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

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] The examples of this application relate to the technical field of alkene polymerization, and more particularly to a main catalyst for producing poly(4-methyl-1-pentene) and its applications. [Background technology]

[0002] Poly(4-methyl-1-pentene) (PMP) is a crystalline resin with a stereoregular structure. Due to its unique structure, it possesses excellent chemical resistance, mechanical properties, processability, electrical insulation, low dielectric properties, optical properties, breathability, and easy release properties. Therefore, poly(4-methyl-1-pentene) has important applications in the fields of textile materials, release agents, high-end medical materials, and electronic materials.

[0003] Poly(4-methyl-1-pentene) is primarily produced by catalyzing the homopolymerization of the 4-methyl-1-pentene monomer. Conventionally, there are three types of catalyst systems used as polymerization catalysts for 4-methyl-1-pentene monomers: Ziegler-Natta catalysts, metallocene catalysts, and late transition metal nickel-palladium catalysts.

[0004] The Ziegler-Natta catalyst effectively catalyzes the polymerization of 4-methyl-1-pentene, yielding highly isotactic crystalline polymers. Furthermore, when used in combination with electron donors, the stereoregularity of the product can be adjusted to achieve isotacticity greater than 95% and a melting temperature above 230°C. However, because the Ziegler-Natta catalyst has multiple active centers, the molecular weight distribution of the resulting polymer is generally very broad (often above 10), and the mechanical properties of the low molecular weight portion are poor, limiting its application in high-end fields.

[0005] Metallocene catalysts can also catalyze the polymerization of 4-methyl-1-pentene, but the structure of the metallocene catalyst greatly affects the isotacticity of poly(4-methyl-1-pentene). C2-symmetric metallocene-type titanium / zirconium complex catalysts reported to date can catalyze the polymerization of 4-methyl-1-pentene, achieving polymer regularity of over 90%. Because the metallocene catalyst has a single metal active center, the resulting poly(4-methyl-1-pentene) generally has a narrow molecular weight distribution of less than 3. On the other hand, metallocene catalysts exhibit significant steric hindrance, making it difficult to insert sterically hindered 4-methyl-1-pentene monomers. Therefore, the catalytic activity of metallocene catalysts towards 4-methyl-1-pentene is low, making it difficult to produce polymers with molecular weights exceeding 100,000.

[0006] When late-stage transition metal nickel-palladium catalysts are used in the polymerization of 4-methyl-1-pentene, they exhibit poor stereocontrol, failing to yield highly regular poly(4-methyl-1-pentene). Furthermore, chain walking occurs during the polymerization catalyzed by the late-stage transition metal nickel-palladium catalyst, resulting in products with complex branching and amorphous polymers that are not expected to have practical commercial applications.

[0007] Therefore, developing a catalytic system that enables the production of poly(4-methyl-1-pentene) possessing a high molecular weight, high isotacticity, and a narrow molecular weight is of great significance. [Overview of the project]

[0008] This application provides a main catalyst for producing poly(4-methyl-1-pentene) and a method for producing the same, wherein 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 having a high molecular weight, a narrow molecular weight distribution, and a high degree of isotacticity.

[0009] The present invention also provides a catalyst for producing poly(4-methyl-1-pentene), which is obtained by compounding the above-mentioned main catalyst and activator. Because the catalyst contains the above-mentioned main catalyst, it has high catalytic activity, and the poly(4-methyl-1-pentene) produced by the catalytic reaction has the advantages of having a high molecular weight, a narrow molecular weight distribution, and a high degree of isotacticity.

[0010] The present invention also provides a method for producing poly(4-methyl-1-pentene), which involves catalyzing the homopolymerization reaction of 4-methyl-1-pentene monomers with the above-mentioned catalyst to produce poly(4-methyl-1-pentene). The poly(4-methyl-1-pentene) produced by this method has the advantages of having a high molecular weight, a narrow molecular weight distribution, and a high degree of isotacticity.

