Dual-center non-metallocene catalyst and preparation method therefor, and 1-butene-based elastomer and preparation method therefor

Abstract

The present invention relates to the technical field of organic synthesis. Disclosed are a dual-center non-metallocene catalyst and a preparation method therefor, and a 1-butene-based elastomer and a preparation method therefor. The dual-center non-metallocene catalyst comprises a structure represented by formula (I). In formula (I), R1-R5 are each independently selected from H and C1-C8 alkyl; R6 is selected from C1-C5 alkyl, aryl, and aryl substituted with C1-C5 alkyl; and R7 is selected from methyl and / or ethyl. When catalyzing a polymerization reaction between 1-butene and a long-chain α-olefin, the dual-center non-metallocene catalyst provided in the present invention can increase the insertion rate of an α-olefin monomer having large steric hindrance, facilitating the growth of a polymer chain, and can enable the preparation of a 1-butene-based elastomer material having large molecular weight, narrow molecular weight distribution, a low glass transition temperature, and a high random copolymer unit content.

Description

Dual-site non-metallocene catalysts, methods of making the same, and butene-1-based elastomers and methods of making the same

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202410848453.3, filed June 27, 2024, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of organic synthesis, in particular to a dual-site non-metallocene catalyst, a method of making the same, and a butene-1-based elastomer and a method of making the same. BACKGROUND

[0004] Thermoplastic elastomers are a kind of polymer materials with rubber elasticity at room temperature, plasticization forming at high temperature, and performance between rubber and resin. They can be divided into polyolefin-based elastomers, urethane-based elastomers, amide-based elastomers, etc. Among them, the copolymer of butene-1 and alpha-olefin in polyolefin-based elastomers is of great concern due to its excellent aging resistance and high added value.

[0005] Currently, butene-1 and alpha-olefin copolymerization mainly uses Ziegler-Natta catalysts. For example, Professor Wang Baochen's research group at Qingdao University of Science and Technology used a supported titanium-based catalyst to catalyze the copolymerization of butene-1 and hexene-1, and synthesized polybutene-1 thermoplastic elastomer. The isotacticity of this elastomer material is between 60-70%, and the crystallinity is between 20-30%. Its structure is similar to that of ethylene-octene copolymer (POE), and it has good application value in the field of toughening modification of brittle materials. However, the polybutene-1 thermoplastic elastomer prepared by using a supported titanium-based catalyst has problems such as wide molecular weight distribution and low copolymer monomer insertion rate.

[0006] Metallocene catalysts can also catalyze the copolymerization of butene-1 and alpha-olefin, but due to the presence of a metallocene structure in the structure of the metallocene catalyst, the space steric hindrance is large, and it is difficult for butene-1 and alpha-olefin monomers with large steric hindrance to insert, resulting in low catalyst activity. At the same time, the molecular weight of the prepared polymer is generally low, and it is difficult to prepare a polymer with a molecular weight exceeding 100,000.

[0007] Non-metallocene catalysts, as a new type of catalyst, have many advantages in alpha-olefin polymerization, such as cheap and easy-to-obtain raw materials, easy synthesis, etc. By changing the structure of the catalyst, the performance of the catalyst can be effectively controlled, thereby better controlling the structure and performance of the obtained polymer; the amount of co-catalyst used is small, which can effectively catalyze the copolymerization reaction.

[0008] However, the single-site non-metallocene catalysts in early studies have the problems of narrow molecular weight distribution and difficult processing of the polymer. The bimetallic catalysts disclosed in the current reports are mainly used in the preparation of ethylene and ethylene copolymer. Since 1-butene has a longer carbon chain and greater steric hindrance than ethylene, it is difficult for such catalysts to efficiently catalyze the polymerization of butene-1 and α-olefin monomers.

[0009] CN116948070A discloses a non-metallocene catalyst for catalyzing the polymerization of butene-1, which comprises the following structure:

[0010] wherein R1, R2 are selected from hydrogen, a hydrocarbon group having 1-10 carbon atoms, R1 and R2 are the same or different, R3 is selected from hydrogen, a hydrocarbon group having 1-10 carbon atoms, and R4 is selected from methyl, ethyl, n-propyl, and Ar is phenyl, naphthyl, an aliphatic hydrocarbon group-substituted phenyl, and an aliphatic hydrocarbon group-substituted naphthyl. The non-metallocene catalyst has a bridged pyridyl amine hafnium structure and is used to catalyze the synthesis of polybutene-1. The catalyst has high catalytic activity, high monomer conversion rate, and the prepared polybutene-1 has high isotacticity and narrow distribution. However, this patent only discloses that the above-mentioned bimetallic catalyst can be used to prepare homopolymer polybutene-1, and the copolymerization performance is not described.

[0011] Currently, the catalysts used for the copolymerization of butene-1 and α-olefins are mainly Ziegler-Natta catalysts. For example, Huang Baochen's research group at Qingdao University of Science and Technology has conducted a series of studies on the copolymerization of 1-butene and 1-hexene (Wang B, Yao W, Zhao YX, et al. Copolymerization of 1-butene and 1-hexene catalyzed by supported titanium system [J]. Synthetic Rubber Industry, 2006(6); Wang HZ, Liu C, Shao HF, et al. Effect of catalyst on structure and performance of 1-butene and 1-hexene copolymer elastomer [J]. Journal of Qingdao University of Science and Technology: Natural Science Edition, 2010(5)). A new type of random thermoplastic elastomer was prepared by using a supported titanium catalyst to catalyze the copolymerization of 1-butene and 1-hexene. However, the experimental results showed that the activity of the supported titanium catalyst used was low, the α-olefin insertion rate of the product was low, and the transparency was poor.

[0012] WO2002002659A1 discloses a copolymer of 1-butene containing copolymer units of α-olefins having 2-10 carbon atoms, which is prepared by using a high-activity supported titanium catalyst to prepare a polymer from α-olefins containing 4 or more carbon atoms. The molded product prepared from the copolymer has excellent heat resistance, low-temperature properties, and handling properties, as well as excellent high-temperature creep resistance, and is particularly suitable for producing pipes. However, the use of a multi-active center titanium catalyst leads to a wide molecular weight distribution of the prepared product.

[0013] In addition, the polymerization reaction of butene-1 and the α-olefin monomer is block copolymerization, and there is no random copolymer unit in the polymerization product. Compared with homopolymerization polybutene-1, the crystallinity of the copolymerization product of butene-1 and the α-olefin is high, and the flexibility is relatively poor.

[0014] Therefore, it is urgent to provide a catalyst for butene-1-based elastomer material which can be applied to long-chain α-olefin polymerization, can improve the monomer insertion rate and catalyst activity, can increase the molecular weight and the content of random copolymer units of the polymerization product, and can narrow the range of molecular weight distribution, and a preparation method thereof. SUMMARY

[0015] The purpose of the present application is to solve the problems of the existing catalysts, such as the difficulty of inserting α-olefin monomers with large steric hindrance, the low weight average molecular weight of the butene-1-based elastomer prepared, the wide molecular weight distribution, and the low content of random copolymer units, when catalyzing the copolymerization of butene-1 and long-chain α-olefin, to provide a bidentate non-metallocene catalyst, a preparation method thereof, and a butene-1-based elastomer and a preparation method thereof.

[0016] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a bidentate non-metallocene catalyst, wherein the catalyst comprises a structure shown in formula I:

[0017] wherein R1-R5 are independently selected from H or C1-C8 alkyl, R6 is selected from C1-C5 alkyl, aryl or aryl containing C1-C5 alkyl substituents, and R7 is selected from methyl and / or ethyl.

