Non-metallocene catalyst, preparation method therefor, and use thereof

Abstract

The present invention provides a non-metallocene catalyst, a preparation method therefor, and a use thereof. The molecular structure of the non-metallocene catalyst is as represented by formula 1. In formula 1, R1 and R2 each are independently one of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The non-metallocene catalyst provided by the present invention has an open spatial structure and a multi-metal active center and can highly actively catalyze a polymerization reaction of butene-1 to prepare a polybutene product having bimodal width distribution.

Description

A non-metallocene catalyst, its preparation method, and its application.

[0001] This application claims priority to Chinese Patent Application No. 202410685185.8, filed on May 29, 2024, entitled “A non-metallocene catalyst and its preparation method and application”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of organic synthesis, and in particular to a non-metallocene catalyst for hydrogenation treatment, its preparation method, and its application. Background Technology

[0003] The industrial development of polybutene-1 is inseparable from the development of olefin polymerization catalysts. Currently, the main catalysts for polybutene-1 are Ziegler-Natta catalysts and metallocene catalysts. Among them, Ziegler-Natta catalysts can effectively catalyze the polymerization of butene-1, thereby obtaining polymers with high isotactic crystallinity. Moreover, Ziegler-Natta catalysts have high catalytic efficiency, produce polymers with good overall performance, and have low cost, making them commonly used catalysts for the industrial production of polybutene-1. Metallocene catalysts can also catalyze the polymerization of butene-1, but due to the single metal center, the molecular weight distribution of polybutene-1 prepared by metallocene catalysts is relatively narrow, generally below 3. In addition, metallocene catalysts have large steric hindrance. Butene-1 has 4 carbon atoms and a long carbon chain, resulting in large steric hindrance, making it difficult for monomers to insert. Therefore, the activity of commonly used metallocene catalysts is low, more than 10 times lower than that of Ziegler-Natta catalysts, making it difficult to prepare polybutene-1 with a molecular weight exceeding 100,000. In addition, the polybutene-1 products prepared by Ziegler-Natta catalyst and metallocene catalyst all have a unimodal molecular weight distribution. The processing difficulty of the unimodal polybutene-1 products increases with the increase of molecular weight.

[0004] Application content

[0005] In view of this, the present invention provides a non-metallocene catalyst with a more open spatial structure and multiple metal active centers, which can catalyze the polymerization reaction of butene-1 with high activity.

[0006] The present invention also provides a method for preparing the above-mentioned non-metallocene catalyst, which can prepare the above-mentioned non-metallocene catalyst and the process is relatively simple.

[0007] The present invention also provides a method for preparing polybutene-1 by using the above-mentioned non-metallocene catalyst to catalyze butene-1, which can produce polybutene-1 products with a bimodal broad distribution of molecular weight distribution ≥7.

[0008] In a first aspect, the present invention provides a non-metallocene catalyst, the molecular structure of which is shown in Formula 1:

[0009] In Formula 1, R1 and R2 are each independently one of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0010] Secondly, the present invention provides a method for preparing the above-mentioned non-metallocene catalyst, comprising the following steps:

[0011] (1) A system containing pentaerythritol, 3,5-dialkylsalicylic acid, p-toluenesulfonic acid, and solvent is subjected to a Schiff base reaction to obtain a catalyst ligand;

[0012] (2) The catalyst ligand undergoes a deprotonation reaction with alkyllithium to obtain a lithium salt, and the lithium salt undergoes a mixed reaction with hafnium tetrachloride to obtain a hafnium trichloride complex;

[0013] (3) The trichlorohafnium complex is subjected to an alkylation reaction with a Grignard reagent to obtain the non-metallocene catalyst;

[0014] In an optional embodiment, in step (1), the molar ratio of pentaerythritol to 3,5-dialkylsalicylaldehyde is 1:4-6;

[0015] And / or, the molar ratio of p-toluenesulfonic acid to pentaerythritol is 1:30-50.

[0016] In an optional embodiment, in step (1), the Schiff base reaction is carried out at a temperature of 100-150°C for 36-60 hours.

[0017] In an optional embodiment, the 3,5-dialkylsalicylaldehyde is selected from at least one of 3,5-di-tert-butylsalicylaldehyde, 3-tert-butylsalicylaldehyde, 5-tert-butylsalicylaldehyde, 3,5-dimethylsalicylaldehyde, 3-methylsalicylaldehyde, 5-methylsalicylaldehyde, 3-propylsalicylaldehyde, and salicylaldehyde.

[0018] In an optional embodiment, in step (2), the molar ratio of the catalyst ligand to alkyl lithium is 1:4-6;

[0019] And / or, the molar ratio of the catalyst ligand to hafnium tetrachloride is 1:4-6.

[0020] In an optional embodiment, in step (2), the deprotonation reaction is carried out at a temperature of 0-30°C for 1-5 hours.

