Main catalyst for producing poly(4-methyl-1-pentene) and its use

Abstract

The present application provides a main catalyst for producing poly(4-methyl-1-pentene) and its use. The main catalyst for producing poly(4-methyl-1-pentene) of the present application has a structure represented by Formula I. In Formula I, R1 is selected from hydrogen or phenyl. When R1 is selected from phenyl, R1 is condensed with the benzene ring in Formula I to form an anthracene ring, and R2 is selected from methyl or isopropyl. When the main catalyst of the present application is used in a catalyst system for catalyzing the homopolymerization reaction of 4-methyl-1-pentene, the catalyst exhibits high catalytic activity, and the produced poly(4-methyl-1-pentene) has a high molecular weight, a narrow molecular weight distribution, and a high isotacticity, so it is expected to be applied to a wide range of markets. 【Chemical 1】 JPEG2025519782000017.jpg41147

Description

Technical Field

[0001] Examples of the present application relate to the technical field of alkene polymerization, and in particular, to a main catalyst for producing poly(4-methyl-1-pentene) and its uses.

Background Art

[0002] Poly(4-methyl-1-pentene) (PMP) is a crystalline resin having a stereoregular structure, and has excellent chemical resistance, mechanical properties, processability, electrical insulation, low dielectric properties, optical properties, air permeability and easy peelability due to its unique structure. Therefore, poly(4-methyl-1-pentene) has important uses in the fields of fiber materials, release materials, high-end medical materials and electronic materials.

[0003] Poly(4-methyl-1-pentene) is mainly produced by catalytically polymerizing 4-methyl-1-pentene monomer alone with a catalyst. Conventionally, there are three types of catalyst systems used as polymerization catalysts for 4-methyl-1-pentene monomer: Ziegler-Natta catalysts, metallocene catalysts and late transition metal nickel-palladium catalysts.

[0004] Ziegler-Natta catalysts can effectively catalyze the polymerization of 4-methyl-1-pentene to obtain a highly isotactic crystalline polymer. Also, when an electron donor is used in combination, the stereoregularity of the product can be adjusted to make the isotacticity of the polymer greater than 95% and the melting temperature 230 °C or higher. However, Ziegler-Natta catalysts have multiple active centers, and the molecular weight distribution of the obtained polymer is generally very wide, generally 10 or more, and the mechanical properties of the low molecular weight part are also poor, so its use in high-end fields is limited.

[0005] Metallocene catalysts can also catalyze the polymerization of 4-methyl-1-pentene, but the structure of the metallocene catalyst has a great influence on the isotacticity of poly(4-methyl-1-pentene). The C2-symmetric metallocene-type titanium / zirconium complex catalysts reported so far can catalyze the polymerization of 4-methyl-1-pentene, and the regularity of the polymer also reaches more than 90%. Since the metallocene catalyst has a single metal active center, the poly(4-methyl-1-pentene) produced using it generally has a molecular weight distribution of less than 3 and is narrow. On the other hand, the steric hindrance of the metallocene catalyst is large, and the 4-methyl-1-pentene monomer with large steric hindrance is difficult to insert. Therefore, the catalytic activity of the metallocene catalyst for 4-methyl-1-pentene is low, and it is difficult to produce polymers with a molecular weight exceeding 100,000.

[0006] When late transition metal nickel / palladium catalysts are used for the polymerization of 4-methyl-1-pentene, the stereocontrol is poor, and poly(4-methyl-1-pentene) with high regularity cannot be obtained. In addition, since chain walking occurs during the process of the late transition metal nickel / palladium catalyst catalyzing the polymerization, the product has complex branches and the obtained is an amorphous polymer, and no actual commercial application is expected.

[0007] Therefore, developing a catalyst system that enables the production of poly(4-methyl-1-pentene) with high molecular weight, high isotacticity, and narrow molecular weight has great significance.

Summary of the Invention

[0008] This application provides a main catalyst for producing poly(4-methyl-1-pentene) and a method for producing the same. The main catalyst has high catalytic activity in the polymerization reaction of 4-methyl-1-pentene, and the poly(4-methyl-1-pentene) obtained by the catalytic reaction has the advantages of high molecular weight, narrow molecular weight distribution, and high isotacticity.

[0009] This application also provides a catalyst for producing poly(4-methyl-1-pentene). The catalyst is obtained by blending the above main catalyst and activator. Since the catalyst contains the above main catalyst, it has high catalytic activity. The poly(4-methyl-1-pentene) produced by the catalytic reaction has the advantages of high molecular weight, narrow molecular weight distribution, and high isotacticity.

[0010] This application also provides a method for producing poly(4-methyl-1-pentene). The method is to carry out the homopolymerization reaction of 4-methyl-1-pentene monomer with the above catalyst to produce poly(4-methyl-1-pentene). The poly(4-methyl-1-pentene) produced by this method has the advantages of high molecular weight, narrow molecular weight distribution, and high isotacticity.

[0011] The first aspect of this application provides a main catalyst for producing poly(4-methyl-1-pentene). The main catalyst has a structure represented by Formula I.

Chemical formula

[0012] The compound represented by Formula I is a non-metallocene bridged iminoamine hafnium complex. Since the complex has a small steric hindrance, it is advantageous for the coordination insertion of 4-methyl-1-pentene monomer with a large steric hindrance, endowing the catalyst with high catalytic activity and enabling the production of poly(4-methyl-1-pentene) with a high molecular weight. Also, due to the single metal active center of the complex, the catalyst has higher selectivity, which helps to obtain poly(4-methyl-1-pentene) with a narrow molecular weight distribution and high isotacticity.

[0013] As a result of research by the present inventors, it has been found that when R2 is selected from isopropyl, the main catalyst exhibits higher catalytic activity, and the poly(4-methyl-1-pentene) obtained by the catalytic reaction has a narrower molecular weight and a higher isotacticity.

[0014] A second aspect of the present application provides a method for producing a main catalyst for producing the above poly(4-methyl-1-pentene), and the reaction route of the method is as shown below.

Chemical formula

[0015] Specifically, it includes Step 1 of reacting methylglyoxal with 2,6-diisopropylaniline to obtain Intermediate A, Step 2 of reacting Intermediate A with α-naphthylamine or α-anthramine to obtain Intermediate B, Step 3 of reacting Intermediate B with an R2-substituted phenyllithium compound to obtain Intermediate C, Step 4 of sequentially reacting Intermediate C with alkyllithium and hafnium tetrahalide to obtain Intermediate D, and Step 5 of reacting Intermediate D with methylmagnesium halide to obtain the main catalyst represented by Formula I.