[0018] The second aspect of the present application provides a preparation method of a bidentate non-metallocene catalyst, wherein the method comprises the following steps:

[0019] (1) Suzuki coupling reaction of 4,4'-diphenyl diboronic acid with halogenated thiophene shown in formula 1-1 to obtain a ligand intermediate shown in formula A; wherein x in formula 1-1 is selected from chlorine, bromine, iodine;

[0020] (2) Schiff base reaction of the ligand intermediate with aniline shown in formula 1-2 to obtain a ligand precursor shown in formula B; wherein R1-R5 in formula 1-2 are independently selected from H or C1-C8 alkyl;

[0021] (3) reduction reaction of the ligand precursor with hydroxyl lithium I with a structure of R6-Li to obtain a catalyst ligand shown in formula C; wherein R6 is selected from C1-C5 alkyl, aryl or aryl containing C1-C5 alkyl substituents;

[0022] (4) the catalyst ligand first deprotonates with the alkyl lithium II, then substitution reaction occurs with hafnium tetrachloride, and then methylation reaction occurs with the Grignard reagent of the structural formula R7MgX, to obtain the non-metallocene catalyst shown in formula D; wherein R7 is selected from methyl or ethyl, and X is selected from chlorine, bromine, iodine;

[0023] The third aspect of the present application provides a method for polymerization of butene-1 and alpha-olefin, wherein butene-1 and alpha-olefin are subjected to copolymerization under the action of a catalyst to obtain butene-1-based elastomer; wherein the catalyst is the catalyst described in the first aspect of the present application or the catalyst prepared by the method described in the second aspect of the present application.

[0024] The fourth aspect of the present application provides the butene-1-based elastomer prepared by the method described in the third aspect of the present application.

[0025] Compared with the prior art, the present application has the beneficial technical effects as follows:

[0026] 1) The bimetallic non-metallocene catalyst provided in the present application can improve the insertion rate of alpha-olefin monomers with large steric hindrance when catalyzing the polymerization of butene-1 and long-chain alpha-olefin, is conducive to the growth of polymerization chains, and can prepare butene-1-based elastomer materials with high random copolymer unit content, large molecular weight, narrow molecular weight distribution, and low glass transition temperature;

[0027] 2) The preparation method of the bimetallic non-metallocene catalyst provided in the present application has the advantages of easy-to-obtain raw materials, simple process flow, mild reaction conditions, and high product yield and purity, and is suitable for industrialization promotion;

[0028] 3) The method for polymerization of butene-1 and alpha-olefin provided in the present application can prepare butene-1-based elastomer with excellent flexibility, mechanical strength, and low-temperature resistance. BRIEF DESCRIPTION OF DRAWINGS

[0029] FIGS. 1-3 are nuclear magnetic resonance hydrogen spectra of the catalyst ligand prepared in catalyst preparation examples 1, 7, and 8, respectively;

[0030] FIGS. 4-6 are nuclear mass spectra of the catalyst prepared in catalyst preparation examples 1, 7, and 8, respectively;

[0031] FIG. 7 is a sample diagram of butene-1-based elastomer material prepared in butene-1-based elastomer preparation example 1;

[0032] FIG. 8 is a nuclear magnetic carbon spectrum of butene-1-based elastomer material prepared in butene-1-based elastomer preparation example 1;

[0033] Figure 9 is a DSC plot of the butene-1 based elastomer material produced in Example 1 of the butene-1 based elastomer production;

[0034] Figure 10 is a GPC plot of the butene-1 based elastomer material produced in Example 1 of the butene-1 based elastomer production. DETAILED DESCRIPTION

[0035] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are provided as approximate values, and the ranges and values are understood to encompass values approximately the same as the stated values. For example, a range from 1 to 6 should be interpreted to include not only the precise ranges from 1 to 6 and 2 to 8, but also other ranges that are approximately equivalent, such as from 1.5 to 5.7, or from 1.75 to 5. 5.5, or from 1.9 to 5.1.

[0036] A first aspect of the present application provides a dual center non-metallocene catalyst, wherein the catalyst comprises a structure as shown in Formula I:

[0037] wherein R1-R5 are each independently selected from H or C1-C8 alkyl, R6 is selected from C1-C5 alkyl, aryl or aryl containing C1-C5 alkyl substituents, and R7 is selected from methyl and / or ethyl.

[0038] In a preferred embodiment of the present application, R1-R5 are each independently selected from H or C1-C5 alkyl.

[0039] In a preferred embodiment of the present application, R1 and R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, t-butyl, and further preferably, R1 and R5 are the same.

[0040] In a preferred embodiment of the present application, R2 and R4 are hydrogen, and R3 is selected from hydrogen, t-butyl, iso-propyl.

[0041] In a preferred embodiment of the present application, R6 is selected from methyl, ethyl, propyl, butyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl.

[0042] wherein in the present application, propyl can be n-propyl or iso-propyl, and butyl can be n-butyl, iso-butyl, sec-butyl and t-butyl. The number of methyl, ethyl, propyl, butyl substituents on the phenyl group in methylphenyl, ethylphenyl, propylphenyl, butylphenyl is 1-5, and the substitution position is not limited, preferably the number of substitution is 1, and the substitution position is ortho. Further preferably, R6 is selected from methyl, iso-propyl, t-butyl, phenyl, 2-iso-propylphenyl, and more preferably 2-iso-propylphenyl.

[0043] In a preferred embodiment of the present application, the structural formula of the catalyst is selected from one or more of the following structural formulae:

[0044] The bimetallic non-metallocene catalyst provided in the present application can improve the insertion rate of α-olefin monomers with large steric hindrance when catalyzing the polymerization of butene-1 and long-chain α-olefins, is conducive to the growth of polymerization chains, and can prepare butene-1-based elastomer materials with large molecular weight, narrow molecular weight distribution, and low glass transition temperature.

[0045] The second aspect of the present application provides a preparation method of a bimetallic non-metallocene catalyst, wherein the method comprises the following steps:

[0046] (1) 4,4'-diphenyl boric acid undergoes a Suzuki coupling reaction with a halogenated thiophene represented by formula 1-1 to obtain a ligand intermediate represented by formula A; wherein X in formula 1-1 is selected from chlorine, bromine, and iodine;

[0047] (2) The ligand intermediate undergoes a Schiff base reaction with an aniline represented by formula 1-2 to obtain a ligand precursor represented by formula B; wherein R1-R5 in formula 1-2 are each independently selected from H or C1-C8 alkyl;

[0048] (3) The ligand precursor undergoes a reduction reaction with a hydrocarbyllithium I having a structural formula of R6-Li to obtain a catalyst ligand represented by formula C; wherein R6 is selected from C1-C5 alkyl, aryl, or aryl containing C1-C5 alkyl substituents;

[0049] (4) The catalyst ligand first undergoes a deprotonation reaction with an alkyl lithium II, then a substitution reaction with hafnium tetrachloride is added, and then a methylation reaction with a Grignard reagent having a structural formula of R7MgX is added to obtain a non-metallocene catalyst represented by formula D; wherein R7 is selected from methyl or ethyl, and X is selected from chlorine, bromine, and iodine;

[0050] In step (1):

[0051] In a preferred embodiment of the present application, the halogenated thiophene represented by formula 1-1 is selected from one or more of 5-chloro-2-thiophene formaldehyde, 5-bromo-2-thiophene formaldehyde, and 5-iodo-2-thiophene formaldehyde, and is preferably 5-bromo-2-thiophene formaldehyde.

[0052] In a preferred embodiment of the present application, the Suzuki coupling reaction is carried out in the presence of a promoter and a Suzuki coupling catalyst; wherein the promoter is an alkaline promoter, and the Suzuki coupling catalyst is a palladium catalyst.