[0021] And / or, the reaction temperature of the mixed reaction is 80-130℃, and the reaction time is 8-16h.

[0022] In an optional embodiment, in step (3), the molar ratio of the trichlorohafnium complex to the Grignard reagent is 1:4-6;

[0023] And / or, the Grignard reagent is selected from MeMgCl, MeMgBr or MeMgI.

[0024] In an optional embodiment, in step (3), the alkylation reaction is carried out at a temperature of 0-50°C for 1-5 hours.

[0025] Thirdly, the present invention provides a method for preparing polybutene material, comprising the following steps:

[0026] Monomer butene-1 undergoes a polymerization reaction under the action of a catalyst to obtain the polybutene material, wherein the catalyst system includes: the non-metallocene catalyst and the boride.

[0027] In one alternative embodiment, the polybutene material has a molecular weight distribution ≥7 and a bimodal molecular weight distribution.

[0028] In one alternative embodiment, the polybutene material has a high weight-average molecular weight ≥ 1.5 million g / mol.

[0029] The non-metallocene catalyst provided by this invention has an open spatial structure and multiple metal active centers, which can catalyze the polymerization reaction of butene-1 with high activity to prepare polybutene products with a bimodal broad distribution.

[0030] The method for preparing non-metallocene catalysts provided by this invention uses pentaerythritol, 3,5-dialkylsalicylaldehyde, hafnium tetrachloride, Grignard reagent, etc. as raw materials to prepare non-metallocene catalysts with multi-metal active centers through Schiff base reaction, reduction reaction and coordination alkylation reaction in sequence. The preparation method has a short process, the raw materials are readily available, the reaction conditions are easy to control, and it has certain industrialization potential.

[0031] The method for preparing polybutene provided by this invention can prepare polybutene materials with a wide molecular weight distribution exhibiting both high and low peaks. This material can effectively combine the advantages of high and low molecular weight fractions, providing both the excellent processing performance of the low molecular weight fraction and the excellent mechanical properties of the high molecular weight fraction. Attached Figure Description

[0032] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0033] Figure 1 shows the carbon NMR spectrum of the polybutene material prepared in Example 38;

[0034] Figure 2 shows the GPC analysis diagram of the polybutene material prepared in Example 38. Detailed Implementation

[0035] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] In this application, the term "and / or" describes the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, or B exists alone. A and B can be singular or plural. The character " / " generally indicates that the related objects before and after are in an "or" relationship.

[0037] In this application, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0038] To address the current situation where polybutene prepared using existing catalysts has a narrow molecular weight distribution, and high molecular weight polybutene is difficult to process, this invention adopts the following technical solution:

[0039] In a first aspect, the present invention provides a non-metallocene catalyst, the molecular structure of which is shown in Formula 1:

[0040] In Formula 1, R1 and R2 are each independently one of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0041] The aforementioned non-metallocene catalyst can be used to prepare high-molecular-weight polybutene with a broad bimodal distribution because: on the one hand, the non-metallocene catalyst has an open spatial structure, which is conducive to the insertion of butene-1 monomer with large steric hindrance. At the same time, the non-metallocene catalyst contains multiple active centers, which is conducive to the growth of polymer chains and can prepare polymers with higher molecular weights; on the other hand, the non-metallocene catalyst contains multiple active centers, and due to steric hindrance, the chain growth rate of each active center is different, so it is possible to prepare polybutene with different molecular weights and a bimodal molecular weight distribution.

[0042] Secondly, the present invention provides a method for preparing the above-mentioned non-metallocene catalyst, comprising the following steps:

[0043] (1) A system containing pentaerythritol, 3,5-dialkylsalicylic acid, p-toluenesulfonic acid, and solvent is subjected to a Schiff base reaction to obtain a catalyst ligand;

[0044] (2) The catalyst ligand undergoes a deprotonation reaction with alkyllithium to obtain a lithium salt, and the lithium salt undergoes a mixed reaction with hafnium tetrachloride to obtain a hafnium trichloride complex;

[0045] (3) The trichlorohafnium complex is subjected to an alkylation reaction with a Grignard reagent to obtain the non-metallocene catalyst;

[0046] In step (1) above, pentaerythritol and 3,5-dialkylsalicylic acid are added to a solvent and reacted under the action of the catalyst p-toluenesulfonic acid. The solvent and its amount are not specifically limited in this invention, and those skilled in the art can adjust them according to the situation. For example, the solvent is selected from one of the non-polar solvents benzene, toluene, and ethylbenzene, and the amount of solvent is 10-20 times the total mass of the reactants.