[0016] In Steps 1 and 2, the condensation reactions of aldehyde and carbonyl in methylglyoxal with an arylamine compound are utilized respectively to obtain an asymmetric aryl-substituted diimine intermediate B. In Step 3, the R2-substituted phenyllithium compound serves as a nucleophile, and through nucleophilic addition to Intermediate B, a bridgehead-substituted iminoamine intermediate C, that is, a ligand of the main catalyst, is obtained. In Step 4, alkyllithium extracts a proton from the secondary amine and further reacts with hafnium tetrahalide to obtain an iminoamine hafnium halide intermediate D. In Step 5, the main catalyst represented by Formula I is obtained through the Grignard reaction of Intermediate D and methylmagnesium halide.

[0017] In Step 4, the alkyllithium is preferably n-butyllithium, and the hafnium tetrahalide is preferably hafnium tetrachloride. In Step 5, the methylmagnesium halide is preferably methylmagnesium bromide.

[0018] The selection of the specific reaction conditions for Steps 1 to 5 is ordinary technology for those skilled in the art with basic knowledge of organic synthesis, and thus the description thereof is omitted here.

[0019] The third aspect of the present application provides a catalyst for producing poly(4-methyl-1-pentene), and the catalyst includes the main catalyst provided according to the first aspect of the present application and an activator.

[0020] Since the catalyst includes the main catalyst provided according to the first aspect of the present application, it has high catalytic activity, and the poly(4-methyl-1-pentene) produced by the catalytic reaction has the advantages of high molecular weight, narrow molecular weight distribution, and high isotacticity.

[0021] Furthermore, the activator of the present application is selected from the composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and alkylaluminum. However, from the viewpoints of catalytic activity, selectivity, cost, etc. of the catalyst, the alkylaluminum compound in the composition is preferably at least one of trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0022] In addition, when tests were conducted on the molar ratio of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate to alkylaluminum in the composition and the molar ratio of the main catalyst to the co-catalyst, it was found that when the molar ratio of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate to alkylaluminum in the composition was 1:(50 to 300) and the molar ratio of the main catalyst to the activator was 1:(1 to 5), the catalyst had higher catalytic activity, and the produced polymer had both higher molecular weight, narrower molecular weight distribution, and higher isotacticity.

[0023] The fourth aspect of the present application provides a method for producing poly(4-methyl-1-pentene), which includes subjecting the homopolymerization reaction of 4-methyl-1-pentene monomer to catalysis with the catalyst provided by the third aspect of the present application to obtain the poly(4-methyl-1-pentene).

[0024] The catalyst of the present application has high catalytic activity and high selectivity in the homopolymerization reaction of 4-methyl-1-pentene. The produced poly(4-methyl-1-pentene) has a high molecular weight, a narrow molecular weight distribution and a high isotacticity, and shows better mechanical properties and thermal stability. Therefore, it is expected to be applied to a wider market.

[0025] In the above homopolymerization reaction, by optimizing conditions such as the molar ratio of 4-methyl-1-pentene monomer to the catalyst, the temperature of the homopolymerization reaction, and the solvent, the obtained poly(4-methyl-1-pentene) can have a higher molecular weight, a narrower molecular weight distribution and a higher isotacticity.

[0026] When an optimization test was carried out, it was found that the molar ratio of 4-methyl-1-pentene monomer to the catalyst is preferably (100~400000):1, more preferably (10000~100000):1, the temperature of the homopolymerization reaction is 20~60°C, and the solvent for the homopolymerization reaction is preferably one or more of 1,2-dichloroethane, chloroform, chlorobenzene, toluene, benzene, and xylene.

[0027] By controlling factors such as the molar ratio of 4-methyl-1-pentene monomer to the catalyst, the polymerization temperature, and the polymerization solvent in the homopolymerization reaction, the produced poly(4-methyl-1-pentene) can have a weight average molecular weight of 500,000 or more, further 500,000~1.63 million, a molecular weight distribution index of 4 or less, further 2.0~4.0, an isotacticity of 95% or more, and a melting temperature of 230°C or more, further 230~240°C.

Advantages of the Invention

[0028] This application has at least the following beneficial effects compared with the prior art.

[0029] 1) The main catalyst provided by this application is a non-metallocene cross-linked iminoamine complex. Since this complex has little steric hindrance, it is advantageous for the coordination insertion of 4-methyl-1-pentene monomer with large steric hindrance, endowing the catalyst with high catalytic activity and enabling the production of poly(4-methyl-1-pentene) with a high molecular weight. Also, due to the single metal active center of this complex, the catalyst has higher selectivity, which is helpful for obtaining poly(4-methyl-1-pentene) with a narrow molecular weight distribution and a high isotacticity.

[0030] 2) When the main catalyst of this application is used in the catalyst system for catalyzing the polymerization of 4-methyl-1-pentene monomer, the poly(4-methyl-1-pentene) obtained by the polymerization has a high molecular weight, a narrow molecular weight distribution, a high isotacticity, and a high melting temperature. Therefore, the obtained polymer has better mechanical properties and thermal stability, and is expected to be applied to a wider market.

[0031] 3) The method for producing poly(4-methyl-1-pentene) provided by this application has the advantages of mild and efficient reaction conditions.

Brief Description of the Drawings

[0032] To make the description of the technical solutions according to the embodiments or the prior art of this application clearer, the drawings used in the description of the embodiments or the prior art are briefly described below. Needless to say, the drawings mentioned in the following description are some embodiments of this application, and those skilled in the art can obtain other drawings from these drawings without creative labor.

Figure 1

Figure 2

Figure 3

DETAILED DESCRIPTION OF THE INVENTION

[0033] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the following uses the embodiments of the present application to clearly and completely describe the technical solutions according to the embodiments of the present application. Needless to say, the described embodiments are some of the embodiments of the present application, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without creative labor shall fall within the protection scope of the present application.

[0034] Hereinafter, specific examples are used to further elaborate in detail the main catalyst for producing poly(4-methyl-1-pentene) provided by the present application and its uses.

[0035] In the following examples, unless otherwise specified, the raw materials used may be commercially available products or those produced by ordinary methods. For test methods for which specific conditions are not described, all are ordinary methods and ordinary conditions well-known in the art.

[0036] The calculation formula for the catalytic activity of the catalysts in the following examples and comparative examples is: catalytic activity = mass of poly(4-methyl-1-pentene) (g) / (amount of main catalyst added (mol) × reaction time (h)).

[0037] The weight average molecular weight and molecular weight distribution index of poly(4-methyl-1-pentene) produced in the following examples and comparative examples are all measured by GPC.

[0038] The melting temperature of poly(4-methyl-1-pentene) produced in the following examples and comparative examples is all measured by the thermal analysis method of DSC.

[0039] The isotacticity of poly(4-methyl-1-pentene) produced in the following examples and comparative examples is all 13 measured by 13C NMR.

[0040] (Example 1) The main catalyst, catalyst and production process of poly(4-methyl-1-pentene) in this example are as follows.