[0053] In a preferred embodiment of the present application, the basic promoter is selected from one or more of ethylamine, ethylenediamine, dimethylamine, pyridine, N,N-dimethylethylenediamine, potassium carbonate, sodium carbonate, preferably potassium carbonate and / or sodium carbonate; and the palladium catalyst is selected from one or more of palladium dichloride, palladium acetate, and dichlorobis(triphenylphosphine)palladium, preferably dichlorobis(triphenylphosphine)palladium.

[0054] In a preferred embodiment of the present application, the molar ratio of 4,4'-biphenyldiboronic acid to the halogenated thiophene of formula 1-1 is 1:1-5, preferably 1:2-3; the amount ratio of 4,4'-biphenyldiboronic acid to the promoter is 10 mmol:0.5-3.5 g, preferably 10 mmol:1-2.5 g; and the amount ratio of 4,4'-biphenyldiboronic acid to the Suzuki coupling catalyst is 10 mmol:10-20 mg, preferably 10 mmol:14-16 mg.

[0055] In a preferred embodiment of the present application, the Suzuki coupling reaction is carried out in solvent I, in which 4,4'-biphenyldiboronic acid, the promoter, and the Suzuki coupling catalyst are mixed uniformly in solvent I, and then the halogenated thiophene solution of formula 1-1 is added dropwise at room temperature.

[0056] In the present application, solvent I is an alcohol solvent selected from one or more of methanol, ethanol, n-propanol, and isopropanol, preferably ethanol. The amount of solvent I is 20-40 mL based on 10 mmol of 4,4'-biphenyldiboronic acid. The solvent in the halogenated thiophene solution of formula 1-1 is selected from one or more of benzene, toluene, and ethylbenzene, and the concentration of the halogenated thiophene of formula 1-1 in the halogenated thiophene solution of formula 1-1 is 0.5-5 mmol / mL.

[0057] In a preferred embodiment of the present application, the reaction temperature of the Suzuki coupling reaction is 70-120°C, preferably 90-100°C; and the reaction time is 8-20 h, preferably 12-16 h.

[0058] In the present application, the equation of the reaction occurring in step (1) is as follows:

[0059] After the Suzuki coupling reaction is completed, the reaction solution is first concentrated, and then purified by silica gel column chromatography to obtain the ligand intermediate. In the present application, when the silica gel column chromatography is performed, the eluent is selected from n-hexane and / or ethyl acetate, preferably n-hexane and ethyl acetate in a volume ratio of 20-30:1.

[0060] In step (2):

[0061] In a preferred embodiment of the present application, in the formula 1-2, R1-R5 are each independently selected from H or C1-C5 alkyl.

[0062] In a preferred embodiment of the present application, R1 and R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, t-butyl, and further preferably, R1 and R5 are the same. R2 and R4 are hydrogen, and R3 is selected from hydrogen, t-butyl, isopropyl.

[0063] In a preferred embodiment of the present application, the aniline represented by the formula 1-2 is selected from one or more of aniline, 2,6-di(isopropyl)aniline, 2-methylaniline, 2-ethylaniline, 2-n-propylaniline, 2-isopropylaniline, 2-t-butylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-di-t-butylaniline, 2-methyl-6-t-butylaniline, 2-methyl-6-ethylaniline, 2,4,6-tri-t-butylaniline, and preferably 2,6-di(isopropyl)aniline.

[0064] In a preferred embodiment of the present application, the Schiff base reaction is carried out in the presence of a Schiff base catalyst; wherein the Schiff base catalyst is an aryl sulfonic acid compound, and is selected from one or more of benzenesulfonic acid, p-toluenesulfonic acid, p-ethylbenzenesulfonic acid, and preferably p-toluenesulfonic acid.

[0065] In a preferred embodiment of the present application, the molar ratio of the ligand intermediate to the aniline represented by the formula 1-2 is 1:1-4, and preferably 1:2-3; and the amount ratio of the ligand intermediate to the Schiff base catalyst is 5 mmol: 5-20 mg, and preferably 5 mmol: 10-15 mg.

[0066] In a preferred embodiment of the present application, the Schiff base reaction is carried out in a solvent II; the ligand intermediate, the aniline represented by the formula 1-2, and the Schiff base catalyst are first mixed uniformly in the solvent II, and then the Schiff base reaction is carried out after being warmed.

[0067] In a preferred embodiment of the present application, the solvent II is a non-polar solvent, and is selected from one or more of benzene, toluene, xylene, and preferably toluene; and the mass ratio of the ligand intermediate to the solvent II is 5 mmol: 40-60 mL.

[0068] In a preferred embodiment of the present application, the reaction temperature of the Schiff base reaction is 110-170°C, and preferably 120-150°C; and the reaction time is 36-60 h, and preferably 45-55 h.

[0069] In the present application, the reaction equation of the Schiff base reaction in step (2) is as follows: In a preferred embodiment of the present application, the reaction equation of the Schiff base reaction in step (2) is as follows:

[0070] After the Schiff base reaction is completed, the reaction solution obtained after the Schiff base reaction is first subjected to rotary evaporation treatment, then eluted with ethanol, and then dried to obtain the ligand precursor.

[0071] In step (3):

[0072] In a preferred embodiment of the present application, in the hydrocarbyllithium I, R6 is selected from methyl, ethyl, propyl, butyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl; further preferably, R6 is selected from methyl, isopropyl, tert-butyl, phenyl, 2-isopropylphenyl, and more preferably, R6 is 2-isopropylphenyl.

[0073] That is, in the present application, the hydrocarbyllithium I is selected from one or more of methyl lithium, ethyl lithium, propyl lithium, butyl lithium, phenyl lithium, methylphenyl lithium, ethylphenyl lithium, propylphenyl lithium, butylphenyl lithium, preferably methyl lithium, isopropyl lithium, tert-butyl lithium, phenyl lithium, 2-isopropylphenyl lithium, and more preferably 2-isopropylphenyl lithium.

[0074] In a preferred embodiment of the present application, the molar ratio of the ligand precursor to hydrocarbyllithium I is 1:2-3, preferably 1:2.2-2.4.

[0075] In a preferred embodiment of the present application, the reduction reaction is carried out in solvent III; wherein the solvent III is selected from one or more of tetrahydrofuran, diethyl ether, isopropyl ether, ethyl acetate, n-butanol, and preferably tetrahydrofuran; the amount ratio of the ligand precursor to solvent III is 5 mmol: 40-60 mL.

[0076] In the present application, the ligand precursor is first dissolved in solvent III, and then hydrocarbyllithium I is added dropwise for reduction reaction; preferably, the hydrocarbyllithium I is added dropwise into the solvent III containing the ligand precursor at -50°C to -30°C, then stirred for 0.5-2.5 h, restored to room temperature, and then subjected to reduction reaction.

[0077] In a preferred embodiment of the present application, the reaction temperature of the reduction reaction is 70-110°C, preferably 90-100°C; the reaction time is 8-20 h, preferably 12-16 h.

[0078] In the present application, after the reduction reaction is completed, quenching is carried out with an aqueous NH4Cl solution under ice bath conditions, then separated, extracted with ethyl acetate, then washed with brine (e.g., NaCl saturated solution), dried with anhydrous Na2SO4, and rotary evaporated to obtain a light yellow catalyst ligand.

[0079] In step (4):

[0080] In a preferred embodiment of the present application, the deprotonation reaction, the substitution reaction and the methylation reaction are carried out in solvent IV; wherein the solvent IV is selected from one or more of benzene, toluene, ethylbenzene, preferably toluene. The amount of solvent IV is 10-30 mL based on 2 mmol of the catalyst ligand.