[0047] In one specific embodiment, in step (1), the molar ratio of pentaerythritol to 3,5-dialkylsalicylaldehyde is 1:4-6;

[0048] And / or, the molar ratio of p-toluenesulfonic acid to pentaerythritol is 1:30-50. This embodiment, by limiting the molar ratio of pentaerythritol to 3,5-dialkylsalicylaldehyde and / or the molar ratio of p-toluenesulfonic acid to pentaerythritol, can further improve the yield of the catalyst ligand, thereby contributing to an increase in the yield of the subsequent non-metallocene catalyst.

[0049] In one specific embodiment, in step (1), the Schiff base reaction is carried out at a temperature of 100-150°C for 36-60 hours. The reaction temperature and time of the Schiff base reaction have a certain influence on the reaction rate and the conversion of raw materials. Therefore, a reaction temperature of 100-150°C and a reaction time of 36-60 hours help to accelerate the reaction rate and improve the conversion rate of raw materials.

[0050] In one specific embodiment, the 3,5-dialkylsalicylaldehyde is selected from at least one of 3,5-di-tert-butylsalicylaldehyde, 3-tert-butylsalicylaldehyde, 5-tert-butylsalicylaldehyde, 3,5-dimethylsalicylaldehyde, 3-methylsalicylaldehyde, 5-methylsalicylaldehyde, 3-propylsalicylaldehyde, and salicylaldehyde.

[0051] It is understood that the reactions involved in step (2) above are all carried out in a liquid system. Therefore, it is generally necessary to add a solvent. The solvent and its amount are not specifically limited in this invention. Those skilled in the art can adjust it according to the situation. For example, the solvent is selected from one of the non-polar solvents benzene, toluene and ethylbenzene. The amount of solvent is 10-20 times the total mass of the reactants.

[0052] In one specific embodiment, in step (2), the molar ratio of the catalyst ligand to alkyl lithium is 1:4-6;

[0053] And / or, the molar ratio of the catalyst ligand to hafnium tetrachloride is 1:4-6. In this embodiment, by limiting the molar ratio of the catalyst ligand to alkyllithium and / or the molar ratio of the catalyst ligand to hafnium tetrachloride, the yield of the trichlorohafnium complex can be further improved, thereby contributing to an increase in the yield of subsequent non-metallocene catalysts.

[0054] In one specific embodiment, in step (2), the deprotonation reaction is carried out at a temperature of 0-30°C for 1-5 hours.

[0055] And / or, the reaction temperature of the mixed reaction is 80-130℃, and the reaction time is 8-16h. The reaction temperature and time of the deprotonation reaction and the mixed reaction have a certain impact on the reaction rate and the conversion of raw materials. Therefore, the reaction conditions within the range of the above embodiments help to accelerate the reaction rate and improve the conversion rate of raw materials.

[0056] In one specific embodiment, in step (3), the molar ratio of the trichlorohafnium complex to the Grignard reagent is 1:4-6;

[0057] And / or, the Grignard reagent is selected from MeMgCl, MeMgBr or MeMgI.

[0058] In an optional embodiment, in step (3), the alkylation reaction is carried out at a temperature of 0-50°C for 1-5 hours. The reaction temperature and time of the alkylation reaction have a certain impact on the reaction rate and the conversion of the raw materials. The reaction conditions within the range of the above embodiments help to accelerate the alkylation reaction rate and improve the conversion rate of the raw materials.

[0059] Thirdly, the present invention provides a method for preparing polybutene material, comprising the following steps:

[0060] Monomer butene-1 undergoes a polymerization reaction under the action of a catalyst to obtain the polybutene material, wherein the catalyst system includes: the non-metallocene catalyst and the boride.

[0061] In one specific embodiment, the boron compound is [Ph3C][B(C6F5)4] and / or B(C6F5)3.

[0062] In one specific embodiment, the catalyst system further includes an alkyl aluminum activator; exemplarily, the alkyl aluminum activator is at least one selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0063] In another specific embodiment, the molar ratio of element B in the boron compound, element Al in the alkyl aluminum activator, and element Hf in the non-metallocene catalyst is 1-3:0-500:1.

[0064] In one specific embodiment, the molar ratio of butene-1 to the non-metallocene catalyst is 10 to 20000:1.

[0065] In one specific embodiment, the polymerization reaction is carried out at a temperature of 25–90°C for 10–120 min.

[0066] In one specific embodiment, the polybutene material has a molecular weight distribution ≥7 and a bimodal molecular weight distribution.

[0067] In one specific embodiment, the polybutene material has a high weight-average molecular weight ≥ 1.5 million g / mol.

[0068] In another specific embodiment, the polybutene material has a tensile strength ≥27 MPa, a flexural modulus ≥500 MPa, a nominal strain at break ≥200%, and a simply supported beam impact strength ≥25 kJ / m. 2 .