[0041] 1) Production of main catalyst P1 The reaction route is as shown below. [Chemical formula]

[0042] The production steps include the following.

[0043] a. Add 0.79 g (11 mmol) of S1 (methylglyoxal), 50 mL of ethanol and a catalytic amount of formic acid to the reaction flask, mix to uniformity, then slowly add 1.77 g (10 mmol) of 2,6-diisopropyl aniline to the reaction flask. After the addition is complete, stir and react for 12 hours. Concentrate the reaction system to remove the solvent, and purify the concentrate by silica gel column chromatography (the eluent is a mixed solvent of n-hexane and ethyl acetate with a volume ratio of 50:1) to obtain compound S2, and the yield was 93%.

[0044] b. Dissolve 0.93 g (4 mmol) of compound S2 in 50 mL of toluene, and slowly add 0.72 g (5 mmol) of α-naphthylamine and a catalytic amount of p-toluenesulfonic acid, heat until reflux, react for 12 hours, cool, then concentrate to remove the solvent, and purify the concentrate by column chromatography (the eluent is a mixed solvent of n-hexane and ethyl acetate with a volume ratio of 50:1) to obtain compound S3, and the yield was 89%.

[0045] c. At -40 °C, 1.78 g (5 mmol) of compound S3 was dissolved in anhydrous diethyl ether, and a diethyl ether solution of 0.76 g (6 mmol) of 2-isopropylphenyllithium was slowly added dropwise. After the addition was complete, the reaction system was allowed to rise to room temperature and reacted overnight. After confirming the completion of the reaction by TLC, a saturated solution of ammonium chloride was added to the reaction system to quench the reaction, and the mixture was extracted three times with anhydrous diethyl ether. The diethyl ether phase was collected, and the diethyl ether phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a concentrate. Ethanol was added to the concentrate for recrystallization to obtain ligand L1, and the yield was 90%.

[0046] The characteristic evaluation data of ligand L1 are as follows. 1 H NMR (CD3Cl, 400 MHz): δ (ppm) 8.44 (d, 1H, Nap-H), 8.12 - 8.08 (d, 3H, Nap-H), 7.97 (d, 1H, Nap-H), 7.70 - 6.87 (m, 9H, Ar-H), 6.71 (s, 1H, CNH), 4.26 (s, 1H, NCH), 3.67 (sept, 2H, CH(CH3)2), 2.94 (sept, 1H, CH(CH3)2), 1.78 (d, 6H, CH(CH3)2), 1.19 (d, 6H, CH(CH3)2), 1.13 (s, 3H, C-CH3), 1.01 (d, 3H, CH(CH3)2), 0.93 (d, 3H, CH(CH3)2). Anal. Calcd for C 34 H 40 N2: C, 85.67; H, 8.46; N, 5.88; Found: C, 85.73; H, 8.45; N, 5.82.

[0047] d. Under a nitrogen atmosphere, 0.93 g (2 mmol) of compound S4 was added to a dried Schlenk flask, 20 mL of toluene was added and dissolved, and an n-butyllithium solution (1.5 mL, 1.6 M) was added dropwise to the Schlenk flask at -50 °C. After the addition was complete, the temperature was allowed to rise to room temperature naturally. When the reaction was complete, the solvent was suction filtered, and a yellow powder precipitated. It was washed three times with n-hexane, and the n-hexane was suction filtered to obtain a yellow lithium salt ligand. The yellow lithium salt ligand was dissolved in toluene and transferred to a reaction flask. A toluene suspension of 0.71 g (2.2 mmol) of HfCl4 was also added to the reaction flask. Next, the temperature was raised to 120 °C and reacted for 6 hours, then allowed to cool naturally to room temperature, and then placed in a low-temperature bath and cooled to -40 °C. Next, MeMgBr (2.5 mL, 3 M) was slowly added dropwise to the reaction system. After the addition was complete, the temperature was allowed to rise to room temperature naturally and stirred for 6 hours. The precipitate was removed by filtration. Next, the precipitate was washed three times with toluene, the filtrates were combined, and the solvent was removed from the filtrate by distillation under reduced pressure to obtain a solid. The solid was washed three times with n-hexane and dried to obtain the main catalyst P1 as a yellow solid, and the yield was 64%.

[0048] The characteristic evaluation data of the main catalyst P1 are as follows. 1 H NMR (C6D6, 400 MHz): δ (ppm) 8.52 (d, 1H, Nap-H), 8.26 (d, 1H, Nap-H), 7.94 (d, 1H, Nap-H), 7.73 (d, 1H, Nap-H), 7.35 - 6.97 (m, 9H, Ar-H), 4.42 (s, 1H, NCH), 3.78 (sept, 1H, CH(CH3)2), 3.02 (sept, 1H, CH(CH3)2), 2.89 (sept, 1H, CH(CH3)2), 1.35 (d, 3H, CH(CH3)2), 1.31 (d, 3H, CH(CH3)2), 1.21 (d, 3H, CH(CH3)2), 1.17 (s, 3H, C-CH3), 1.12 (d, 3H, CH(CH3)2), 0.97 (s, 3H, Hf-CH3), 0.73 (d, 3H, CH(CH3)2), 0.66 (s, 3H, Hf-CH3), 0.34 (d, 3H, CH(CH3)2). MS-EI (m / z): 684.3 (M +). Anal. Calcd for C 36 H 44 N2Hf: C, 63.28; H, 6.49; N, 4.10; Found: C, 63.32; H, 6.44; N, 4.03.

[0049] 2) Preparation of Catalysts C1-3 Using Compound P1 as the main catalyst and a composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:67) as the activator, the activator was marked as A3, and the main catalyst P1 and the activator A3 were blended at a molar ratio of 1:1.5 to obtain Catalyst C1-3.

[0050] 3) Preparation of Poly(4-methyl-1-pentene) The specific steps are as follows. The Schlenk flask equipped with a magnetic stirrer was subjected to continuous vacuum pumping and dried with an infrared lamp for 2 hours, then allowed to cool naturally, and after that, nitrogen replacement was carried out 3 times until normal pressure was reached. Next, 7 mL of toluene and 3 mL of 4-methyl-1-pentene monomer were added to the Schlenk flask in this order, the temperature was set to 40 °C in a water bath and stirred for 30 minutes. Subsequently, 1 μmol of Catalyst C1-3 (the molar ratio of 4-methyl-1-pentene monomer to Catalyst C1-3 was 24000:1) was added to the system to initiate polymerization, and after polymerizing for 5 minutes, a 10% ethanol solution oxidized with hydrochloric acid was added to stop the polymerization. The polymerization system was filtered, then washed 3 times with ethanol, and dried under vacuum until a constant weight was obtained to obtain poly(4-methyl-1-pentene).