[0081] In the present application, the specific operation of step (4) comprises: adding the hydrocarbyllithium II dropwise into the solvent IV containing the catalyst ligand under ice bath condition to carry out the deprotonation reaction, adding hafnium tetrachloride into the reaction solution after a period of time to carry out the substitution reaction, and then adding the Grignard reagent R7MgX into the reaction solution after a period of time to carry out the substitution reaction, thereby obtaining the bimetallic non-metallocene catalyst.

[0082] In a preferred embodiment of the present application, the hydrocarbyllithium II is selected from one or more of n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, propyllithium, phenyllithium, preferably n-butyllithium. In the present application, the hydrocarbyllithium I and the hydrocarbyllithium II can be the same or different.

[0083] In a preferred embodiment of the present application, the molar ratio of the catalyst ligand to the hydrocarbyllithium II is 1:2-3.3, preferably 1:2.2-2.8.

[0084] In a preferred embodiment of the present application, the reaction temperature of the deprotonation reaction is room temperature-50°C, preferably room temperature; and the reaction time is 2-5 h, preferably 2.5-3.5 h. In the present application, room temperature has the known meaning, for example 15-35°C.

[0085] In a preferred embodiment of the present application, the molar ratio of the catalyst ligand to the hafnium tetrachloride is 1:2-3.1, preferably 1:2.1-2.5.

[0086] In a preferred embodiment of the present application, the reaction temperature of the substitution reaction is 70-110°C, preferably 90-100°C; and the reaction time is 8-16 h, preferably 10-14 h.

[0087] In a preferred embodiment of the present application, the Grignard reagent is selected from one or more of MeMgCl, EtMgCl, MeMgBr, EtMgBr, preferably MeMgCl and / or EtMgCl.

[0088] In a preferred embodiment of the present application, the molar ratio of the catalyst ligand to the Grignard reagent is 1:2.75-4.5, preferably 1:3.5-4.

[0089] In a preferred embodiment of the present application, the reaction temperature of the methylation reaction is room temperature to 50°C, preferably room temperature; and the reaction time is 1-5h, preferably 2-4h.

[0090] In the present application, after the methylation reaction, solid-liquid separation is performed, and the product is washed with n-hexane for several times, then crystallization is performed at -50°C to -25°C, followed by filtration, washing and drying to obtain the bimetallic non-metallocene catalyst.

[0091] In a preferred embodiment of the present application, steps (1)-(4) are performed under inert gas protection. The inert gas is selected from one or more of nitrogen, helium and argon.

[0092] The third aspect of the present application provides a method for polymerization of butene-1 and α-olefin, wherein the butene-1 and α-olefin are subjected to copolymerization under the action of a catalyst to obtain butene-1-based elastomer; wherein the catalyst is the catalyst of the first aspect of the present application or is prepared by the method of the second aspect of the present application.

[0093] In the present application, the α-olefin is selected from C6-C 10 The α-olefin can be one or more of hexene-1, octene-1 and decene-1. The operating conditions for the polymerization of butene-1 and α-olefin are not particularly limited in the present application, and the reaction can be performed according to the known operation, which will not be described herein. The use of the bimetallic non-metallocene catalyst provided in the present application to catalyze the polymerization of butene-1 and α-olefin can significantly improve the insertion rate of monomers with large steric hindrance, and can significantly increase the weight average molecular weight of the prepared polymer, reduce the molecular weight distribution range and decrease the glass transition temperature.

[0094] In a preferred embodiment of the present application, the amount of the α-olefin added accounts for 3-30wt% of the total mass of butene-1 and α-olefin, for example, 3%, 5%, 8%, 10%, 12%, 15%, 17%, 20%, 23%, 25%, 26%, 30%, and any number between these values.

[0095] The fourth aspect of the present application provides a butene-1-based elastomer prepared by the method of the third aspect of the present application.

[0096] In a preferred embodiment of the present application, the weight average molecular weight of the butene-1-based elastomer is ≥47×10 4 g / mol, preferably 47-65×10 4 g / mol; and the molecular weight distribution index is 1.5-3.5, preferably 1.8-3.

[0097] In a preferred embodiment of the present application, the glass transition temperature of the butene-1-based elastomer is ≤-20℃, preferably -35℃ to -20℃.

[0098] In a preferred embodiment of the present application, the α-olefin insertion rate is ≥9%, preferably 9-29%, and the content of random copolymerization units of butene-1 and α-olefin is ≥1 wt%, preferably 1.5-13 wt%, calculated based on 100% of the mass of the butene-1-based elastomer.

[0099] In a preferred embodiment of the present application, the density of the butene-1-based elastomer is 0.83-0.86 g / cm 3 , preferably 0.83-0.85 g / cm 3 .

[0100] The present application will be described in detail below through examples. In the examples and comparative examples, the drugs used are commercially available, analytically pure products.

[0101] Preparation Example 1 of catalyst

[0102] (1) Under a nitrogen atmosphere, 10 mmol of 4,4'-diphenyl boronic acid, 30 mL of ethanol, 15 mg of bis(triphenylphosphine) palladium dichloride and 2 g of K2CO3 were added to a reaction bottle and mixed uniformly, then 20 mL of a toluene solution containing 22 mmol of 5-bromo-2-thiophene formaldehyde was slowly added dropwise to the reaction bottle, after the dropwise addition was completed, the temperature was raised to 90℃, and the reaction was stirred for 12 h, then the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent was a mixture of n-hexane and ethyl acetate at a volume ratio of 25:1) to obtain a ligand intermediate shown in formula A', with a yield of 96%;

[0103] (2) Under a nitrogen atmosphere, 5 mmol of the ligand intermediate, 11 mmol of 2,6-di(isopropyl) aniline and 10 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene, and then subjected to water reflux at 125℃ for 48 h, after which it was spin-dried, washed with ethanol and dried to obtain a ligand precursor shown in formula B', with a yield of 91%;

[0104] (3) Under a nitrogen atmosphere, 5 mmol of the ligand precursor was dissolved in 50 mL of dry tetrahydrofuran, and 11 mmol of 2-isopropyl benzyl lithium was slowly added dropwise to the tetrahydrofuran solution at -40℃, stirred for 1 h, then slowly returned to room temperature, heated to 90℃ for reflux for 12 h, quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with saturated aqueous sodium chloride solution, dried over anhydrous Na2SO4, and spin-dried to obtain a light yellow catalyst ligand shown in formula C', with a yield of 89%;

[0105] (4) In a Schlenk flask filled with nitrogen, 2 mmol of catalyst ligand was dissolved in 20 mL of dry toluene, 5 mmol of n-butyllithium solution was added dropwise at 0°C, after the dropwise addition was completed, it was naturally warmed to room temperature, and the deprotonation reaction was carried out at room temperature. After 3 h of reaction, 4.4 mmol of HfCl4 was added to the Schlenk flask, and the temperature was raised to 90°C for substitution reaction. After 12 h of reaction, it was lowered to room temperature, 7.5 mmol of MeMgCl was added dropwise to the Schlenk flask, and the methylation reaction was carried out at room temperature. After 3 h of reaction, solid-liquid separation was carried out, the solid was washed with n-hexane for 3 times, and the n-hexane filtrate was collected after filtration. Crystallization was carried out at -35°C overnight, and the crystals were filtered, washed and dried to obtain the bimetallic non-metallocene catalyst represented by formula D’ with a yield of 74%.

[0106] The reaction equation involved in the catalyst preparation example 1 is as follows:

[0107] The catalyst ligand prepared in step (3) was tested by nuclear magnetic resonance hydrogen spectrum, and the obtained nuclear magnetic hydrogen spectrum was as follows: 1 H NMR (CD3Cl, 400 MHz): δ (ppm) 1.20 (d, 36H, Ar-C-CH3), 2.87 (m, 6H, Ar-CH), 4.0 (s, 2H, N-H), 5.19 (s, 2H, N-CH-Ar), 6.83-7.18 (m, 14H, N-Ar-H), 6.83-7.31 (m, 4H, Thio-H), 7.25-7.85 (d, 8H, Ar-H). It can be seen from the nuclear magnetic hydrogen spectrum that the prepared catalyst ligand C’ is consistent with the theoretical structure.