[0069] In this invention, the tensile strength and nominal strain at break of the above-mentioned polybutene material are determined according to standard GB / T 1040.1-2018, the flexural modulus is determined according to standard GB / T 9341-2008, and the impact strength of simply supported beam is determined according to standard GB / T18743.1-2022.

[0070] The present invention will be further described below with reference to specific embodiments:

[0071] The present invention is further illustrated below with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of protection claimed by the present invention.

[0072] Example 1

[0073] This example provides a non-metallocene catalyst, Cat1, whose preparation route is shown below:

[0074] Its preparation process includes the following steps:

[0075] (1) Under a nitrogen atmosphere, 5 mmol of pentaerythritol, 22 mmol of 3,5-di-tert-butylsalicylaldehyde and 20 mg of p-toluenesulfonic acid were dissolved in 100 mL of toluene. The mixture was refluxed at 130 °C for 48 h, the solvent was evaporated, the mixture was washed with ethanol and dried to obtain catalyst ligand A with a yield of 95%.

[0076] The characterization data for catalyst ligand A are as follows: 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.35 (s, 72H, C-(CH3)3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 7.48-7.52 (s, 8H, Ar-H), 8.56 (s, 4H, N=CH-).

[0077] (2) In a Schlenk flask filled with nitrogen, 2 mmol of catalyst ligand A was weighed and dissolved in 20 mL of toluene. 9 mmol of methyl lithium solution was added dropwise at 0 °C. After the addition was complete, the mixture was naturally heated to room temperature and refluxed for 3 h. The toluene was dried, and the mixture was washed with n-hexane. The supernatant was poured off to obtain a yellow lithium salt. The lithium salt was redissolved in toluene. 9 mmol of hafnium tetrachloride (HfCl4) was transferred into the reaction system. The temperature was raised to 100 °C and the reaction was carried out for 12 h. The solution temperature was then lowered to room temperature to obtain a reaction solution containing a trichlorohafnium complex.

[0078] (3) Add MeMgCl solution dropwise to the above reaction solution (where MeMgCl 9 mmol, n 三氯铪配合 物 :n MeMgCl =1:4.5), stirred at room temperature for 3 h. The solvent was removed, the solid was washed three times with n-hexane, filtered, and the n-hexane filtrate was collected and crystallized overnight at -35°C. The crystals were filtered, washed, and dried to obtain the non-metallocene catalyst Cat1 in 86% yield.

[0079] MS-EI(m / z): 1887.8.

[0080] Example 2

[0081] This example provides a non-metallocene catalyst, Cat2, with the structure shown below:

[0082] The preparation steps of the non-metallocene catalyst Cat2 are basically the same as those in Example 1. The difference is that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 3-tert-butylsalicylaldehyde. The yield of catalyst ligand C obtained in step (1) is 97%, and the yield of non-metallocene catalyst Cat2 in step (3) is 89%.

[0083] The structural formula of catalyst ligand C is as follows:

[0084] The characterization data of catalyst ligand C are as follows:

[0085] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.35 (s, 36H, C-(CH3)3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 7.00-7.46 (m, 12H, Ar-H), 8.56 (s, 4H, N=CH-).

[0086] The characterization data for the non-metallocene catalyst Cat2 are as follows:

[0087] MS-EI(m / z): 1663.4.

[0088] Example 3

[0089] This example provides a non-metallocene catalyst, Cat3, with the structure shown below:

[0090] The preparation steps of the non-metallocene catalyst Cat3 are basically the same as those in Example 1. The difference is that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 5-tert-butylsalicylaldehyde. The catalyst ligand D prepared has a yield of 96% in step (1) and a yield of 87% in step (3).

[0091] The structural formula of catalyst ligand D is as follows:

[0092] The characterization data for catalyst ligand D are as follows:

[0093] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 1.35 (s, 36H, C-(CH3)3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 6.94-7.72 (m, 12H, Ar-H), 8.56 (s, 4H, N=CH-).

[0094] The characterization data for the non-metallocene catalyst Cat3 are as follows:

[0095] MS-EI(m / z): 1663.4.

[0096] Example 4

[0097] This example provides a non-metallocene catalyst, Cat4, with the structure shown below:

[0098] The preparation steps of the non-metallocene catalyst Cat4 are basically the same as those in Example 1, except that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 3,5-dimethylsalicylaldehyde. The yield of catalyst ligand E obtained in step (1) is 98%, and the yield of non-metallocene catalyst Cat4 in step (3) is 81%.

[0099] The structural formula of catalyst ligand E is as follows:

[0100] The characterization data for catalyst ligand E are as follows:

[0101] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 2.15 (s, 12H, -CH3), 2.34 (s, 12H, -CH3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 7.02-7.30 (d, 8H, Ar-H), 8.56 (s, 4H, N=CH-).

[0102] The characterization data for the non-metallocene catalyst Cat4 are as follows:

[0103] MS-EI(m / z): 1551.2.