[0051] As a result of calculation, the catalytic activity of Catalyst C1-3 in the above homopolymerization reaction was 14.5 kg of polymer / (mmol Hf·h).

[0052] The characteristic evaluation data of the poly(4-methyl-1-pentene) produced in Example 1 were detected. Figure 1 shows the 1313C NMR spectrum, Figure 2 is the DSC curve of poly(4-methyl-1-pentene) prepared in Example 1, Figure 3 is the GPC curve of poly(4-methyl-1-pentene) prepared in Example 1. As can be seen from the analysis of Figures 1 to 3, the poly(4-methyl-1-pentene) prepared in Example 1 had a weight-average molecular weight of 705 kg / mol, a molecular weight distribution index of 2.3, a melting temperature of 238 °C, and an isotacticity of 98%.

[0053] (Example 2) The production of the main catalyst and the catalyst in this example are both the same as those in Example 1.

[0054] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that the polymerization temperature was changed from 40 °C to 20 °C.

[0055] The catalytic activity of catalyst C1-3 in this example was 3.1 kg of polymer / (mmol Hf·h), and the poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 733 kg / mol, a molecular weight distribution index of 4.0, a melting temperature of 240 °C, and an isotacticity exceeding 99%.

[0056] (Example 3) The production of the main catalyst and the catalyst in this example are both the same as those in Example 1.

[0057] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that the polymerization temperature was changed from 40 °C to 60 °C.

[0058] The catalytic activity of catalyst C1-3 in this example was 6.5 kg of polymer / (mmol Hf·h), and the poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 821 kg / mol, a molecular weight distribution index of 2.0, a melting temperature of 237 °C, and an isotacticity of 97%.

[0059] (Example 4) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0060] The step of producing poly(4-methyl-1-pentene) in this example is the same as in Example 1, except that the 4-methyl-1-pentene monomer added in the homopolymerization reaction is 0.0125 mL (the molar ratio of the 4-methyl-1-pentene monomer to catalyst C1-3 is 100:1).

[0061] In this example, the catalytic activity of catalyst C1-3 is 4.8 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 501 kg / mol, a molecular weight distribution index of 2.0, a melting temperature of 239 °C, and an isotacticity of 99%.

[0062] (Example 5) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0063] The step of producing poly(4-methyl-1-pentene) in this example is the same as in Example 1, except that the 4-methyl-1-pentene monomer added in the homopolymerization reaction is 0.125 mL (the molar ratio of the 4-methyl-1-pentene monomer to catalyst C1-3 is 1000:1).

[0064] In this example, the catalytic activity of catalyst C1-3 is 13.8 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 538 kg / mol, a molecular weight distribution index of 2.2, a melting temperature of 239 °C, and an isotacticity of 99%.

[0065] (Example 6) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0066] The step of producing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that the amount of 4-methyl-1-pentene monomer added in the homopolymerization reaction is 1 mL (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 8000:1).

[0067] In this example, the catalytic activity of catalyst C1-3 is 9.2 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight-average molecular weight of 686 kg / mol, a molecular weight distribution index of 2.3, a melting temperature of 238 °C, and an isotacticity of 98%.

[0068] (Example 7) The production of the main catalyst and the catalyst in this example are both the same as those in Example 1.

[0069] The step of producing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that the amount of 4-methyl-1-pentene monomer added in the homopolymerization reaction is 5 mL (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 40000:1).

[0070] In this example, the catalytic activity of catalyst C1-3 is 29.6 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight-average molecular weight of 830 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0071] (Example 8) The production of the main catalyst and the catalyst in this example are both the same as those in Example 1.

[0072] The step of producing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that the polymerization solvent is changed from toluene to benzene.

[0073] In this example, the catalytic activity of catalyst C1-3 was 8.3 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 811 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0074] (Example 9) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0075] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent was changed from toluene to xylene.

[0076] In this example, the catalytic activity of catalyst C1-3 was 10.5 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 785 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0077] (Example 10) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0078] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent was changed from toluene to 1,2-dichloroethane.

[0079] In this example, the catalytic activity of catalyst C1-3 was 12.1 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 738 kg / mol, a molecular weight distribution index of 2.6, a melting temperature of 237 °C, and an isotacticity of 97%.

[0080] (Example 11) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0081] The steps for producing the poly(4-methyl-1-pentene) of this example are the same as those of Example 1, except that the polymerization solvent is changed from toluene to chloroform.

[0082] In this example, the catalytic activity of catalyst C1-3 was 9.8 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 765 kg / mol, a molecular weight distribution index of 2.6, a melting temperature of 237 °C, and an isotacticity of 97%.

[0083] (Example 12) The production of the main catalyst and the catalyst in this example are both in agreement with those in the case of Example 1.

[0084] The steps for producing the poly(4-methyl-1-pentene) of this example are the same as those of Example 1, except that the polymerization solvent is changed from toluene to chlorobenzene.

[0085] In this example, the catalytic activity of catalyst C1-3 was 10.9 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 857 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0086] (Example 13) The production of the main catalyst and the catalyst in this example are both in agreement with those in the case of Example 1.

[0087] The steps for producing the poly(4-methyl-1-pentene) of this example are the same as those of Example 1, except that the polymerization solvent is changed from toluene to a mixed solvent of toluene and benzene with a volume ratio of 1:1.

[0088] In this example, the catalytic activity of catalyst C1-3 was 7.8 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight average molecular weight of 778 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0089] (Example 14) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0090] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent was changed from toluene to a mixed solvent of toluene and xylene with a volume ratio of 1:1.

[0091] In the homopolymerization reaction of this example, the catalytic activity of catalyst C1-3 was 8.7 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight average molecular weight of 749 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0092] (Example 15) The production of the main catalyst and the catalyst in this example are both the same as in Example 1.

[0093] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent was changed from toluene to a mixed solvent of 1,2-dichloroethane and chloroform with a volume ratio of 1:1.

[0094] In this example, the catalytic activity of catalyst C1-3 was 7.1 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight average molecular weight of 794 kg / mol, a molecular weight distribution index of 2.6, a melting temperature of 237 °C, and an isotacticity of 97%.

[0095] (Example 16) The main catalyst and the production of the catalyst in this example are both the same as those in Example 1.

[0096] The step of producing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that the polymerization solvent is changed from toluene to a mixed solvent of chlorobenzene and benzene with a volume ratio of 1:1.

[0097] In this example, the catalytic activity of catalyst C1-3 is 8.1 kg of polymer / (mmol Hf·h), and the poly(4-methyl-1-pentene) produced has a weight average molecular weight of 843 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0098] (Example 17) The main catalyst in this example is the same as that in Example 1.