[0011] A first aspect of the present application provides a main catalyst for producing poly(4-methyl-1-pentene), the main catalyst having a structure represented by formula I, [ka] In formula I, R1 is selected from hydrogen or phenyl. If R1 is selected from phenyl, R1 condenses with the naphthalene ring in formula I to form an anthracene ring, and R2 is selected from methyl or isopropyl.

[0012] The compound represented by formula I is a non-metallocene-bridged iminoamine hafnium complex. Because this complex has low steric hindrance, it is favorable for the coordination insertion of sterically hindered 4-methyl-1-pentene monomers. This allows the catalyst to exhibit high catalytic activity, enabling the production of poly(4-methyl-1-pentene) with high molecular weight. Furthermore, the single metal active center of the complex gives the catalyst higher selectivity, which helps in obtaining poly(4-methyl-1-pentene) with a narrow molecular weight distribution and high isotacticity.

[0013] As a result of the 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] The 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 phenyl lithium compound to obtain Intermediate C, Step 4 of sequentially reacting Intermediate C with an alkyllithium and a 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 reaction of aldehyde and carbonyl in methylglyoxal by an arylamine compound is utilized respectively to obtain an asymmetric aryl-substituted diimine intermediate B. In Step 3, the R2-substituted phenyl lithium compound serves as a nucleophile, and by nucleophilic addition to Intermediate B, a bridgehead-substituted iminoamine intermediate C, that is, a ligand of the main catalyst, is obtained. In Step 4, the alkyllithium extracts a proton from the secondary amine and further reacts with the hafnium tetrahalide to obtain an iminoamine hafnium halide intermediate D. In Step 5, the main catalyst represented by Formula I is obtained by 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 methyl magnesium halide is preferably methyl magnesium 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, so the description 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 contains 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 triphenylmethylium 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] Also, the molar ratio of triphenylmethylium tetrakis(pentafluorophenyl)borate and alkylaluminum in the composition, and the main catalyst and ActivatorTests on the molar ratio revealed that when the molar ratio of triphenylmethylium tetrakis(pentafluorophenyl) borate to alkylaluminum in the composition was 1:(50-300) and the molar ratio of the main catalyst to the activator was 1:(1-5), the catalyst exhibited higher catalytic activity, and the resulting polymer possessed a higher molecular weight, a narrower molecular weight distribution, and a higher degree of isotacticity.

[0023] A fourth aspect of the present application provides a method for producing poly(4-methyl-1-pentene), the method comprising catalyzing the homopolymerization reaction of a 4-methyl-1-pentene monomer with a catalyst provided in a third aspect of the present application to obtain the poly(4-methyl-1-pentene).

[0024] The catalyst of this invention exhibits high catalytic activity and selectivity in the homopolymerization reaction of 4-methyl-1-pentene. The resulting poly(4-methyl-1-pentene) possesses a high molecular weight, a narrow molecular weight distribution, and high isotacticity, resulting in better mechanical properties and thermal stability, thus making it suitable for a wider range of markets.

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

[0026] Optimization tests revealed that the molar ratio of 4-methyl-1-pentene monomer to catalyst is preferably (100-400,000):1, more preferably (10,000-100,000):1, the temperature of the homopolymerization reaction is preferably 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 catalyst, polymerization temperature, and polymerization solvent in a homopolymerization reaction, the produced poly(4-methyl-1-pentene) can have a weight-average molecular weight of 500,000 or more, and even between 500,000 and 1,630,000; a molecular weight dispersion index of 4 or less, and even between 2.0 and 4.0; an isotacticity of 95% or more; and a melting temperature of 230°C or more, and even between 230 and 240°C. [Effects of the Invention]

[0028] This invention has at least the following beneficial effects compared to the prior art.