[0104] Example 5

[0105] This example provides a non-metallocene catalyst, Cat5, with the structure shown below:

[0106] The preparation steps of the non-metallocene catalyst Cat5 are basically the same as those in Example 1. The difference is that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 3-methylsalicylaldehyde. The catalyst ligand F prepared in step (1) has a yield of 98% and a yield of 87% for the non-metallocene catalyst Cat5 in step (3).

[0107] The structural formula of catalyst ligand F is as follows:

[0108] The characterization data of catalyst ligand F are as follows:

[0109] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 2.15 (s, 12H, -CH3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 6.96-7.47 (m, 12H, Ar-H), 8.56 (s, 4H, N=CH-).

[0110] The characterization data for the non-metallocene catalyst Cat5 are as follows:

[0111] MS-EI(m / z): 1495.3.

[0112] Example 6

[0113] This example provides a non-metallocene catalyst, Cat6, with the structure shown below:

[0114] The preparation steps of the non-metallocene catalyst Cat6 are basically the same as those in Example 1, except that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 5-methylsalicylaldehyde. The catalyst ligand G prepared has a yield of 98% in step (1) and a yield of 85% in step (3).

[0115] The structural formula of catalyst ligand G is as follows:

[0116] The characterization data of catalyst ligand G are as follows:

[0117] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 2.34 (s, 12H, -CH3), 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 6.90-7.49 (m, 12H, Ar-H), 8.56 (s, 4H, N=CH-).

[0118] The characterization data for the non-metallocene catalyst Cat6 are as follows:

[0119] MS-EI(m / z): 1495.1.

[0120] Example 7

[0121] This example provides a non-metallocene catalyst, Cat7, with the structure shown below:

[0122] The preparation steps of the non-metallocene catalyst Cat7 are basically the same as those in Example 1. The difference is that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with 3-propylsalicylaldehyde. The yield of catalyst ligand H obtained in step (1) is 97%, and the yield of non-metallocene catalyst Cat7 in step (3) is 82%.

[0123] The structural formula of catalyst ligand H is as follows:

[0124] The characterization data of catalyst ligand H are as follows:

[0125] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 0.90 (t, CH3, 12H), 1.65 (m, CH2, 8H), 2.62 (t, CH2, 8H), 3 .47(s,8H,N-CH2-C),5.35(s,4H,-OH),7.03-7.41(m,12H,Ar-H),8.56(s,4H,N=CH-).

[0126] The characterization data for the non-metallocene catalyst Cat7 are as follows:

[0127] MS-EI (m / z): 1607.6

[0128] Example 8

[0129] This example provides a non-metallocene catalyst, Cat8, with the structure shown below:

[0130] The preparation steps of the non-metallocene catalyst Cat8 are basically the same as those in Example 1. The difference is that 3,5-di-tert-butylsalicylaldehyde in step (1) is replaced with salicylaldehyde to prepare catalyst ligand I. The yield of catalyst ligand I in step (1) is 98%, and the yield of non-metallocene catalyst Cat8 in step (3) is 94%.

[0131] The structural formula of catalyst ligand I is as follows:

[0132] The characterization data for catalyst ligand I are as follows:

[0133] 1 H NMR (CD3Cl, 400MHz): δ (ppm) 3.47 (s, 8H, N-CH2-C), 5.35 (s, 4H, -OH), 7.02-7.66 (m, 16H, Ar-H), 8.56 (s, 4H, N = CH-).

[0134] The characterization data for the non-metallocene catalyst Cat8 are as follows:

[0135] MS-EI (m / z): 1439.3

[0136] Example 9

[0137] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of 3,5-di-tert-butylsalicylaldehyde in step (1) is adjusted to 20 mmol, and the yield of catalyst ligand A in step (1) is 89%; the amount of methyllithium in step (2) is adjusted to 8 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) is 72%.

[0138] Example 10

[0139] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1Cat1 described in Example 1. The difference is that in step (1), the amount of 3,5-di-tert-butylsalicylaldehyde is adjusted to 25 mmol, and the yield of catalyst ligand A in step (1) is 95.7%; in step (2), the amount of methyllithium is adjusted to 10 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.7%.

[0140] Example 11

[0141] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that in step (1), the amount of 3,5-di-tert-butylsalicylaldehyde was adjusted to 30 mmol, and the yield of catalyst ligand A in step (1) was 95.9%; in step (2), the amount of methyllithium was adjusted to 12 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) was 87.1%.

[0142] Example 12

[0143] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of p-toluenesulfonic acid in step (1) is adjusted to 17.2 mg, and the yield of catalyst ligand A in step (1) is 71.5%; the amount of hafnium tetrachloride in step (2) is adjusted to 8 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) is 69.2%.