[0099] The catalyst in this example is obtained by blending the main catalyst P1 and the activator A3 at a molar ratio of 1:1, and the obtained catalyst is marked as catalyst C1-7.

[0100] The step of producing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that catalyst C1-3 is replaced with catalyst C1-7.

[0101] In this example, the catalytic activity of catalyst C1-7 is 6.8 kg of polymer / (mmol Hf·h), and the poly(4-methyl-1-pentene) produced has a weight average molecular weight of 688 kg / mol, a molecular weight distribution index of 2.5, a melting temperature of 238 °C, and an isotacticity of 98%.

[0102] (Example 18) The main catalyst in this example is the same as that in Example 1.

[0103] The catalyst in this example is obtained by blending the main catalyst P1 and the activator A3 at a molar ratio of 1:3, and the obtained catalyst is marked as catalyst C1-8.

[0104] The step of manufacturing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that catalyst C1-3 is replaced with catalyst C1-8.

[0105] In this example, the catalytic activity of catalyst C1-8 is 7.2 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight average molecular weight of 744 kg / mol, a molecular weight distribution index of 2.6, a melting temperature of 238 °C, and an isotacticity of 98%.

[0106] (Example 19) The main catalyst in this example is the same as that in Example 1.

[0107] The catalyst in this example is obtained by blending the main catalyst P1 and the activator A3 at a molar ratio of 1:5, and the obtained catalyst is marked as catalyst C1-9.

[0108] The step of manufacturing poly(4-methyl-1-pentene) in this example is the same as that in Example 1, except that catalyst C1-3 is replaced with catalyst C1-9.

[0109] In this example, the catalytic activity of catalyst C1-9 is 8.8 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight average molecular weight of 798 kg / mol, a molecular weight distribution index of 2.7, a melting temperature of 238 °C, and an isotacticity of 98%.

[0110] (Example 20) The main catalyst in this example is the same as that in Example 1.

[0111] The catalyst in this example uses compound P1 as the main catalyst and a composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:50) as the activator. The activator is marked as A4. The main catalyst P1 and the activator A4 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-4.

[0112] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-4.

[0113] In this example, the catalytic activity of catalyst C1-4 is 8.3 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 667 kg / mol, a molecular weight distribution index of 2.8, a melting temperature of 238 °C, and an isotacticity of 98%.

[0114] (Example 21) The main catalyst in this example is the same as that in Example 1.

[0115] The catalyst in this example uses compound P1 as the main catalyst and a composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:150) as the activator. The activator is marked as A5, and the main catalyst P1 and the activator A5 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-5.

[0116] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-5.

[0117] In this example, the catalytic activity of catalyst C1-5 is 8.9 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 601 kg / mol, a molecular weight distribution index of 3.0, a melting temperature of 238 °C, and an isotacticity of 98%.

[0118] (Example 22) The main catalyst in this example is the same as that in Example 1.

[0119] The catalyst of this example uses compound P1 as the main catalyst, and a composition of triphenylmethyltetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:300) as the activator. The activator is marked as A6, and the main catalyst P1 and the activator A6 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-6.

[0120] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-6.

[0121] In this example, the catalytic activity of catalyst C1-6 is 7.4 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) has a weight-average molecular weight of 519 kg / mol, a molecular weight distribution index of 3.5, a melting temperature of 238 °C, and an isotacticity of 98%.

[0122] (Example 23) The main catalyst of this example is the same as that in Example 1.

[0123] The catalyst of this example uses compound P1 as the main catalyst, and a composition of triphenylmethyltetrakis(pentafluorophenyl)borate and trimethylaluminum (molar ratio 1:67) as the activator. The activator is marked as A1, and the main catalyst P1 and the activator A1 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-1.

[0124] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-1.

[0125] In this example, the catalytic activity of catalyst C1-1 is 7.8 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) has a weight-average molecular weight of 556 kg / mol, a molecular weight distribution index of 3.0, a melting temperature of 238 °C, and an isotacticity of 98%.

[0126] (Example 24) The main catalyst of this example is the same as that of Example 1.

[0127] The catalyst of this example uses compound P1 as the main catalyst and a composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and triethylaluminum (molar ratio 1:67) as the activator. The activator is marked as A2, and the main catalyst P1 and the activator A2 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-2.

[0128] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-2.

[0129] The catalytic activity of catalyst C1-2 in this example is 9.4 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight average molecular weight of 618 kg / mol, a molecular weight distribution index of 2.8, a melting temperature of 238 °C, and an isotacticity of 98%.

[0130] (Example 25) The main catalyst, catalyst, and manufacturing process of poly(4-methyl-1-pentene) in this example are as follows.

[0131] 1) Production of main catalyst P2 The structural formula of main catalyst P2 is as follows.

Chemical formula

[0132] The steps for producing main catalyst P2 are the same as the steps for producing main catalyst P1 described in Example 1, except that 2-isopropylphenyl lithium in step c is replaced with methylphenyl lithium, the product of step c is ligand L2, the yield of step c is 91%, and the yield of step d is 68%.

[0133] The structural formula of ligand L2 is as follows. [Chemical formula]

[0134] The characteristic evaluation data of ligand L2 are as follows. 1 H NMR(CD3Cl, 400 MHz): δ(ppm) 8.24(d, 1H, Nap-H), 8.19 - 8.16(d, 3H, Nap-H), 8.00(d, 1H, Nap-H), 7.63 - 7.08(m, 9H, Ar-H), 6.80(s, 1H, CNH), 4.01(s, 1H, NCH), 3.77(sept, 2H, CH(CH3)2), 3.01(sept, 1H, CH(CH3)2), 2.96(d, 3H, C(CH3)2), 1.78(d, 6H, CH(CH3)2), 1.19(d, 6H, CH(CH3)2), 1.01(d, 3H, CH(CH3)2). Anal. Calcd for C 32 H 36 N2: C, 85.67; H, 8.09; N, 6.24; Found: C, 85.73; H, 8.05; N, 6.20.

[0135] The characteristic evaluation data of the main catalyst P2 are as follows. 1 H NMR(C6D6, 400 MHz): δ(ppm) 8.42(d, 1H, Nap-H), 8.18(d, 1H, Nap-H), 8.05(d, 1H, Nap-H), 7.76(d, 1H, Nap-H), 7.41 - 6.99(m, 9H, Ar-H), 4.12(s, 1H, NCH), 3.12(sept, 1H, CH(CH3)2), 2.93(sept, 1H, CH(CH3)2), 2.37(s, 3H, C-CH3), 2.01(s, 3H, NC-CH3), 1.33(d, 3H, CH(CH3)2), 1.21(d, 3H, CH(CH3)2), 1.13(d, 3H, CH(CH3)2), 0.90(s, 3H, Hf-CH3), 0.87(d, 3H, CH(CH3)2), 0.78(s, 3H, Hf-CH3). MS-EI(m / z): 656.27(M + ). Anal. Calcd for C34 H 40 N2Hf: C, 62.33; H, 6.15; N, 4.28; Found: C, 62.40; H, 6.12; N, 4.25.