[0108] The bimetallic non-metallocene catalyst prepared in step (4) was tested by mass spectrometry, and the test results were as follows: MS-EI (m / z): 1346.5. It can be seen from the mass spectrometry test results that 1346.5 is the molecular ion peak of the catalyst D’. Combined with the nuclear magnetic hydrogen spectrum of the catalyst ligand and the mass spectrometry test results of the bimetallic non-metallocene catalyst, it can be seen that the compound represented by formula D’ is synthesized in the catalyst preparation example 1.

[0109] Catalyst preparation example 2

[0110] (1) 10 mmol of 4,4'-diphenylboronic acid, 30 mL of ethanol, 14 mg of bis(triphenylphosphine)palladium dichloride and 1.2 g of K2CO3 were added into a reaction bottle under nitrogen atmosphere, and mixed uniformly, then 20 mL of toluene solution containing 30 mmol of 5-bromo-2-thiophenecarboxaldehyde was slowly added dropwise into the reaction bottle, and after the dropwise addition was completed, the temperature was raised to 100°C, and after stirring for 16 h, the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent: a mixture of n-hexane and ethyl acetate at a volume ratio of 25:1) to obtain a ligand intermediate, and the yield was 92%;

[0111] (2) 5 mmol of the ligand intermediate, 12.5 mmol of 2,6-di(isopropyl)aniline and 15 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene under nitrogen atmosphere, and after water refluxing at 140°C for 52 h, it was rotary dried, washed with ethanol, and dried to obtain a ligand precursor, and the yield was 92%;

[0112] (3) 5 mmol of the ligand precursor was dissolved in 50 mL of dry tetrahydrofuran under nitrogen atmosphere, and 12 mmol of 2-isopropylbenzene lithium was slowly added dropwise into the tetrahydrofuran solution at -40°C, and after stirring for 1 h, it was slowly returned to room temperature, heated to 100°C for refluxing for 16 h, quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with saturated aqueous NaCl solution, dried over anhydrous Na2SO4, and rotary dried to obtain a yellowish catalyst ligand, and the yield was 90%;

[0113] (4) 2 mmol of the catalyst ligand was dissolved in 20 mL of dry toluene in a nitrogen-filled Schlenk bottle, and 5.6 mmol of n-butyllithium solution was added dropwise at 0°C, and after the dropwise addition was completed, it was naturally warmed to room temperature, and deprotonation was carried out at room temperature for 2.5 h, then 4.6 mmol of HfCl4 was added into the Schlenk bottle, and the temperature was raised to 100°C for substitution reaction, and after reaction for 10 h, the temperature was lowered to room temperature, 8 mmol of MeMgCl was added dropwise into the Schlenk bottle, and methylation was carried out at room temperature for 2 h, then solid-liquid separation was carried out, the solid was washed with n-hexane for 3 times, and after filtration, the n-hexane filtrate was crystallized at -35°C overnight, the crystals were filtered, washed and dried to obtain a bimetallic non-metallocene catalyst, and the yield was 72%.

[0114] Catalyst Preparation Example 3

[0115] (1) 10 mmol of 4,4'-diphenylboronic acid, 30 mL of ethanol, 16 mg of bis(triphenylphosphine)palladium dichloride and 2.4 g of K2CO3 were added into a reaction bottle under nitrogen atmosphere, and mixed uniformly, then 20 mL of toluene solution containing 25 mmol of 5-bromo-2-thiophenecarboxaldehyde was slowly added dropwise into the reaction bottle, and after the dropwise addition was completed, the temperature was raised to 95°C, and after stirring for 14 h, the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent: a mixture of n-hexane and ethyl acetate at a volume ratio of 25:1) to obtain a ligand intermediate, and the yield was 90%;

[0116] (2) 5 mmol of the ligand intermediate, 15 mmol of 2,6-di(isopropyl)aniline and 12 mg of p-toluenesulfonic acid were dissolved in 50 mL of toluene under nitrogen atmosphere, and subjected to water reflux at 150°C for 55 h, and then dried, washed with ethanol and dried to obtain a ligand precursor, and the yield was 89%;

[0117] (3) 5 mmol of the ligand precursor was dissolved in 50 mL of dry tetrahydrofuran under nitrogen atmosphere, and 11.5 mmol of 2-isopropylbenzene lithium was slowly added dropwise into the tetrahydrofuran solution at -40°C, and after stirring for 1 h, the temperature was slowly returned to room temperature, and heated to 95°C for reflux for 14 h; quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with saturated aqueous NaCl solution, dried over anhydrous Na2SO4, and dried to obtain a light yellow catalyst ligand, and the yield was 91%;

[0118] (4) 2 mmol of the catalyst ligand was dissolved in 20 mL of dry toluene in a nitrogen-filled Schlenk bottle, and 4.4 mmol of n-butyllithium solution was added dropwise at 0°C, and after the dropwise addition was completed, the temperature was naturally raised to room temperature, and deprotonation was carried out at room temperature, and after reaction for 3.5 h, 4.8 mmol of HfCl4 was added into the Schlenk bottle, and the temperature was raised to 95°C, and substitution reaction was carried out, and after reaction for 14 h, the temperature was lowered to room temperature, and 7 mmol of MeMgCl was added dropwise into the Schlenk bottle, and methylation was carried out at room temperature, and after reaction for 2 h, solid-liquid separation was carried out, the solid was washed with n-hexane for 3 times, and after filtration, the n-hexane filtrate was crystallized at -35°C overnight, and the crystals were filtered, washed and dried to obtain a bimetallic non-metallocene catalyst, and the yield was 69%.

[0119] Catalyst Preparation Example 4

[0120] (1) 10 mmol of 4,4'-diphenylboronic acid, 30 mL of ethanol, 18 mg of palladium acetate and 3 g of ethylamine were added into a reaction bottle under nitrogen atmosphere, and mixed uniformly, then 20 mL of toluene solution containing 15 mmol of 5-bromo-2-thiophenecarboxaldehyde was slowly added dropwise into the reaction bottle, after the dropwise addition was completed, the temperature was raised to 70°C, and the reaction was stirred for 8 h, then the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent was a mixture of n-hexane and ethyl acetate in a volume ratio of 25:1) to obtain a ligand intermediate, and the yield was 81%;

[0121] (2) 5 mmol of the ligand intermediate, 5 mmol of 2,6-di(isopropyl)aniline and 5.6 mg of benzenesulfonic acid were dissolved in 50 mL of benzene under nitrogen atmosphere, and subjected to water reflux at 160°C for 42 h, then rotary evaporation was performed, and ethanol was used for elution and drying to obtain a ligand precursor, and the yield was 80%;

[0122] (3) 5 mmol of the ligand precursor was dissolved in 50 mL of dry diethyl ether under nitrogen atmosphere, and 15 mmol of 2-isopropylbenzene lithium was slowly added dropwise into the diethyl ether solution at -40°C, and stirred for 1 h, then slowly returned to room temperature, heated to 80°C for reflux for 18 h, then quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with saturated aqueous NaCl solution, dried over anhydrous Na2SO4, and rotary evaporation was performed to obtain a light yellow catalyst ligand, and the yield was 83%;

[0123] (4) 2 mmol of the catalyst ligand was dissolved in 20 mL of dry ethylbenzene in a nitrogen-filled Schlenk bottle, and 4 mmol of n-butyllithium solution was added dropwise at 0°C, then after the dropwise addition was completed, the temperature was naturally raised to 40°C, and deprotonation was performed, and after the reaction for 4 h, 5.4 mmol of HfCl4 was added into the Schlenk bottle, and the temperature was raised to 80°C, and substitution reaction was performed, and after the reaction for 8 h, the temperature was lowered to room temperature, and 6 mmol of MeMgCl was added dropwise into the Schlenk bottle, and methylation was performed at 40°C, and after the reaction for 1 h, solid-liquid separation was performed, the solid was washed with n-hexane for 3 times, and after filtration, the n-hexane filtrate was crystallized at -35°C overnight, and the crystals were filtered, washed and dried to obtain a bimetallic non-metallocene catalyst, and the yield was 56%.