[0029] 1) The main catalyst provided by this application is a non-metallocene-bridged iminoamine complex, which has low steric hindrance and is therefore advantageous for the coordination insertion of 4-methyl-1-pentene monomers, which have high steric hindrance. This allows the catalyst to have high catalytic activity and yield poly(4-methyl-1-pentene) with a high molecular weight. Furthermore, because the catalyst has a single metal active center, it has higher selectivity and is useful for obtaining poly(4-methyl-1-pentene) with a narrow molecular weight distribution and high isotacticity.

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

[0031] 3) The method for producing poly(4-methyl-1-pentene) provided by this application has the advantage of being mild and efficient in terms of reaction conditions. [Brief explanation of the drawing]

[0032] To make the description of the embodiments of the present application or the technical solutions relating to the prior art clearer, the drawings used in the description of the embodiments or the prior art will be briefly described below. Needless to say, the drawings that appear in the following description are some embodiments of the present application, and a person skilled in the art can obtain other drawings from these drawings without any creative work. [Figure 1] Figure 1 shows the 13C NMR spectrum of poly(4-methyl-1-pentene) produced in Example 1. [Figure 2] Figure 2 shows the DSC curve of poly(4-methyl-1-pentene) produced in Example 1. [Figure 3] Figure 3 shows the GPC curve of poly(4-methyl-1-pentene) produced in Example 1. [Modes for carrying out the invention]

[0033] To further clarify the purpose, technical solutions, and advantages of the embodiments of this application, the technical solutions relating to the embodiments of this application will be clearly and completely described below using the embodiments of this application. Needless to say, the embodiments described are not all embodiments, but only some of the embodiments of this application. All other embodiments that a person skilled in the art may obtain without creative work based on the embodiments of this application shall fall within the scope of protection of this application.

[0034] The main catalyst for producing poly(4-methyl-1-pentene) provided by this application and its applications will be described in more detail below using specific examples.

[0035] In the following examples, unless otherwise specified, the raw materials used may be commercially available products or those manufactured by conventional methods. Test methods for which specific conditions are not described are all conventional methods and conditions well known in this field.

[0036] The formula for calculating 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 dispersion index of the poly(4-methyl-1-pentene) produced in the following examples and comparative examples are all: Gel Permeation Chromatography GPC ) Measure it using this method.

[0038] The melting temperatures of the poly(4-methyl-1-pentene) produced in the following examples and comparative examples were all Differential Scanning Calorimeter DSC ) It is measured using the thermal analysis method.

[0039] The isotacticity of the poly(4-methyl-1-pentene) produced in the following examples and comparative examples was as follows: 13 C Nuclear Magnetic Resonance NMR ) Measure it using this method.

[0040] (Example 1) The production process for the main catalyst, catalyst, and poly(4-methyl-1-pentene) in this embodiment is as follows.

[0041] 1) Production of main catalyst P1 The reaction pathway is as follows: [ka]

[0042] The manufacturing 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 a reaction flask and mix until homogenized. Next, slowly add 1.77 g (10 mmol) of 2,6-diisopropylaniline dropwise to the reaction flask. After the addition is complete, stir and allow to react for 12 hours. Concentrate the reaction system to remove the solvent, and purify the concentrate by silica gel column chromatography (using a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 50:1) to obtain compound S2, with a yield of 93%.

[0044] b. 0.93 g (4 mmol) of compound S2 was dissolved in 50 mL of toluene, and 0.72 g (5 mmol) of α-naphthylamine and a catalytic amount of p-toluenesulfonic acid were slowly added dropwise. The mixture was heated under reflux and reacted for 12 hours. After cooling, the mixture was concentrated to remove the solvent, and the concentrate was purified by column chromatography (using a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 50:1) to obtain compound S3, with a yield of 89%.

