A procatalyst for the preparation of poly(4-methyl-1-pentene) and use thereof

Abstract

The application provides a kind of main catalyst for preparing poly (4-methyl-1-pentene) and its application.The main catalyst for preparing poly (4-methyl-1-pentene) of the application has the structure shown in formula I, in formula I, R1 is selected from hydrogen or phenyl, when R1 is selected from phenyl, R1 is fused with the benzene ring in formula I to form anthracene ring;R2 is selected from methyl or isopropyl.The main catalyst of the application is applied in catalytic system for catalyzing the homopolymerization reaction of 4-methyl-1-pentene, the catalyst shows high catalytic activity, and the poly (4-methyl-1-pentene) prepared has high molecular weight, narrow molecular weight distribution and high stereoregularity, and has broad market application prospect.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization and relates to a main catalyst for the preparation of poly(4-methyl-1-pentene) and its application. Background Technology

[0002] Poly(4-methyl-1-pentene) (PMP) is a crystalline resin with a stereoregular structure. Its unique structure endows it with excellent chemical resistance, mechanical properties, processability, electrical insulation properties, low dielectric properties, optical properties, air permeability, and easy peeling properties. Therefore, PMP has important applications in fiber materials, release materials, high-end medical materials, and electronic materials.

[0003] Poly(4-methyl-1-pentene) is mainly prepared by homopolymerization of 4-methyl-1-pentene monomers catalyzed by catalysts. Currently, there are three types of catalyst systems used for the polymerization of 4-methyl-1-pentene monomers: Ziegler-Natta catalysts, metallocene catalysts, and post-transition metal nickel-palladium catalysts.

[0004] Ziegler-Natta catalysts can effectively catalyze the polymerization of 4-methyl-1-pentene to obtain polymers with high isotactic crystallinity. In addition, the stereoregularity of the product can be adjusted by adding an electron donor, so that the isotacticity of the polymer is greater than 95% and the melting temperature reaches above 230°C. However, Ziegler-Natta catalysts have multiple active centers, and the resulting polymers have a very wide molecular weight distribution, usually greater than 10. The low molecular weight fraction has poor mechanical properties, which limits 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 has a significant impact on the isotacticity of poly(4-methyl-1-pentene). Currently reported C2-symmetric titanoceramsite / zirconium catalysts can catalyze the polymerization of 4-methyl-1-pentene, achieving a polymer regularity of over 90%. However, due to the presence of a single metal active center, the molecular weight distribution of the poly(4-methyl-1-pentene) prepared by these catalysts is relatively narrow, typically below 3. Furthermore, the large steric hindrance of metallocene catalysts makes it difficult for sterically hindered 4-methyl-1-pentene monomers to insert, resulting in low activity of metallocene catalysts for 4-methyl-1-pentene polymerization and making it difficult to prepare polymers with molecular weights exceeding 100,000.

[0006] The post-transition metal nickel-palladium catalyst exhibits poor stereocontrol when used for the polymerization of 4-methyl-1-pentene, failing to yield poly(4-methyl-1-pentene) with high regularity. Furthermore, the post-transition metal nickel-palladium catalyst exhibits chain walking during the catalytic polymerization process, leading to complex branching of the product and resulting in a non-crystalline polymer that is difficult to commercialize.

[0007] Therefore, it is of great significance to develop a catalytic system that can prepare poly(4-methyl-1-pentene) with high molecular weight, high isotacticity and narrow molecular weight. Summary of the Invention

[0008] This invention provides a main catalyst for preparing poly(4-methyl-1-pentene) and a method thereof. 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 catalysis has the advantages of high molecular weight, narrow molecular weight distribution, and high isotacticity.

[0009] The present invention also provides a catalyst for preparing poly(4-methyl-1-pentene), which is obtained by compounding the above-mentioned main catalyst and activator. Since the catalyst includes the above-mentioned main catalyst, it has the advantages of high catalytic activity and the poly(4-methyl-1-pentene) prepared by catalysis has the advantages of high molecular weight, narrow molecular weight distribution and high isotacticity.

[0010] The present invention also provides a method for preparing poly(4-methyl-1-pentene), which uses the above-mentioned catalyst to catalyze the homopolymerization reaction of 4-methyl-1-pentene monomer to prepare poly(4-methyl-1-pentene). Therefore, the poly(4-methyl-1-pentene) prepared by this method has the advantages of high molecular weight, narrow molecular weight distribution and high isotacticity.

[0011] A first aspect of the present invention provides a main catalyst for the preparation of poly(4-methyl-1-pentene), said main catalyst having the structure shown in Formula I:

[0012]

[0013] In Formula I, R1 is selected from hydrogen or phenyl. When R1 is selected from phenyl, R1 fuses with the naphthalene ring in Formula I to form an anthracene ring; R2 is selected from methyl or isopropyl.

[0014] The compound shown in Formula I is a non-necrobridged imine amino hafnium complex. This complex has small steric hindrance, which is conducive to the coordination insertion of the sterically hindered 4-methyl-1-pentene monomer. This enables the catalyst to obtain high catalytic activity and high molecular weight poly(4-methyl-1-pentene). At the same time, the single metal active center of this complex can make the catalyst more selective, which is conducive to obtaining poly(4-methyl-1-pentene) with narrow molecular weight distribution and high isotacticity.