[0144] Example 13

[0145] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of p-toluenesulfonic acid in step (1) is adjusted to 21.5 mg, and the yield of catalyst ligand A in step (1) is 95.6%; the amount of hafnium tetrachloride in step (2) is adjusted to 10 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.8%.

[0146] Example 14

[0147] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of p-toluenesulfonic acid in step (1) is adjusted to 28.0 mg, and the yield of catalyst ligand A in step (1) is 95.8%; the amount of hafnium tetrachloride in step (2) is adjusted to 12 mmol, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.9%.

[0148] Example 15

[0149] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that in step (1), toluene is replaced with ethylbenzene, and the yield of catalyst ligand A in step (1) is 92.9%; in step (2), the deprotonation reaction temperature is adjusted to 0℃, and the yield of non-metallocene catalyst Cat1 in step (3) is 79.7%.

[0150] Example 16

[0151] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that in step (1), toluene is replaced with benzene, and the yield of catalyst ligand A in step (1) is 87.5%; in step (2), the deprotonation reaction temperature is adjusted to 10°C, and the yield of non-metallocene catalyst Cat1 in step (3) is 82.6%.

[0152] Example 17

[0153] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of toluene in step (1) is adjusted to 67 ml, and the yield of catalyst ligand A in step (1) is 89.2%; the deprotonation reaction temperature in step (2) is adjusted to 30 °C, and the yield of non-metallocene catalyst Cat1 in step (3) is 79.9%.

[0154] Example 18

[0155] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the amount of toluene in step (1) is adjusted to 130 ml, and the yield of catalyst ligand A in step (1) is 93.9%; the deprotonation reaction time in step (2) is adjusted to 1 h, and the yield of non-metallocene catalyst Cat1 in step (3) is 77.8%.

[0156] Example 19

[0157] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction temperature in step (1) is adjusted to 100℃, and the yield of catalyst ligand A in step (1) is 67.1%; the deprotonation reaction time in step (2) is adjusted to 5h, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.6%.

[0158] Example 20

[0159] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction temperature in step (1) is adjusted to 120°C, and the yield of catalyst ligand A in step (1) is 88.9%; after hafnium tetrachloride is transferred into the reaction system in step (2), the reaction temperature is adjusted to 80°C, and the yield of non-metallocene catalyst Cat1 in step (3) is 65.4%.

[0160] Example 21

[0161] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction temperature in step (1) is adjusted to 140°C, and the yield of catalyst ligand A in step (1) is 95.3%; after hafnium tetrachloride is transferred into the reaction system in step (2), the reaction temperature is adjusted to 90°C, and the yield of non-metallocene catalyst Cat1 in step (3) is 75.9%.

[0162] Example 21

[0163] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction temperature in step (1) is adjusted to 150°C, and the yield of catalyst ligand A in step (1) is 95.7%; after hafnium tetrachloride is transferred into the reaction system in step (2), the reaction temperature is adjusted to 120°C, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.8%.

[0164] Example 22

[0165] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction time in step (1) is adjusted to 36 h, and the yield of catalyst ligand A in step (1) is 88.3%; after hafnium tetrachloride is transferred into the reaction system in step (2), the reaction temperature is adjusted to 130 °C, and the yield of non-metallocene catalyst Cat1 in step (3) is 87.0%.

[0166] Example 23

[0167] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction time in step (1) is adjusted to 60 h, and the yield of catalyst ligand A in step (1) is 95.7%; after hafnium tetrachloride is transferred into the reaction system in step (2), the reaction time is adjusted to 8 h, and the yield of non-metallocene catalyst Cat1 in step (3) is 71.3%.

[0168] Example 24

[0169] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that after transferring hafnium tetrachloride into the reaction system in step (2), the reaction time is adjusted to 10h, and the yield of non-metallocene catalyst Cat1 in step (3) is 80.6%.

[0170] Example 25

[0171] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that after transferring hafnium tetrachloride into the reaction system in step (2), the reaction time is adjusted to 14h, and the yield of the non-metallocene catalyst Cat1 in step (3) is 86.8%.

[0172] Example 26

[0173] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that after transferring hafnium tetrachloride into the reaction system in step (2), the reaction time is adjusted to 16h, and the yield of non-metallocene catalyst Cat1 in step (3) is 86.9%.

[0174] Example 27

[0175] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that in step (3), MeMgCl is replaced with MeMgBr and the amount is adjusted to 8 mmol. The yield of the non-metallocene catalyst Cat1 in step (3) is 73.2%.

[0176] Example 28

[0177] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that in step (3), MeMgCl is replaced with MeMgI and the amount is adjusted to 10 mmol. The yield of the non-metallocene catalyst Cat1 in step (3) is 86.4%.