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

[0046] The characteristic evaluation data for ligand L1 is as follows: 1 H NMR(CD3Cl,400MHz):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(s ept,2H,CH(CH3)2),2.94(sept,1H,CH(CH3)2),1.78(d,6H,CH(CH3)2),1.19(d,6 H,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 40N2: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, place 0.93 g (2 mmol) of the solution into a dry Schlenk flask. Ligand L1 Add the following, dissolve in 20 mL of toluene, add n-butyllithium solution (1.5 mL, 1.6 M) dropwise to a Schlenk flask at -50°C, and after the dropwise addition is complete, allow the temperature to rise to room temperature, and once the reaction is complete, filter the solvent by suction to precipitate a yellow powder, wash it three times with n-hexane, filter the n-hexane by suction to obtain a yellow lithium salt ligand, dissolve the yellow lithium salt ligand in toluene and transfer it to the reaction flask, add 0.71 g (2.2 mmol) of a toluene suspension of HfCl4 to the reaction flask, and then The temperature was raised to 120°C and the reaction was carried out for 6 hours, then allowed to cool naturally to room temperature, and then cooled in a low-temperature bath to -40°C. Next, MeMgBr (2.5 mL, 3 M) was slowly added dropwise to the reaction system, and after the addition was complete, the temperature was allowed to rise naturally to room temperature and stirred for 6 hours. The precipitate was removed by filtration, and then 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, which was a yellow solid, with a yield of 64%.

[0048] The characterization data for the main catalyst P1 is as follows: 1H NMR(C6D6,400MHz):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,1 H,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),1.1 2(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) Production of catalyst C1-3 Compound P1 was used as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:67) was used as the activator. The activator was marked as A3, and catalyst C1-3 was obtained by mixing the main catalyst P1 and activator A3 in a molar ratio of 1:1.5.

[0050] 3) Production of poly(4-methyl-1-pentene) The specific steps are as follows. A Schlenk flask equipped with a magnetic stirrer is subjected to continuous vacuum pumping and dried with an infrared lamp for 2 hours. After natural cooling, it is purged with nitrogen three times until normal pressure is reached. Next, 7 mL of toluene and 3 mL of 4-methyl-1-pentene monomer are added to the Schlenk flask in this order. The temperature is 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 is 24000:1) is added to the system to initiate polymerization. After polymerization for 5 minutes, a 10% ethanol solution oxidized with hydrochloric acid is added to stop the polymerization. The polymerization system is filtered And obtain a precipitate , then washed three times with ethanol, and dried under vacuum until a constant weight is 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 is the 13 13C NMR spectrum of the poly(4-methyl-1-pentene) produced in Example 1, Figure 2 is the DSC curve of the poly(4-methyl-1-pentene) produced in Example 1, Figure 3 is the GPC curve of the poly(4-methyl-1-pentene) produced in Example 1. As can be seen from the analysis of Figures 1 to 3, the poly(4-methyl-1-pentene) produced 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) Both the production of the main catalyst and the catalyst in this example are the same as in the case of Example 1.

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

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

[0056] (Example 3) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

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

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

[0059] (Example 4) The manufacturing process for both the main catalyst and the catalyst in this embodiment is 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 0.0125 mL of 4-methyl-1-pentene monomer is added in the homopolymerization reaction (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 100:1).

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

[0062] (Example 5) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

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

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

[0065] (Example 6) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

[0066] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that 1 mL of 4-methyl-1-pentene monomer is added in the homopolymerization reaction (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 was 9.2 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 686 kg / mol, a molecular weight dispersion index of 2.3, a melting temperature of 238°C, and an isotactic degree of 98%.

[0068] (Example 7) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

[0069] The step of producing poly(4-methyl-1-pentene) in this example is the same as in Example 1, except that 5 mL of 4-methyl-1-pentene monomer is added in the homopolymerization reaction (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 was 29.6 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 830 kg / mol, a molecular weight dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

[0071] (Example 8) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

[0072] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent is replaced 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 dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

[0074] (Example 9) The manufacturing process for both the main catalyst and the catalyst in this embodiment is 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 is replaced 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 dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

[0077] (Example 10) The manufacturing process for both the main catalyst and the catalyst in this embodiment is 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 is replaced 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 dispersion index of 2.6, a melting temperature of 237°C, and an isotactic degree of 97%.