[0015] The inventors discovered that when R2 is selected from isopropyl, the main catalyst exhibits higher catalytic activity, and the resulting poly(4-methyl-1-pentene) has a narrower molecular weight and higher isotacticity.

[0016] A second aspect of the present invention provides a method for preparing the above-mentioned main catalyst for preparing poly(4-methyl-1-pentene), the preparation route of which is shown below:

[0017]

[0018] The specific steps include: 1) reacting methylglyoxal with 2,6-diisopropylaniline to obtain intermediate A; 2) reacting intermediate A with α-naphthylamine or α-anthramine to obtain intermediate B; 3) reacting intermediate B with an R2-substituted phenyl lithium compound to obtain intermediate C; 4) reacting intermediate C sequentially with alkyllithium and hafnium tetrahalide to obtain intermediate D; 5) reacting intermediate D with methylmagnesium halide to obtain the main catalyst shown in Formula I.

[0019] Steps 1) and 2) involve using arylamine compounds to condense the aldehyde and carbonyl groups in methylglyoxal to obtain an asymmetric aryl-substituted diimine intermediate B. In step 3), an R2-substituted phenyl lithium compound is used as a nucleophile to nucleophilically add to intermediate B to obtain a bridgehead-substituted imine amine intermediate C, which is the ligand of the main catalyst. In step 4), alkyllithium is deprotonated from the secondary amine and then reacted with hafnium tetrahalide to obtain imine amine hafnium halide intermediate D. In step 5), intermediate D undergoes a Grignard reaction with methyl magnesium halide to obtain the main catalyst shown in Formula I.

[0020] In step 4), the alkyl lithium is preferably n-butyllithium, the hafnium tetrahalide is preferably hafnium tetrachloride, and in step 5), the methyl magnesium halide is preferably methyl magnesium bromide.

[0021] The selection of specific reaction conditions in steps 1) to 5) is a routine procedure for those skilled in the art with a background in organic synthesis, and will not be elaborated here.

[0022] A third aspect of the present invention provides a catalyst for preparing poly(4-methyl-1-pentene), the catalyst comprising the main catalyst and activator provided in the first aspect of the present invention.

[0023] Since the catalyst includes the main catalyst provided in the first aspect of the present invention, it has the advantages of high catalytic activity and the poly(4-methyl-1-pentene) prepared by the catalyst has the advantages of high molecular weight, narrow molecular weight distribution and high isotacticity.

[0024] Furthermore, the activator of the present invention is selected from a combination of triphenylcarbium tetra(pentafluorobenzene)borate and alkyl aluminum. Specifically, considering factors such as catalyst activity, selectivity, and cost, the alkyl aluminum compound in the composition is preferably at least one of trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0025] Furthermore, through experimental exploration of the molar ratio of triphenylcarbazide tetra(pentafluorobenzene)borate to alkylaluminum in the composition, as well as the molar ratio of the main catalyst to the co-catalyst, it was found that when the molar ratio of triphenylcarbazide tetra(pentafluorobenzene)borate to alkylaluminum in the composition is 1:(50-300), and the molar ratio of the main catalyst to the activator is 1:(1-5), the catalyst has higher catalytic activity, and the prepared polymer has higher molecular weight, narrower molecular weight distribution, and higher isotacticity.

[0026] The fourth aspect of the present invention provides a method for preparing poly(4-methyl-1-pentene), the method comprising: using the catalyst provided in the third aspect of the present invention to catalyze the homopolymerization reaction of 4-methyl-1-pentene monomer to obtain the poly(4-methyl-1-pentene).

[0027] The catalyst of this invention exhibits high catalytic activity and high selectivity in the homopolymerization reaction of 4-methyl-1-pentene. The poly(4-methyl-1-pentene) prepared has high molecular weight, narrow molecular weight distribution and high isotacticity, and shows better mechanical properties and thermal stability, thus having a broader market application prospect.

[0028] In the above homopolymerization reaction, the molar ratio of 4-methyl-1-pentene monomer to catalyst, the temperature of the homopolymerization reaction, the solvent and other conditions can be optimized to obtain poly(4-methyl-1-pentene) with higher molecular weight, narrower molecular weight distribution and higher isotacticity.

[0029] After optimization experiments, it was found that the molar ratio of 4-methyl-1-pentene monomer to catalyst is preferably (100-400000):1, and more preferably (10000-100000):1; the temperature of homopolymerization reaction is 20-60℃; the solvent for homopolymerization reaction is preferably one or more of 1,2-dichloroethane, chloroform, chlorobenzene, toluene, benzene, and xylene.

[0030] By controlling factors such as the molar ratio of 4-methyl-1-pentene monomer to catalyst, polymerization temperature, and polymerization solvent in the homopolymerization reaction, poly(4-methyl-1-pentene) with a weight-average molecular weight ≥ 500,000, further ranging from 500,000 to 1,630,000; a molecular weight distribution index ≤ 4, further ranging from 2.0 to 4.0; isotacticity ≥ 95%; and a melting temperature ≥ 230℃, further ranging from 230 to 240℃ can be obtained.