[0178] Example 29

[0179] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the amount of MeMgCl in step (3) is adjusted to 12 mmol, and the yield of the non-metallocene catalyst Cat1 in step (3) is 87.1%.

[0180] Example 30

[0181] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction temperature in step (3) is adjusted to 0°C, and the yield of the non-metallocene catalyst Cat1 in step (3) is 63.7%.

[0182] Example 31

[0183] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction temperature in step (3) is adjusted to 10°C and the yield of the non-metallocene catalyst Cat1 in step (3) is 68.2%.

[0184] Example 32

[0185] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction temperature in step (3) is adjusted to 30°C, and the yield of the non-metallocene catalyst Cat1 in step (3) is 85.4%.

[0186] Example 33

[0187] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction temperature in step (3) is adjusted to 50°C and the yield of the non-metallocene catalyst Cat1 in step (3) is 71.6%.

[0188] Example 34

[0189] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the preparation steps of the non-metallocene catalyst Cat1 recorded in Example 1. The difference is that the reaction time in step (3) is adjusted to 1 h, and the yield of the non-metallocene catalyst Cat1 in step (3) is 64.2%.

[0190] Example 35

[0191] The preparation steps of the non-metallocene catalyst in this embodiment are basically the same as those of the non-metallocene catalyst Cat1 described in Example 1. The difference is that the reaction time in step (3) is adjusted to 5h, and the yield of the non-metallocene catalyst Cat1 in step (3) is 86.4%.

[0192] Example 36

[0193] This embodiment provides a polybutene material and its preparation method, the steps of which are as follows:

[0194] The 2L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 600g of butene-1 monomer and 1.28mol of triethylaluminum (Hf:Al = 1:300) were added, and the temperature was maintained at 60℃ with stirring for half an hour. Subsequently, a mixture of 1.07mmol of non-metallocene catalyst Cat1 and 8.57mmol of [Ph3C][B(C6F5)4] (Hf:B = 1:2) was injected into the high-pressure reactor (the molar ratio of butene-1 monomer to non-hafnium-ceramic catalyst was 10000:1) to initiate the polymerization reaction. After 60 minutes of polymerization, an ethanol solution acidified with hydrochloric acid was added to terminate the polymerization. The polymer was obtained by filtration, washed three times with ethanol, and dried under vacuum to constant weight.

[0195] In this embodiment, the non-metallocene catalyst Cat1 exhibited a catalytic activity of 59.7 kgPB / (mmol Hf·h). The prepared polybutene had a weight-average molecular weight of 2.53 million g / mol, a molecular weight distribution index of 7.9, a melt flow rate of 9.8 g / min, a tensile strength of 38 MPa, a flexural modulus of 695 MPa, a nominal strain at break of 340%, and a simply supported beam impact strength of 32 kJ / m. 2 .

[0196] The polybutene material prepared in this embodiment was analyzed by carbon NMR and GPC, and the results are shown in Figure 1. Figure 1 shows that characteristic absorption peaks of polybutene appear at chemical shifts of 40.2 ppm, 35.0 ppm, 27.7 ppm, and 10.8 ppm, indicating that the polymerization product is homopolymer polybutene-1. Figure 2 shows that the weight-average molecular weight of polybutene is 2.53 million g / mol, and the molecular weight distribution index is 7.9.

[0197] Examples 37-43

[0198] Examples 37-43 describe the catalytic polymerization method for butene-1 as being the same as in Example 36, except for the different structure of the non-hafnium-based catalyst. The characteristics of the non-hafnium-based catalyst and the polybutene product are shown in Table 1.

[0199] Table 1:

[0200] Comparative Example 1

[0201] This comparative example uses Ziegler-Natta catalyst (Z-N118) to catalyze the polymerization reaction of butene-1. The specific steps are as follows:

[0202] The 2L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 600g of butene-1 monomer and 0.5mol of triisobutylaluminum were added, and the temperature was maintained at 70℃ with stirring for half an hour. Subsequently, 1.69g of Ziegler-Natta catalyst was injected into the high-pressure reactor to start the copolymerization reaction. After 120 minutes of polymerization, the reaction was terminated by adding an ethanol solution acidified with hydrochloric acid. The polymer was obtained by filtration, washed three times with ethanol, and dried under vacuum to constant weight.

[0203] In this comparative example, the catalytic activity of the Ziegler-Natta catalyst was 26.1 kg polymer / (mol Ti·h), and the weight-average molecular weight of the prepared polybutene-1 was 504,000, with a molecular weight distribution index of 3.7.

[0204] Comparative Example 2

[0205] This comparative example uses a non-necroneometallic catalyst with a single metal active center to catalyze the polymerization reaction of butene-1. The structural formula of this non-necroneometallic catalyst is shown in Formula 2 below:

[0206] The catalysts described above were prepared according to the references (Journal American Chemistry Society 2008, 130, 10354–10368; Organometallics 2011, 30, 3318–3329; ACS Catalysis. 2017, 7, 6930-6937).