[0080] (Example 11) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

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

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

[0083] (Example 12) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

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

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

[0086] (Example 13) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

[0087] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that the polymerization solvent is replaced from toluene to a mixed solvent of toluene and benzene in 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 778 kg / mol, a molecular weight dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

[0089] (Example 14) The manufacturing process for both the main catalyst and the catalyst in this embodiment is 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 is replaced from toluene to a mixed solvent of toluene and xylene in 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 749 kg / mol, a molecular weight dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

[0092] (Example 15) The manufacturing process for both the main catalyst and the catalyst in this embodiment is 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 is replaced from toluene to a mixed solvent of 1,2-dichloroethane and chloroform in 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 794 kg / mol, a molecular weight dispersion index of 2.6, a melting temperature of 237°C, and an isotactic degree of 97%.

[0095] (Example 16) The manufacturing process for both the main catalyst and the catalyst in this embodiment is the same as in Example 1.

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

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

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

[0099] The catalyst in this embodiment was obtained by combining the main catalyst P1 and the activator A3 in a molar ratio of 1:1, and the resulting catalyst was marked as catalyst C1-7.

[0100] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 6.8 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 688 kg / mol, a molecular weight dispersion index of 2.5, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0103] The catalyst in this embodiment was obtained by combining the main catalyst P1 and the activator A3 in a molar ratio of 1:3, and the resulting catalyst was marked as catalyst C1-8.

[0104] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 7.2 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 744 kg / mol, a molecular weight dispersion index of 2.6, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0107] The catalyst in this embodiment was obtained by combining the main catalyst P1 and the activator A3 in a molar ratio of 1:5, and the resulting catalyst was marked as catalyst C1-9.

[0108] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 8.8 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 798 kg / mol, a molecular weight dispersion index of 2.7, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0111] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:50) as the activator. The activator was marked as A4, and catalyst C1-4 was obtained by blending the main catalyst P1 and activator A4 in a mass ratio of 1:1.5.

[0112] The steps for producing poly(4-methyl-1-pentene) in this embodiment are the same as 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 was 8.3 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 667 kg / mol, a molecular weight dispersion index of 2.8, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0115] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:150) as the activator. The activator was marked as A5, and catalyst C1-5 was obtained by blending the main catalyst P1 and activator A5 in a mass ratio of 1:1.5.

[0116] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 8.9 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 601 kg / mol, a molecular weight dispersion index of 3.0, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0119] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:300) as the activator. The activator was marked as A6, and catalyst C1-6 was obtained by blending the main catalyst P1 and activator A6 in a mass ratio of 1:1.5.

[0120] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 7.4 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 519 kg / mol, a molecular weight dispersion index of 3.5, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0123] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and trimethylaluminum (molar ratio 1:67) as the activator. The activator was marked as A1, and catalyst C1-1 was obtained by blending the main catalyst P1 and activator A1 in a mass ratio of 1:1.5.

[0124] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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 was 7.8 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 556 kg / mol, a molecular weight dispersion index of 3.0, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0127] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triethylaluminum (molar ratio 1:67) as the activator. The activator was marked as A2, and catalyst C1-2 was obtained by blending the main catalyst P1 and activator A2 in a mass ratio of 1:1.5.

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

[0129] In this example, the catalytic activity of catalyst C1-2 was 9.4 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 618 kg / mol, a molecular weight dispersion index of 2.8, a melting temperature of 238°C, and an isotactic degree of 98%.

[0130] (Example 25) The production process for the main catalyst, catalyst, and poly(4-methyl-1-pentene) in this embodiment is as follows.

