropylphenyl.

2. A method for preparing the bridged bipyridylamino hafnium compound according to claim 1, characterized in that: The preparation method of the bridged bipyridylamino hafnium compound comprises the following steps: 1) A pyridone (aldehyde) compound is subjected to a coupling reaction with 1,3-phenylboronic acid to obtain a phenyl-disubstituted 1,3-phenyl-dipyridone (aldehyde) compound, 2) 1,3-phenyl-dipyridone (aldehyde) compound undergoes condensation reaction with 2,6-diisopropylaniline to obtain a pyridine diimine compound, 3) subjecting the pyridine diimine compound to a reduction reaction with a strong reducing agent such as trimethylaluminum or 2-isopropylphenyl lithium to obtain a pyridine amino compound ligand, 4) The pyridinylamino compound ligand reacts with n-butyl lithium to undergo a deprotonation reaction, and then a metal salt of hafnium tetrachloride is added to obtain a pyridinylamino hafnium chloride compound. 5) the pyridylamino hafnium chloride compound reacts with methylmagnesium bromide to obtain a bridged pyridylamino hafnium compound, 3. A non-metallocene catalyst, characterized in that include: The bridged bipyridylamine hafnium compound, co-catalyst and activator according to claim 1; the co-catalyst is a boron compound selected from at least one of [Ph3C][B(C6F5)4] and B(C6F5)3; the activator is an alkyl aluminum selected from at least one of trimethylaluminum, triethylaluminum and triisobutylaluminum; in the non-metallocene catalyst, the molar ratio of the bridged bipyridylamine hafnium compound, the boron compound and the alkyl aluminum is Hf: B: Al=1: (1~3): (0~900).

4. The non-metallocene catalyst according to claim 3, characterized in that The co-catalyst is [Ph3C][B(C6F5)4]; the activator is triisobutylaluminum.

5. The non-metallocene catalyst according to claim 3, characterized in that In the non-metallocene catalyst, the molar ratio of the bridged bipyridylamine hafnium compound, the boron compound, and the alkyl aluminum is Hf: B: Al=1: (1.2~2): (100~600).

6. A method for preparing a polybutene-1 elastomer, characterized in that: The method comprises the following steps: copolymerizing butene-1 and alpha-olefin comonomers, using the non-metallocene catalyst according to any one of claims 3 to 5 as a catalyst, adding a molecular weight regulator, and adopting a bulk polymerization process to obtain a polybutene-1 elastomer.

7. The preparation method according to claim 6, characterized in that When the copolymerization product is a binary copolymer, the α-olefin comonomer is selected from butene-1 and one of hexene-1, octene-1 or decene-1.

8. The preparation method according to claim 6, characterized in that When the copolymerization product is a terpolymer, the α-olefin comonomer is selected from two of ethylene, butene-1 and hexene-1, octene-1 or decene-1.

9. The preparation method according to claim 6, characterized in that The molar ratio of butene-1 to the non-metallocene catalyst is 2000-31800:1, and the mass ratio of butene-1 to the α-olefin comonomer is 100:10-60; the molecular weight regulator is H2, and the polymerization pressure of H2 is 0-0.1 MPa; the temperature of the polymerization reaction is 25-100°C.

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