[0207] The specific steps of the polymerization reaction in this comparative example are as follows:

[0208] The 2L reactor was continuously purged with N2 for 30 minutes to ensure the removal of water and oxygen. Then, 600g of butene-1 monomer and 1.28mol of triisobutylaluminum were added, and the temperature was maintained at 60℃ with stirring for half an hour. Subsequently, 5.12mmol of a single-center non-metallocene catalyst and 8.57mmol of [Ph3C][B(C6F5)4] were mixed and injected into the high-pressure reactor to initiate the copolymerization reaction. After 60 minutes of polymerization, an ethanol solution acidified with hydrochloric acid was added to terminate the polymerization reaction. The polymer was obtained by filtration, washed three times with ethanol, and dried under vacuum to constant weight.

[0209] In this comparative example, the catalytic activity of the single-center non-metallocene catalyst was 38.4 kg polymer / (mol Hf·h), and the weight-average molecular weight of the prepared polybutene-1 was 679,000, with a molecular weight distribution index of 2.2.

[0210] In summary, as can be seen from the above examples and comparative examples, the non-metallocene catalyst of the present invention exhibits higher catalytic activity in the polymerization of butene-1 compared to the Ziegler-Natta catalyst and the single-center non-metallocene catalyst. The polybutene product prepared has a higher molecular weight, and bimodal polybutene products with a wide molecular weight distribution can be prepared. Since the polymerized product has both high and low molecular weights, it possesses excellent properties of both high and low molecular weights, exhibiting good processing rheological properties and excellent mechanical properties.

[0211] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A non-metallocene catalyst, characterized in that, Its molecular structure is shown in Formula 1: In Formula 1, R1 and R2 are each independently one of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

2. A method for preparing a non-metallocene catalyst as described in claim 1, characterized in that, Includes the following steps: (1) A system containing pentaerythritol, 3,5-dialkylsalicylic acid, p-toluenesulfonic acid, and solvent is subjected to a Schiff base reaction to obtain a catalyst ligand; (2) The catalyst ligand undergoes a deprotonation reaction with alkyllithium to obtain a lithium salt, and the lithium salt undergoes a mixed reaction with hafnium tetrachloride to obtain a hafnium trichloride complex; (3) The trichlorohafnium complex is subjected to an alkylation reaction with a Grignard reagent to obtain the non-metallocene catalyst; 3. The preparation method according to claim 2, characterized in that, In step (1), the molar ratio of pentaerythritol to 3,5-dialkylsalicylaldehyde is 1:4-6; And / or, the molar ratio of p-toluenesulfonic acid to pentaerythritol is 1:30-50.

4. The preparation method according to claim 2, characterized in that, In step (1), the Schiff base reaction is carried out at a temperature of 100-150℃ and for a time of 36-60h.

5. The preparation method according to claim 2, characterized in that, The 3,5-dialkylsalicylaldehyde is selected from at least one of 3,5-di-tert-butylsalicylaldehyde, 3-tert-butylsalicylaldehyde, 5-tert-butylsalicylaldehyde, 3,5-dimethylsalicylaldehyde, 3-methylsalicylaldehyde, 5-methylsalicylaldehyde, 3-propylsalicylaldehyde, and salicylaldehyde.

6. The preparation method according to claim 2, characterized in that, In step (2), the molar ratio of the catalyst ligand to alkyl lithium is 1:4-6; And / or, the molar ratio of the catalyst ligand to hafnium tetrachloride is 1:4-6.

7. The preparation method according to claim 2, characterized in that, In step (2), the deprotonation reaction is carried out at a temperature of 0-30°C for 1-5 hours. And / or, the reaction temperature of the mixed reaction is 80-130℃, and the reaction time is 8-16h.

8. The preparation method according to claim 2, characterized in that, In step (3), the molar ratio of the trichlorohafnium complex to the Grignard reagent is 1:4-6; And / or, the Grignard reagent is selected from MeMgCl, MeMgBr or MeMgI.

9. The preparation method according to claim 2, characterized in that, In step (3), the alkylation reaction is carried out at a temperature of 0-50°C for 1-5 hours.

10. A method for preparing a polybutene material, characterized in that, Includes the following steps: Monomer butene-1 undergoes a polymerization reaction under the action of a catalyst to obtain the polybutene material, wherein the catalyst system comprises: the non-metallocene catalyst of claim 1 and a boride.

11. A polybutene material prepared by the method of claim 10, characterized in that, The polybutene material has a molecular weight distribution ≥7 and a bimodal molecular weight distribution.

12. The polybutene material according to claim 11, characterized in that, The polybutene material has a high weight-average molecular weight ≥ 1.5 million g / mol.

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