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

[0132] The step of producing the main catalyst P2 is the same as the step of producing the main catalyst P1 described in Example 1, except that 2-isopropylphenyllithium in step c is replaced with methylphenyllithium, 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 for ligand L2 is as follows: [ka]

[0134] The characterization data for ligand L2 is as follows: 1H NMR(CD3Cl,400MHz): 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,NC). H), 3.77(sept,2H,CH(CH3)2), 3.01(sept,1H,CH(CH3)2), 2.96(d,3H,C(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

[0135] The storage range of the P2 is one of them. 1 H NMR(C6D6,400MHz): δ(ppm) 8.42(d,1H,Nap-H),8.18(d,1H,Nap-H),8.05(d,1H,Nap-H),7.76(d,100). 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(CH). 3)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 C 34 H 40 N2Hf:C,62.33;H,6.15;N,4.28;Found:C,62.40;H,6.12;N,4

[0136] 2)Install the C2-3 switch Compound P2 was used as the main catalyst, and catalyst C2-3 was obtained by combining the main catalyst P2 with activator A3 in a molar ratio of 1:1.5.

[0137] 3) Production 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 C2-3.

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

[0139] (Example 26) The production process for the main catalyst, catalyst, and poly(4-methyl-1-pentene) in this embodiment is as follows.

[0140] 1) Production of main catalyst P3 The structural formula of the main catalyst P3 is as follows: [ka]

[0141] The step of producing the main catalyst P3 is the same as the step of producing the main catalyst P1 described in Example 1, except that naphthylamine in step b is replaced with anthramine.

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

[0143] The structural formula of ligand L3 is as follows: [ka]

[0144] The characterization data for ligand L3 is as follows: 1 H NMR(C6D6,400MHz):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 P3 also didn't seem to be able to recover anymore. 1 H NMR(CD3Cl,400MHz):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 46N2Hf:C,65.52;H,6.32;N,3.82;Found:C,65.59;H,6.29;N,3.80.

[0146] 2) Production of catalyst C3-3 Compound P3 was used as the main catalyst, and catalyst system C3-3 was obtained by combining the main catalyst P3 with activator A3 in a molar ratio of 1:1.5.

[0147] 3) Production 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 C3-3.

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

[0149] (Example 27) The production process for the main catalyst, catalyst, and poly(4-methyl-1-pentene) in this embodiment is as follows.

[0150] 1) Production of the main catalyst P4 The structural formula of the main catalyst P4 is as follows: [ka]

[0151] The steps for producing the main catalyst P4 are the same as those for the main catalyst P3 described in Example 26, except that 2-isopropylphenyllithium in step c is replaced with methylphenyllithium, 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: [ka]

[0153] The characteristic evaluation data for ligand L4 is 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,C H(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 characterization data for the main catalyst P4 is as follows: 1 H NMR(C6D6,400MHz):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,C H(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 H42 N2Hf:C,64.72;H,6.00;N,3.97;Found:C,64.80;H,6.04;N,4.02.

[0155] 2) Production of catalyst C4-3 Compound P4 was used as the main catalyst, and catalyst system C4-3 was obtained by combining the main catalyst P4 with activator A3 in a molar ratio of 1:1.5.

[0156] 3) Production 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 produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 1084 kg / mol, a molecular weight dispersion index of 3.8, a melting temperature of 230°C, and an isotactic degree of 95%.

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

[0159] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:25) as the activator. The activator was marked as A4, and catalyst C1-10 was obtained by blending the main catalyst P1 and activator A4 in a mass ratio of 1:1.5.

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

[0161] In this example, the catalytic activity of catalyst C1-10 was 9.5 kg of polymer / (mmol Hf·h), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 345 kg / mol, a molecular weight dispersion index of 2.4, a melting temperature of 238°C, and an isotactic degree of 98%.

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

[0163] In this example, the catalyst used compound P1 as the main catalyst, and a composition of triphenylmethylium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (molar ratio 1:450) as the activator. The activator was marked as A6, and catalyst C1-11 was obtained by blending the main catalyst P1 and activator A6 in a mass ratio of 1:1.5.