[0136] 2) Preparation of Catalyst C2-3 Using compound P2 as the main catalyst, the main catalyst P2 and the activator A3 were blended at a molar ratio of 1:1.5 to obtain catalyst C2-3.

[0137] 3) Preparation of Poly(4-methyl-1-pentene) The specific steps are the same as those in Example 1, except that catalyst C1-3 was replaced with catalyst C2-3.

[0138] In this example, the catalytic activity of catalyst C2-3 was 0.6 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 1634 kg / mol, a molecular weight distribution index of 4.0, a melting temperature of 231 °C, and an isotacticity of 95%.

[0139] (Example 26) The main catalyst, catalyst, and the manufacturing process of poly(4-methyl-1-pentene) in this example are as follows.

[0140] 1) Preparation of Main Catalyst P3 The structural formula of the main catalyst P3 is as follows.

Chemical formula

[0141] The steps for preparing the main catalyst P3 are the same as those for preparing the main catalyst P1 described in Example 1, except that the naphthylamine in step b was replaced with anthramine.

[0142] The ligand obtained in step c was L3. The yield of step c was 87%, and the yield of step d was 59%.

[0143] The structural formula of ligand L3 is as follows. [Chemical formula]

[0144] The characteristic evaluation data of ligand L3 are as follows. 1 H NMR (C6D6, 400 MHz): δ (ppm) 8.49 (d, 2H, An-H), 8.21 (d, 2H, An-H), 8.13 (d, 1H, An-H), 7.68 (d, 1H, An-H), 7.49 - 6.95 (m, 10H, Ar-H), 6.02 (s, 1H, CNH), 4.17 (s, 1H, NCH), 3.42 (sept, 2H, CH(CH3)2), 2.81 (sept, 1H, CH(CH3)2), 1.79 - 1.71 (d, 6H, CH(CH3)2), 1.23 (d, 6H, CH(CH3)2), 1.06 (s, 3H, C-CH3), 1.02 (d, 3H, CH(CH3)2), 0.91 (d, 3H, CH(CH3)2). Anal. Calcd for C 38 H 42 N2: C, 86.64; H, 8.04; N, 5.32; Found: C, 86.70; H, 8.07; N, 5.35.

[0145] The characteristic evaluation data of the main catalyst P3 are as follows. 11H NMR (CD3Cl, 400 MHz): δ (ppm) 8.58 (d, 1H, An-H), 8.41 (d, 1H, An-H), 8.13 (d, 1H, An-H), 8.02 (d, 1H, An-H), 7.64 (d, 1H, An-H), 7.49 - 6.84 (m, 10H, Ar-H), 4.18 (s, 1H, NCH), 3.16 (sept, 1H, CH(CH3)2), 2.96 (sept, 1H, CH(CH3)2), 2.84 (sept, 1H, CH(CH3)2), 1.37 (d, 3H, CH(CH3)2), 1.32 (d, 3H, CH(CH3)2), 1.20 (d, 3H, CH(CH3)2), 1.15 (s, 3H, C-CH3), 1.11 (d, 3H, CH(CH3)2), 0.90 (s, 3H, Hf-CH3), 0.76 (d, 3H, CH(CH3)2), 0.62 (s, 3H, Hf-CH3), 0.29 (d, 3H, CH(CH3)2). MS-EI (m / z): 732.31 (M + ). Anal. Calcd for C 40 H 46 N2Hf: C, 65.52; H, 6.32; N, 3.82; Found: C, 65.59; H, 6.29; N, 3.80.

[0146] 2) Preparation of Catalyst C3-3 Using Compound P3 as the main catalyst, the main catalyst P3 and the activator A3 were blended at a molar ratio of 1:1.5 to obtain Catalyst System C3-3.

[0147] 3) Preparation of Poly(4-methyl-1-pentene) The specific steps were the same as in Example 1, except that Catalyst C1-3 was replaced with Catalyst C3-3.

[0148] In this example, the catalytic activity of Catalyst C3-3 was 8.3 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 637 kg / mol, a molecular weight distribution index of 3.0, a melting temperature of 236 °C, and an isotacticity of 97%.

[0149] (Example 27) The main catalyst, catalyst, and manufacturing process of poly(4-methyl-1-pentene) in this example are as follows.

[0150] 1) Manufacture of main catalyst P4 The structural formula of main catalyst P4 is as follows.

Chemical formula

[0151] The steps for manufacturing main catalyst P4 are the same as those of main catalyst P3 described in Example 26, except that 2-isopropylphenyllithium in step c is replaced with methyllithium phenyl, the product obtained in step c is ligand L4, the yield of step c is 89%, and the yield of step d is 61%.

[0152] The structural formula of ligand L4 is as follows.

Chemical formula

[0153] The characteristic evaluation data of ligand L4 are as follows. 1 H NMR(CD3Cl,400MHz):δ(ppm)8.47(d,2H,An-H),8.19(d,2H,An-H),8.09(d,1H,An-H),7.46(d,1H,An-H),7.40 - 6.65(m,10H,Ar-H),6.17(s,1H,CNH),3.99(s,1H,NCH),3.18(sept,2H,CH(CH3)2),2.41(s,3H,C-CH3),1.56 - 1.53(d,6H,CH(CH3)2),1.01(s,3H,C-CH3),0.97(d,3H,CH(CH3)2),0.87(d,3H,CH(CH3)2). Anal.Calcd for C 36 H 38 N2:C,86.70;H,7.68;N,5.62;Found:C,86.74;H,7.66;N,5.59.

[0154] The characteristic evaluation data of the main catalyst P4 are as follows. 1 H NMR (C6D6, 400 MHz): δ (ppm) 8.51 (d, 1H, An-H), 8.38 (d, 1H, An-H), 8.15 (d, 1H, An-H), 7.98 (d, 1H, An-H), 7.57 (d, 1H, An-H), 7.45 - 6.96 (m, 10H, Ar-H), 4.11 (s, 1H, NCH), 3.21 (sept, 1H, CH(CH3)2), 3.01 (sept, 1H, CH(CH3)2), 2.41 (s, 3H, C-CH3), 2.17 (s, 3H, NC-CH3), 1.37 (d, 3H, CH(CH3)2), 1.28 (d, 3H, CH(CH3)2), 1.13 (d, 3H, CH(CH3)2), 0.86 (s, 3H, Hf-CH3), 0.81 (d, 3H, CH(CH3)2), 0.71 (s, 3H, Hf-CH3). MS-EI (m / z): 706.28 (M + ). Anal. Calcd for C 38 H 42 N2Hf: C, 64.72; H, 6.00; N, 3.97; Found: C, 64.80; H, 6.04; N, 4.02.