[0124] Catalyst Preparation Example 5

[0125] (1) 10 mmol of 4,4'-diphenylboronic acid, 30 mL of methanol, 20 mg of palladium acetate and 0.8 g of ethylenediamine were added into a reaction bottle under nitrogen atmosphere, and mixed uniformly, then 20 mL of a toluene solution containing 35 mmol of 5-bromo-2-thiophenecarboxaldehyde was slowly added dropwise into the reaction bottle, after the dropwise addition was completed, the temperature was raised to 80°C, and the reaction was stirred for 20 h, then the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent was a mixture of n-hexane and ethyl acetate at a volume ratio of 25:1) to obtain a ligand intermediate, and the yield was 86%;

[0126] (2) 5 mmol of the ligand intermediate, 17 mmol of 2,6-di(isopropyl)aniline and 18 mg of benzenesulfonic acid were dissolved in 50 mL of ethylbenzene under nitrogen atmosphere, and subjected to water reflux at 110°C for 36 h, then dried, washed with ethanol, and dried to obtain a ligand precursor, and the yield was 75%;

[0127] (3) 5 mmol of the ligand precursor was dissolved in 50 mL of dry ethyl acetate under nitrogen atmosphere, 10.5 mmol of 2-isopropylbenzene lithium was slowly added dropwise into the ethyl acetate solution at -40°C, stirred for 1 h, then slowly returned to room temperature, heated to 110°C and refluxed for 20 h, then quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with a saturated aqueous NaCl solution, dried over anhydrous Na2SO4, and dried to obtain a light yellow catalyst ligand, and the yield was 80%;

[0128] (4) 2 mmol of the catalyst ligand was dissolved in 20 mL of dry ethylbenzene in a nitrogen-filled Schlenk bottle, 6.0 mmol of n-butyllithium solution was added dropwise at 0°C, after the dropwise addition was completed, the temperature was naturally raised to 45°C, deprotonation was carried out, the reaction was carried out for 2 h, then 6.2 mmol of HfCl4 was added into the Schlenk bottle, the temperature was raised to 110°C, substitution reaction was carried out, the reaction was carried out for 16 h, then the temperature was lowered to room temperature, 6.5 mmol of MeMgCl was added dropwise into the Schlenk bottle, methylation reaction was carried out at 45°C, the reaction was carried out for 5 h, then solid-liquid separation was carried out, the solid was washed with n-hexane for 3 times, the n-hexane filtrate was collected after filtration, and the crystals were filtered, washed and dried at -35°C overnight to obtain a bimetallic non-metallocene catalyst, and the yield was 61%.

[0129] Catalyst Preparation Example 6

[0130] (1) 10 mmol of 4,4'-diphenyl boric acid, 30 mL of n-propanol, 12 mg of dichloropalladium and 3.5 g of dimethylamine were added into a reaction bottle under nitrogen atmosphere, and mixed uniformly, then 20 mL of a toluene solution containing 45 mmol of 5-bromo-2-thiophene carboxaldehyde was slowly added dropwise into the reaction bottle, after the dropwise addition was completed, the temperature was raised to 120°C, and the reaction was stirred for 10 h, then the reaction liquid in the reaction bottle was concentrated to remove ethanol and toluene, and the concentrate was purified by silica gel column chromatography (eluent: a mixture of n-hexane and ethyl acetate at a volume ratio of 25:1) to obtain a ligand intermediate, and the yield was 79%;

[0131] (2) 5 mmol of the ligand intermediate, 20 mmol of 2,6-di(isopropyl) aniline and 20 mg of benzenesulfonic acid were dissolved in 50 mL of ethylbenzene under nitrogen atmosphere, and subjected to water reflux at 170°C for 60 h, then dried, washed with ethanol, and dried to obtain a ligand precursor, and the yield was 71%;

[0132] (3) 5 mmol of the ligand precursor was dissolved in 50 mL of dry n-butanol under nitrogen atmosphere, 10 mmol of 2-isopropyl lithium was slowly added dropwise into the n-butanol solution at -40°C, and after stirring for 1 h, the temperature was slowly returned to room temperature, and heated to 70°C for reflux for 8 h; quenched with an aqueous NH4Cl solution in an ice water bath, separated, extracted with ethyl acetate, washed with saturated aqueous NaCl solution, dried over anhydrous Na2SO4, and dried to obtain a light yellow catalyst ligand, and the yield was 76%;

[0133] (4) 2 mmol of the catalyst ligand was dissolved in 20 mL of dry ethylbenzene in a nitrogen-filled Schlenk bottle, 6.6 mmol of n-butyllithium solution was added dropwise at 0°C, after the dropwise addition was completed, the temperature was naturally raised to 50°C, and deprotonation was performed, the reaction was performed for 5 h, then 5.8 mmol of HfCl4 was added into the Schlenk bottle, the temperature was raised to 70°C, and substitution reaction was performed, the reaction was performed for 16 h, then the temperature was lowered to room temperature, 8.5 mmol of MeMgCl was added dropwise into the Schlenk bottle, and methylation was performed at 50°C, the reaction was performed for 1 h, then solid-liquid separation was performed, the solid was washed with n-hexane for 3 times, the n-hexane filtrate was collected after filtration, and the crystals were filtered, washed and dried at -35°C overnight to obtain a bimetallic non-metallocene catalyst, and the yield was 57%.

[0134] Catalyst preparation example 7

[0135] The same as example 1, except that 2-isopropyl lithium in step (3) was replaced by an equimolar amount of tert-butyllithium.

[0136] The structural formula of the catalyst ligand obtained in step (3) is as follows:

[0137] The catalyst ligand prepared in step (3) was subjected to nuclear magnetic resonance hydrogen spectrum test, and the obtained nuclear magnetic hydrogen spectrum was as follows: 1 H NMR (CD3Cl, 400 MHz): δ (ppm) 1.20 (d, 24H, Ar-C-CH3), 0.94 (s, 18H, C-CH3), 2.87 (m, 4H, Ar-CH), 3.85 (s, 2H, N-CH), 4.0 (s, 2H, N-H), 6.83-7.31 (m, 4H, Thio-H), 6.83-6.90 (m, 6H, N-Ar-H), 7.25-7.85 (d, 8H, Ar-H). It can be seen from the nuclear magnetic resonance hydrogen spectrum that the prepared catalyst ligand is consistent with the theoretical structure.

[0138] The structural formula of the bimetallic non-metallocene catalyst prepared in step (4) is as follows:

[0139] The non-metallocene catalyst obtained in step (4) was subjected to mass spectrum analysis, and the results were as follows: MS-EI (m / z): 1222.1. It can be seen from the mass spectrum test results that 1222.1 is the molecular ion peak of the catalyst prepared in catalyst preparation example 7. It can be seen from the nuclear magnetic resonance hydrogen spectrum of the catalyst ligand and the mass spectrum test results of the bimetallic non-metallocene catalyst that the compound with the above structure is synthesized in catalyst preparation example 7.