[0164] The steps for producing poly(4-methyl-1-pentene) in this example are the same as 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 402 kg / mol, a molecular weight dispersion index of 4.0, a melting temperature of 239°C, and an isotactic degree of 98%.

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

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

[0168] The steps for producing poly(4-methyl-1-pentene) in this example are the same as in Example 1, except that catalyst C1-3 is 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 348 kg / mol, a molecular weight dispersion index of 2.3, a melting temperature of 238°C, and an isotactic degree of 98%.

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

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

[0172] The steps for producing poly(4-methyl-1-pentene) in this embodiment are the same as in Example 1, except that catalyst C1-3 is 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), and the produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 301 kg / mol, a molecular weight dispersion index of 3.0, a melting temperature of 238°C, and an isotactic degree of 98%.

[0174] (Example 32) The production methods for both the main catalyst and the catalyst in this embodiment 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 in Example 1, except that 0.025 mL of 4-methyl-1-pentene monomer is added in the homopolymerization reaction (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 200:1).

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

[0177] (Example 33) The production methods for both the main catalyst and the catalyst in this embodiment are the same as those in Example 1.

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

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

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

[0181] A Schlenk flask equipped with a magnetic stirrer was continuously evacuated and dried under an infrared lamp for 2 hours. After natural cooling, it was purged with nitrogen three times until it reached atmospheric pressure. 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 500 μmol of triethylaluminum were added in that order, stirred, and held in a water bath at a constant temperature of 40°C for 30 minutes. 20 mg of Ziegler-Natta catalyst was added to the reaction system and the timer was started. Polymerization was allowed for 2 hours, then 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, the mixture was filtered. And obtain a precipitateThe material was washed three times with ethanol and dried under vacuum until it reached a certain weight 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 produced poly(4-methyl-1-pentene) had a weight-average molecular weight of 1004 kg / mol, a molecular weight dispersion index of 13.7, a melting temperature of 237°C, and an isotactic degree of 96%.

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

[0184] The catalyst described above may also be obtained by referring to the method described in reference 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 continuously evacuated and dried under an infrared lamp for 2 hours. After natural cooling, nitrogen purging was performed 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 that order, stirred, and held at a constant temperature of 40°C in a water bath for 30 minutes. 10 μmol of metallocene-type zirconium complex catalyst was added to the reaction system and the timer was started. After polymerization 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, the solution was filtered. And obtain a precipitate The material was washed three times with ethanol and dried under vacuum until it reached a certain weight to obtain poly(4-methyl-1-pentene).

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

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

[0188] The catalyst described above may also 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 continuously evacuated and dried under an infrared lamp for 2 hours. After natural cooling, nitrogen purging was performed three times until atmospheric 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 held at a constant temperature of 40°C in a water bath for 30 minutes. 10 μmol of late-stage transition metal nickel catalyst was added to the reaction system and timing was started. After polymerization 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, the solution was filtered. And obtain a precipitate The material was washed three times with ethanol and dried under vacuum until it reached a certain weight to obtain poly(4-methyl-1-pentene).

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

[0191] For ease of comparison, Table 1 summarizes the catalytic activity of the catalysts produced in the above examples and comparative examples, as well as the weight-average molecular weight, molecular weight dispersion index, melting temperature, and isotacticity of the produced poly(4-methyl-1-pentene).

[0192] In Table 1, the active unit M for catalysts in Examples 1 to 33 is Hf, in Comparative Example 1 M is Ti, in Comparative Example 2 M is Zr, and in Comparative Example 3 M is Ni.