[0155] 2) Preparation of catalyst C4-3 Using compound P4 as the main catalyst, the main catalyst P4 and the activator A3 were blended at a molar ratio of 1:1.5 to obtain the catalyst system C4-3.

[0156] 3) Preparation of poly(4-methyl-1-pentene) The specific steps are the same as in Example 1, except that catalyst C1-3 was replaced with catalyst C4-3.

[0157] In this example, the catalytic activity of C4-3 was 0.4 kg of polymer / (mmol Hf·h), and the poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 1084 kg / mol, a molecular weight distribution index of 3.8, a melting temperature of 230 °C, and an isotacticity of 95%.

[0158] (Example 28) The main catalyst of this example is the same as that of Example 1.

[0159] The catalyst of this example uses compound P1 as the main catalyst, and a composition of triphenylmethyltetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:25) as the activator. The activator is marked as A4, and the main catalyst P1 and the activator A4 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-10.

[0160] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-10.

[0161] The catalytic activity of catalyst C1-10 in this example is 9.5 kg of polymer / (mmol Hf·h). The poly(4-methyl-1-pentene) produced has a weight-average molecular weight of 345 kg / mol, a molecular weight distribution index of 2.4, a melting temperature of 238 °C, and an isotacticity of 98%.

[0162] (Example 29) The main catalyst of this example is the same as that of Example 1.

[0163] The catalyst of this example uses compound P1 as the main catalyst, and a composition of triphenylmethyltetrakis(pentafluorophenyl)borate and triisobutylaluminum (molar ratio 1:450) as the activator. The activator is marked as A6, and the main catalyst P1 and the activator A6 are blended at a mass ratio of 1:1.5 to obtain catalyst C1-11.

[0164] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-11.

[0165] In this example, the catalytic activity of catalyst C1-11 was 6.9 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 402 kg / mol, a molecular weight distribution index of 4.0, a melting temperature of 239 °C, and an isotacticity of 98%.

[0166] (Example 30) The main catalyst of this example is the same as that of Example 1.

[0167] The catalyst of this example was obtained by blending the main catalyst P1 and the activator A3 at a molar ratio of 2:1, and the obtained catalyst was marked as catalyst C1-12.

[0168] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 was replaced with catalyst C1-12.

[0169] In this example, the catalytic activity of catalyst C1-12 was 2.9 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 348 kg / mol, a molecular weight distribution index of 2.3, a melting temperature of 238 °C, and an isotacticity of 98%.

[0170] (Example 31) The main catalyst of this example is the same as that of Example 1.

[0171] The catalyst of this example was obtained by blending the main catalyst P1 and the activator A3 at a molar ratio of 1:7, and the obtained catalyst was marked as catalyst C1-13.

[0172] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that catalyst C1-3 was replaced with catalyst C1-13.

[0173] In this example, the catalytic activity of catalyst C1-13 was 9.9 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 301 kg / mol, a molecular weight distribution index of 3.0, a melting temperature of 238 °C, and an isotacticity of 98%.

[0174] (Example 32) Both the production of the main catalyst and the catalyst in this example are the same as those in Example 1.

[0175] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that the 4-methyl-1-pentene monomer added in the homopolymerization reaction was 0.025 mL (the molar ratio of the 4-methyl-1-pentene monomer to catalyst C1-3 was 200:1).

[0176] In this example, the catalytic activity of catalyst C1-3 was 0.6 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 324 kg / mol, a molecular weight distribution index of 2.0, a melting temperature of 234 °C, and an isotacticity of 98%.

[0177] (Example 33) Both the production of the main catalyst and the catalyst in this example are the same as those in Example 1.

[0178] The steps for producing poly(4-methyl-1-pentene) in this example are the same as those in Example 1, except that the 4-methyl-1-pentene monomer added in the homopolymerization reaction was 7.5 mL (the molar ratio of the 4-methyl-1-pentene monomer to catalyst C1-3 was 60000:1).

[0179] In this example, the catalytic activity of catalyst C1-3 was 27.4 kg of polymer / (mmol Hf·h). The produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 940 kg / mol, a molecular weight distribution index of 2.9, a melting temperature of 238 °C, and an isotacticity of 97%.

[0180] (Comparative Example 1) In this comparative example, the homopolymerization reaction of 4-methyl-1-pentene was catalyzed by a Ziegler-Natta catalyst (commercially available product, product number CS-2), and the specific steps are as follows.

[0181] A Schlenk flask equipped with a magnetic stirrer was continuously evacuated and dried with an infrared lamp for 2 hours, allowed to cool naturally, and then nitrogen substitution was performed three times until normal pressure was reached. 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 500 μmol of triethylaluminum were added in this order, stirred, and kept at a constant temperature of 40 °C in a water bath for 30 minutes. 20 mg of the Ziegler-Natta catalyst was added to the reaction system, timing was started, and polymerization was carried out for 2 hours. Then, the reaction flask was opened, a 10% ethanol solution oxidized with hydrochloric acid was added to stop the polymerization, and after stirring for 3 hours, filtration was performed, washing was carried out three times with ethanol, and drying was carried out under vacuum until a constant weight was obtained to obtain poly(4-methyl-1-pentene).

[0182] In this comparative example, the catalytic activity of the Ziegler-Natta catalyst was 275 g of polymer / (mmol Ti·h), and the poly(4-methyl-1-pentene) produced had a weight average molecular weight of 1004 kg / mol, a molecular weight distribution index of 13.7, a melting temperature of 237 °C, and an isotacticity of 96%.

[0183] (Comparative Example 2) In this comparative example, the homopolymerization reaction of 4-methyl-1-pentene was catalyzed by a metallocene-type zirconium complex catalyst, and the structural formula of the metallocene-type zirconium complex catalyst is as follows.

Chemical formula

[0184] The above catalyst may be obtained with reference to the method described in the literature J.Mol.Catal.A 1996,112:37.

[0185] The specific steps of the homopolymerization reaction in this comparative example are as follows. A Schlenk flask equipped with a magnetic stirrer was subjected to continuous vacuum pumping and dried with an infrared lamp for 2 hours. After natural cooling, it was purged with nitrogen three times until atmospheric pressure was reached. 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 20 mmol of methylaluminoxane (MAO) were added in this order, stirred, and maintained at a constant temperature of 40 °C in a water bath for 30 minutes. 10 μmol of a metallocene zirconium complex catalyst was added to the reaction system and timing was started. After polymerizing for 7 hours, the reaction flask was opened, and a 10% ethanol solution oxidized with hydrochloric acid was added to stop the polymerization. After stirring for 3 hours, it was filtered, washed three times with ethanol, and dried under vacuum until a constant weight was obtained to obtain poly(4-methyl-1-pentene).