[0140] Catalyst preparation example 8

[0141] The same as example 1, except that the lithium of 2-isopropylbenzene in step (2) is replaced by methyllithium in equimolar amount, and MeMgCl in step (4) is replaced by EtMgCl in equimolar amount.

[0142] The structural formula of the catalyst ligand obtained in step (3) is as follows:

[0143] The catalyst ligand prepared in step (3) was subjected to nuclear magnetic resonance hydrogen spectrum test, and the obtained nuclear magnetic hydrogen spectrum was as follows: 1 H NMR (CD3Cl, 400 MHz): δ (ppm) 1.20 (d, 24H, Ar-C-CH3), 1.41 (d, 6H, C-CH3), 2.87 (m, 4H, Ar-CH), 4.0 (s, 2H, N-H), 4.08 (m, 2H, N-CH), 6.83-7.31 (m, 4H, Thio-H), 6.83-6.90 (m, 6H, N-Ar-H), 7.25-7.85 (d, 8H, Ar-H). It can be seen from the nuclear magnetic resonance hydrogen spectrum that the prepared catalyst ligand is consistent with the theoretical structure.

[0144] The structure of the bimetallic non-metallocene catalyst prepared in step (4) is as follows:

[0145] The bimetallic non-metallocene catalyst obtained in step (4) was subjected to mass spectrometric analysis, and the results were as follows: MS-EI (m / z): 1294.4. It can be known from the mass spectrometric test results that 1294.4 is the molecular ion peak of the catalyst prepared in Catalyst Preparation Example 8. It can be known from the mass spectrometric test results of the catalyst ligand and the bimetallic non-metallocene catalyst that the compound with the above structure is synthesized in Catalyst Preparation Example 8.

[0146] Catalyst Preparation Comparative Example 1

[0147] The structure of the metallocene catalyst is as follows:

[0148] The above catalyst can be prepared according to the literature (J. Mol. Catal. A 1996, 112: 37).

[0149] Catalyst Preparation Comparative Example 2

[0150] The catalyst is a single-metal active center non-metallocene catalyst, and the structure is as follows:

[0151] The above catalyst can be prepared according to the literature (Journal American Chemistry Society 2008, 130, 10354-10368; Organometallics 2011, 30, 3318-3329; ACS Catalysis. 2017, 7, 6930-6937).

[0152] Butene-1-based elastomer preparation example 1

[0153] The 2L high-pressure reactor was replaced with N2, and the replacement was continuously performed for 30 min to ensure that the water and oxygen in the high-pressure reactor were removed; then 480 g of butene-1 monomer, 120 g of hexene-1 monomer, and 0.13 mol of triisobutylaluminum were added, the temperature was maintained at 70°C, and stirring was performed for 30 min;

[0154] Then 0.55 mmol of the bimetallic non-metallocene catalyst prepared in Example 1 was mixed with 1.1 mmol of [Ph3C][B(C6F5)4] and injected into the high-pressure reactor, and the copolymerization reaction was started. After 30 min of polymerization, hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction; after filtration, ethanol was used for washing three times, and vacuum drying was performed until the constant weight was obtained, to obtain a butene-1-based elastomer.

[0155] Butene-1-based elastomer preparation example 2

[0156] The same as butene-1-based elastomer preparation example 1, except that the catalyst is the bimetallic non-metallocene catalyst prepared in example 7.

[0157] Butene-1-based elastomer preparation example 3

[0158] The same as butene-1-based elastomer preparation example 1, except that the catalyst is the bimetallic non-metallocene catalyst prepared in example 8.

[0159] Butene-1-based elastomer preparation examples 4-5

[0160] The same as butene-1-based elastomer preparation example 1, except that the equal mass of hexene-1 monomer is replaced by octene-1 and decene-1, respectively.

[0161] Butene-1-based elastomer preparation examples 6-7

[0162] The same as butene-1-based elastomer preparation example 2, except that the equal mass of hexene-1 monomer is replaced by octene-1 and decene-1, respectively.

[0163] Butene-1-based elastomer preparation examples 8-9

[0164] The same as butene-1-based elastomer preparation example 3, except that the equal mass of hexene-1 monomer is replaced by octene-1 and decene-1, respectively.

[0165] Butene-1-based elastomer preparation examples 10-13

[0166] The same as butene-1-based elastomer preparation example 1, except that the amount of hexene-1 monomer is adjusted so that m(hexene-1) / m(hexene-1+butene-1) is 10%, 15%, 25%, and 30%, respectively.

[0167] Butene-1-based elastomer preparation comparative example 1

[0168] The 2L high-pressure reactor was replaced with N2for 30min to ensure the removal of water and oxygen in the high-pressure reactor; then 480g of butene-1 monomer, 120g of hexene-1 monomer, 1.1mol of methylaluminoxane (MAO) were added, the temperature was kept at 70℃, and stirred for 30min;

[0169] Then 0.55mmol of metallocene catalyst was injected into the high-pressure reactor to start the copolymerization reaction, and after 360min of polymerization, hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction; after filtration, it was washed with ethanol three times, and vacuum dried to constant weight to obtain butene-1-based elastomer.

[0170] Butene-1 based elastomer preparation comparative example 2

[0171] The 2L high-pressure reactor was replaced with N2 for 30 minutes to ensure that the water and oxygen in the high-pressure reactor were removed; then 480g of butene-1 monomer, 120g of hexene-1 monomer, 0.11mol of triisobutylaluminum were added, the temperature was kept at 70℃, and stirring was performed for 30min;

[0172] Then 1.1mmol of single-site non-metallocene catalyst and 1.1mmol of [Ph3C][B(C6F5)4] were injected into the high-pressure reactor to start the copolymerization reaction, and after 30min of polymerization, hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction; after filtration, ethanol was used for washing three times, and vacuum drying was performed until the weight was constant to obtain the butene-1 based elastomer.

[0173] Test example 1

[0174] The catalytic activity of the catalyst in the above polymerization reaction was calculated, and the calculation results are shown in Table 1. The calculation formula of the catalytic activity of the catalyst is as follows:

[0175] Wherein, Act. represents the catalytic activity, m polymer represents the mass of the polymer prepared after polymerization, and n metal center represents the amount of active center Hf of the catalyst added during polymerization.

[0176] Table 1

[0177] As can be seen from Table 1, compared with the metallocene and single-site non-metallocene catalyst in the comparative examples, the catalyst prepared in the present application can catalyze the copolymerization of 1-butene and alpha olefin with high activity, can significantly improve the catalytic activity, and is suitable for the polymerization reaction of long-chain, large steric hindrance olefin.

[0178] Test example 2

[0179] The butene-1 based elastomers prepared in butene-1 based elastomer preparation examples 1-13 and butene-1 based elastomer preparation comparative examples 1-2 were subjected to nuclear magnetic carbon spectrum, DSC and GPC analysis, and the density was tested according to the provisions of GB / T 1033.1-2008, and the test results are shown in Table 2.

[0180] Taking butene-1 based elastomer preparation example 1 as an example, the nuclear magnetic carbon spectrum, DSC and GPC analysis results are shown in Figures 8, 9 and 10. As can be seen from Figure 8, the alpha-olefin insertion amount in the butene-1 based elastomer is 18.1wt%, and the random copolymer unit content is 3.4wt%. As can be seen from Figure 9, the glass transition temperature is-26.47℃. As can be seen from Figure 10, the weight average molecular weight of the butene-1 based elastomer is 527,000, and the molecular weight distribution index is 2.2.

[0181] Table 2

[0182] Note: Real 1-13 respectively represent the butene-1 based elastomer prepared in butene-1 based elastomer preparation examples 1-13. Pair 1-2 respectively represent the butene-1 based elastomer prepared in butene-1 based elastomer preparation comparative examples 1-2.