[0193] [Table 1] JPEG0007900524000013.jpg37130

[0194] As can be seen from Table 1, this application by Iminoaminehafniu Mu catalyst This catalyst can catalyze the polymerization of 4-methyl-1-pentene with high activity, exhibiting higher activity than Ziegler-Natta catalysts, metallocene catalysts, and late transition metal catalysts. Furthermore, the poly(4-methyl-1-pentene) product prepared using the hafnium-based catalyst according to this invention has the advantages of high molecular weight, a narrow molecular weight distribution, and high isotacticity. .

[0195] The above embodiments are intended to illustrate the technical solutions of the present application and are not intended to limit them. While the present application is described in detail with reference to the embodiments described above, those skilled in the art will understand that the technical solutions described in the embodiments above may still be modified, or some or all of their technical features may be replaced with equivalent ones. Such modifications or replacements will not cause the intent of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application. Cross-references to related applications.

[0196] This application claims priority to the Chinese patent application filed with the China National Intellectual Property Administration on September 8, 2022, application number 202211099369.3, titled "Main catalyst for the production of poly(4-methyl-1-pentene) and its uses," which is incorporated in its entirety by reference.

Claims

1. A main catalyst for producing poly(4-methyl-1-pentene), Having the structure shown by formula I, 【Chemistry 1】 In equation I, R １ R is selected from hydrogen or phenyl, １ If R is selected from phenyl, １ It condenses with the naphthalene ring in formula I to form an anthracene ring, R ２ The main catalyst is selected from methyl or isopropyl.

2. Step 1 involves reacting methylglyoxal with 2,6-diisopropylaniline to obtain intermediate A, Step 2 involves reacting intermediate A with α-naphthylamine or α-antramine to obtain intermediate B, Intermediate B and 2nd place R ２ Step 3 involves reacting a substituted phenyllithium compound to obtain intermediate C, Step 4 involves sequentially reacting intermediate C with alkyllithium and hafnium tetrahalide to obtain intermediate D, The process includes step 5, in which intermediate D is reacted with methylmagnesium halide to obtain the main catalyst represented by formula I. R ２ It is selected from methyl or isopropyl. 【Chemistry 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, hafnium tetrahalide is tetrachlorohafnium and / or, A method for producing a main catalyst for producing poly(4-methyl-1-pentene) according to claim 2, wherein in step 5, the methylmagnesium halide is methylmagnesium bromide.

4. A catalyst for producing poly(4-methyl-1-pentene), comprising an activator and the main catalyst described in claim 1, wherein the activator is a composition of triphenylmethylium tetrakis(pentafluorophenyl) borate and alkylaluminum.

5. The catalyst according to claim 4, wherein the molar ratio of triphenylmethylium tetrakis(pentafluorophenyl) borate to the alkylaluminum in the composition is 1:(50-300).

6. The catalyst according to claim 4 or 5, wherein the molar ratio of the main catalyst to the activator is 1:(1 to 5).

7. A method for producing poly(4-methyl-1-pentene), comprising catalyzing the homopolymerization reaction of a 4-methyl-1-pentene monomer with the catalyst described in claim 4 to obtain poly(4-methyl-1-pentene).

8. The manufacturing method according to claim 7, wherein the molar ratio of the 4-methyl-1-pentene monomer to the catalyst is (100 to 400,000):

1.

9. The manufacturing method according to claim 8, wherein the molar ratio of the 4-methyl-1-pentene monomer to the catalyst is (10,000 to 100,000):

1.

10. The manufacturing method according to claim 7, wherein the temperature of the homopolymerization reaction is 20 to 60°C.

11. The manufacturing method according to claim 7, wherein the poly(4-methyl-1-pentene) has a weight-average molecular weight of 500,000 or more, a molecular weight dispersion index of 4 or less, an isotacticity of 95% or more, and a melting temperature of 230°C or higher.

12. The manufacturing method according to claim 11, wherein the poly(4-methyl-1-pentene) has a weight-average molecular weight of 500,000 to 1,630,000, a molecular weight dispersion index of 2.0 to 4.0, an isotacticity of 95% or more, and a melting temperature of 230 to 240°C.

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