[0186] In this comparative example, the catalytic activity of the metallocene zirconium complex catalyst was 10.9 g of polymer / (mmol Zr·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 17 kg / mol, a molecular weight distribution index of 2.9, a melting temperature of 214 °C, and an isotacticity of 90%.

[0187] (Comparative Example 3) In this comparative example, the homopolymerization reaction of 4-methyl-1-pentene was catalyzed by a late transition metal nickel catalyst, and the structural formula of the catalyst is as follows.

Chemical formula

[0188] The above catalyst may be obtained by referring to the method described in the literature Macromolecules 2000, 33, 2320.

[0189] The specific steps of the homopolymerization reaction in this comparative example are as follows. A Schlenk flask equipped with a magnetic stirrer was subjected to continuous vacuum pumping and dried with an infrared lamp for 2 hours. After natural cooling, it was purged with nitrogen three times until normal pressure was reached. 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 2.5 mmol of diethylaluminum chloride were added in this order, stirred, and maintained at a constant temperature of 40 °C in a water bath for 30 minutes. 10 μmol of a late-transition metal nickel catalyst was added to the reaction system and timing was started. After polymerizing for 1 hour, the reaction flask was opened, and a 10% ethanol solution oxidized with hydrochloric acid was added to stop the polymerization. After stirring for 3 hours, it was filtered, washed three times with ethanol, and dried under vacuum until a constant weight was obtained to obtain poly(4-methyl-1-pentene).

[0190] In this comparative example, the catalytic activity of the late-transition metal nickel catalyst was 105 g of polymer / (mmol Ni·h). The poly(4-methyl-1-pentene) produced had a weight-average molecular weight of 175 kg / mol, a molecular weight distribution index of 1.5, an unknown melting temperature, the product was a random polymer, and the isotacticity was less than 10%.

[0191] For easy comparison, the values of the catalytic activity of the catalysts produced in the above examples and comparative examples, and the weight-average molecular weight, molecular weight distribution index, melting temperature, isotacticity, etc. of the poly(4-methyl-1-pentene) produced are summarized in Table 1.

[0192] In Table 1, M is Hf in the catalytic activity units of the catalysts of Examples 1 to 33, M is Ti in Comparative Example 1, M is Zr in Comparative Example 2, and M is Ni in Comparative Example 3.

[0193]

Table 1

[0194] As can be seen from Table 1, when using the iminoamine hafnium-based catalyst of the present application, compared with the case of obtaining poly(4-methyl-1-pentene) by the catalytic reaction with a Ziegler-Natta catalyst, it has higher catalytic activity and a narrower molecular weight distribution, shows higher catalytic activity compared with a metallocene-type zirconium complex catalyst, the produced poly(4-methyl-1-pentene) has a higher molecular weight and isotacticity, shows higher catalytic activity compared with a late transition metal nickel catalyst, and the produced polymer (4-methyl-1-pentene) has a higher isotacticity.

[0195] In addition, the above-mentioned examples are for explaining the technical solutions of the present application and not for limitation. Although the present application has been described in detail with reference to the above-mentioned examples, those skilled in the art can understand that they may still change the technical solutions described in the above-mentioned examples, or equivalently substitute some or all of the technical features thereof. It can be understood that even with these changes or substitutions, the gist of the corresponding technical solutions will not deviate from the scope of the technical solutions of the examples of the present application. Cross-reference of related applications

[0196] This application claims the priority of a Chinese patent application filed with the China National Intellectual Property Administration on September 8, 2022, with an application number of 202211099369.3 and an application title of "Main Catalyst for Producing Poly(4-Methyl-1-Pentene) and Its Use", the whole of which is incorporated herein by reference.

Claims

1. A main catalyst for producing poly(4-methyl-1-pentene), which has a structure represented by Formula I, 【Chemical 1】 In formula I, R １ is selected from hydrogen or phenyl, and when R １ is selected from phenyl, R １ is condensed with the naphthalene ring in formula I to form an anthracene ring, and R ２ is a main catalyst selected from methyl or isopropyl.

2. Step 1 of reacting methylglyoxal with 2,6-diisopropyl aniline to obtain Intermediate A; Step 2 of reacting Intermediate A with α-naphthylamine or α-anthramine to obtain Intermediate B; Intermediate B and R at the 2-position ２ Step 3 of reacting a substituted phenyllithium compound to obtain Intermediate C, Step 4 of sequentially reacting Intermediate C with alkyllithium and hafnium tetrahalide to obtain Intermediate D; Step 5 of reacting Intermediate D with methylmagnesium halide to obtain the main catalyst represented by Formula I, 【Chemical 2】 A method for producing a main catalyst for producing poly(4-methyl-1-pentene) according to Claim 1.

3. In Step 4, the alkyllithium is n-butyllithium, and / or In Step 4, the hafnium tetrahalide is hafnium tetrachloride, and / or In Step 5, the methylmagnesium halide is methylmagnesium bromide. A method for producing a main catalyst for producing poly(4-methyl-1-pentene) according to Claim 2.

4. A catalyst for producing poly(4-methyl-1-pentene), comprising an activator and the main catalyst according to Claim 1.

5. The catalyst according to Claim 4, wherein the activator is selected from a composition of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate and alkylaluminum.

6. The catalyst according to Claim 5, wherein the molar ratio of triphenylmethyl lithium tetrakis(pentafluorophenyl)borate to the alkylaluminum in the composition is 1:(50 - 300).

7. The catalyst according to any one of Claims 4 to 6, wherein the molar ratio of the main catalyst to the activator is 1:(1 - 5).

8. A method for producing poly(4-methyl-1-pentene), comprising catalyzing a homopolymerization reaction of 4-methyl-1-pentene monomer with the catalyst according to any one of Claims 5 to 7 to obtain poly(4-methyl-1-pentene).

9. The production method according to Claim 8, wherein the molar ratio of the 4-methyl-1-pentene monomer to the catalyst is (100 - 400000):

1.

10. The production method according to Claim 9, wherein the molar ratio of the 4-methyl-1-pentene monomer to the catalyst is (10000 - 100000):

1.

11. The temperature of the homopolymerization reaction is 20 to 60°C, and the production method according to any one of claims 8 to 10.

12. The poly(4-methyl-1-pentene) has a weight-average molecular weight of 500,000 or more, a molecular weight distribution index of 4 or less, an isotacticity of 95% or more, and a melting temperature of 230°C or more, and the production method according to any one of claims 8 to 11.

13. The poly(4-methyl-1-pentene) has a weight-average molecular weight of 500,000 to 1,630,000, a molecular weight distribution index of 2.0 to 4.0, an isotacticity of 95% or more, and a melting temperature of 230 to 240°C, and the production method according to claim 12.

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