[0183] As can be seen from Table 2, the dual center non-metallocene catalyst prepared in the application can significantly improve the insertion rate of α-olefin monomer with large steric hindrance when catalyzing butene-1 and α-olefin copolymerization, wherein the insertion rate of α-olefin monomer is more than 9%, which can be as high as 9-29%.

[0184] The random copolymer unit content of butene-1 based elastomer prepared by using the dual center non-metallocene catalyst prepared in the application to catalyze butene-1 and α-olefin copolymerization is between 1.5-13wt%, indicating that the crystallinity of butene-1 based elastomer is low, and the butene-1 based elastomer has better flexibility. The weight average molecular weight is between 400-610 thousand, and the molecular weight distribution is between 1.8-3, indicating that the butene-1 based elastomer has excellent mechanical strength. The glass transition temperature is between -35℃ to -20℃, indicating that the butene-1 based elastomer has good low temperature resistance.

[0185] When catalyzing butene-1 and α-olefin copolymerization, the dual center non-metallocene catalyst prepared in the application can significantly improve the weight average molecular weight of butene-1 based elastomer, the insertion rate of α-olefin monomer and the content of random copolymer unit compared with metallocene catalyst and single center non-metallocene catalyst.

[0186] The above describes the preferred embodiments of the application in detail, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application, and all belong to the protection scope of the application.

Claims

1. A dual-site non-metallocene metal catalyst characterized in that, The catalyst comprises a structure represented by Formula I: wherein R1-R5 are each independently selected from H or C1-C8 alkyl, R6 is selected from C1-C5 alkyl, aryl or aryl containing C1-C5 alkyl substituents, and R7 is selected from methyl and / or ethyl.

2. The catalyst of claim 1, wherein, The R1-R5 are each independently selected from H or C1-C5 alkyl.

3. The catalyst of claim 2, wherein, The R1 and R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, t-butyl, the R2 and R4 are hydrogen, and the R3 is selected from hydrogen, isopropyl, t-butyl.

4. The catalyst of claim 1, wherein, The R6 is selected from methyl, ethyl, propyl, butyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl.

5. The catalyst of claim 1, wherein, The structural formula of the catalyst is selected from one or more of the following structural formulas:

6. A method for preparing a dual-site non-metallocene metal catalyst, characterized by, The method comprises the following steps: (1) 4,4'-diphenylboronic acid undergoes Suzuki coupling reaction with halogenated thiophene shown in formula 1-1 to obtain ligand intermediate shown in formula A; wherein X in formula 1-1 is selected from chlorine, bromine, iodine; (2) the ligand intermediate is subjected to a Schiff base reaction with an aniline of Formula 1-2 to obtain a ligand precursor of Formula B; wherein R1-R5 of Formula 1-2 are each independently selected from H or C1-C8 alkyl; (3) the ligand precursor is reduced with a hydrocarbyllithium I having the structural formula R6-Li to obtain a catalyst ligand shown in formula C; wherein R6 is selected from a C1-C5 alkyl group, an aryl group, or an aryl group containing a C1-C5 alkyl substituent; (4) the catalyst ligand first deprotonates with the alkyl lithium II, then substitution reaction occurs with the addition of hafnium tetrachloride, and then methylation reaction occurs with the addition of Grignard reagent with the structure of R7MgX, to obtain the non-metallocene catalyst shown in formula D; wherein R7 is selected from methyl or ethyl, and X is selected from chlorine, bromine, iodine; 7. The production method according to claim 6, wherein The halogenated thiophene represented by the formula 1-1 is selected from one or more of 5-chloro-2-thiophene carboxaldehyde, 5-bromo-2-thiophene carboxaldehyde, 5-iodo-2-thiophene carboxaldehyde.

8. The production method according to claim 6, wherein The Suzuki coupling reaction is carried out in the presence of a promoter and a Suzuki coupling catalyst; wherein the promoter is a basic promoter, and the Suzuki coupling catalyst is a palladium catalyst.

9. The production method according to claim 8, wherein The basic promoter is selected from one or more of ethylamine, ethylenediamine, dimethylamine, pyridine, N,N-dimethylethylenediamine, potassium carbonate, sodium carbonate; and the palladium catalyst is selected from one or more of palladium dichloride, palladium acetate, bis(triphenylphosphine)palladium dichloride.

10. The production method according to claim 8, wherein The molar ratio of the 4,4'-biphenyldiboronic acid to the halogenated thiophene represented by the formula 1-1 is 1:1-5; the usage ratio of the 4,4'-biphenyldiboronic acid to the promoter is 10 mmol:0.5-3.5 g; and the usage ratio of the 4,4'-biphenyldiboronic acid to the Suzuki coupling catalyst is 10 mmol:10-20 mg. The reaction temperature of the Suzuki coupling reaction is 70-120°C, and the reaction time is 8-20 h.

11. The production method according to claim 6, wherein The aniline represented by the formula 1-2 is selected from one or more of 2,6-di(isopropyl)aniline, 2-methylaniline, 6-methylaniline, 2-ethylaniline, 2-n-propylaniline, 2-isopropylaniline, 2-t-butylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-di-t-butylaniline, 2-methyl-6-t-butylaniline, 2-methyl-6-ethylaniline, 2,4,6-tri-t-butylaniline.

12. The method of making according to claim 6, wherein, The Schiff base reaction is carried out in the presence of a Schiff base catalyst; wherein the Schiff base catalyst is an aryl sulfonic acid compound, and is selected from one or more of benzenesulfonic acid, p-toluenesulfonic acid, p-ethylbenzenesulfonic acid.

13. The method of making according to claim 12, wherein, The molar ratio of the ligand intermediate to the aniline represented by the formula 1-2 is 1:1-4, and the usage ratio of the ligand intermediate to the Schiff base catalyst is 5 mmol:5-20 mg. The reaction temperature of the Schiff base reaction is 110-170°C, and the reaction time is 36-60 h.

14. The production method according to claim 6, wherein, The hydrocarbyllithium I is selected from one or more of methyllithium, ethyllithium, propyllithium, butyllithium, phenyllithium, methylphenyllithium, butylphenyllithium, 2-isopropylphenyllithium. The molar ratio of the ligand precursor to the hydrocarbyllithium I is 1:2-3. The reaction temperature of the reduction reaction is 70-110°C, and the reaction time is 8-20 h.

15. The method of making according to claim 6, wherein, The hydrocarbyllithium II is selected from one or more of n-butyllithium, iso-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, propyllithium, phenyllithium; The molar ratio of the catalyst ligand to the hydrocarbyllithium II is 1:2-3.3; The reaction temperature of the deprotonation reaction is room temperature-50℃, and the reaction time is 2-5h.

16. The method of making according to claim 6, wherein, The molar ratio of the catalyst ligand to the hafnium tetrachloride is 1:2-3.1; The reaction temperature of the substitution reaction is 70-110℃, and the reaction time is 8-16h.

17. The method of making according to claim 6, wherein, The Grignard reagent is selected from one or more of MeMgCl, EtMgCl, MeMgBr, EtMgBr; The molar ratio of the catalyst ligand to the Grignard reagent is 1:2.75-4.5; The reaction temperature of the methylation reaction is room temperature-50℃, and the reaction time is 1-5h.

18. A process for the polymerization of butene-1 with alpha-olefins, characterized in that, Butene-1 and an α-olefin are subjected to a copolymerization reaction under the action of a catalyst to obtain a butene-1-based elastomer; wherein the catalyst is prepared by the method of any one of claims 1-5 or claims 6-17.

19. A butene-1-based elastomer prepared by the method of claim 18.

20. The butene-1 based elastomer according to claim 19, wherein, The weight average molecular weight of the butene-1-based elastomer is ≥47×104g / mol, and the molecular weight distribution index is 1.5-3.5.

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