[0031] Compared with the prior art, the present invention has at least the following beneficial effects:

[0032] 1) The main catalyst provided by this invention is a non-necrobridged imine amine complex. This complex has small steric hindrance, which is conducive to the coordination insertion of sterically hindered 4-methyl-1-pentene monomers. This enables the catalyst to obtain high catalytic activity and high molecular weight poly(4-methyl-1-pentene). At the same time, the single metal active center of this complex can make the catalyst more selective, which is conducive to obtaining poly(4-methyl-1-pentene) with narrow molecular distribution and high isotacticity.

[0033] 2) The main catalyst of the present invention is applied to the catalytic system to catalyze the polymerization of 4-methyl-1-pentene monomer. The resulting poly(4-methyl-1-pentene) has high molecular weight, narrow molecular weight distribution, high isotacticity and high melting temperature. Therefore, the polymer has better mechanical properties and thermal stability and has a broader application prospect.

[0034] 3) The poly(4-methyl-1-pentene) preparation method provided by the present invention has the advantages of mild and efficient reaction conditions. Attached Figure Description

[0035] Figure 1 The poly(4-methyl-1-pentene) prepared in Example 1 13 C NMR spectrum;

[0036] Figure 2 The image shows the DSC curve of poly(4-methyl-1-pentene) prepared in Example 1.

[0037] Figure 3 The image shows the GPC curve of poly(4-methyl-1-pentene) prepared in Example 1. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0039] The following detailed description, in conjunction with specific embodiments, of the main catalyst provided by the present invention for the preparation of poly(4-methyl-1-pentene) and its application.

[0040] It should be noted that, unless otherwise specified, the raw materials used in the following embodiments can be obtained by commercial purchase or conventional methods, and the experimental methods without specific conditions are all conventional methods and conditions well known in the art.

[0041] The catalytic activity of the catalysts in the following examples and comparative examples is calculated using the following formula: Catalytic activity = mass of poly(4-methyl-1-pentene) (g) / (amount of main catalyst added (mol) × reaction time (h)).

[0042] The weight-average molecular weight and molecular weight distribution index of poly(4-methyl-1-pentene) prepared in the following examples and comparative examples were determined by GPC.

[0043] The melting temperatures of the poly(4-methyl-1-pentene) prepared in the following examples and comparative examples were determined by DSC thermal analysis.

[0044] The isotacticity of the poly(4-methyl-1-pentene) prepared in the following examples and comparative examples is all based on... 13 CNMR was used for measurement.

[0045] Example 1

[0046] The preparation process of the main catalyst, the catalyst itself, and poly(4-methyl-1-pentene) in this embodiment is as follows:

[0047] 1) Preparation of main catalyst P1

[0048] The preparation route is shown below:

[0049]

[0050] The preparation steps include:

[0051] 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, mix well, and then slowly add 1.77 g (10 mmol) of 2,6-diisopropylaniline to the reaction flask. After the addition is complete, stir the reaction for 12 h, concentrate the reaction system to remove the solvent, and purify the concentrate by silica gel column chromatography (eluent is a mixed solvent of n-hexane and ethyl acetate with a volume ratio of 50:1) to obtain compound S2 with a yield of 93%.

[0052] b. Dissolve 0.93 g (4 mmol) of compound S2 in 50 mL of toluene, then slowly add 0.72 g (5 mmol) of α-naphthylamine and a catalytic amount of p-toluenesulfonic acid, heat to reflux, react for 12 h, cool and concentrate to remove solvent, purify the concentrate by column chromatography (eluent is a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 50:1) to give compound S3 in 89% yield;

[0053] c. At -40°C, 1.78 g (5 mmol) of compound S3 was dissolved in anhydrous diethyl ether, and a solution of 0.76 g (6 mmol) of 2-isopropylphenyllithium in diethyl ether was slowly added dropwise. After the addition was complete, the reaction system was allowed to rise naturally to room temperature and reacted overnight. After the reaction was detected by TLC, a saturated solution of ammonium chloride was added to the reaction system to quench the reaction. The mixture was extracted three times with anhydrous diethyl ether, and the diethyl ether phase was collected. 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 and recrystallized to obtain ligand L1 in 90% yield.

[0054] The characterization data for ligand L1 are as follows:

[0055] 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).

[0056] 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

[0057] d. Under a nitrogen atmosphere, 0.93 g (2 mmol) of compound S4 was added to a dry Schlenk flask and dissolved in 20 mL of toluene. A 1.5 mL (1.6 M) solution of n-butyllithium was added dropwise to the Schlenk flask at -50 °C. After the addition was complete, the flask was allowed to cool naturally to room temperature. Once the reaction was complete, the solvent was removed by vacuum, and a yellow powder precipitated. The powder was washed three times with n-hexane, and after removing the hexane, a yellow lithium salt ligand was obtained. The yellow lithium ligand was dissolved in toluene and transferred to a reaction flask. HfCl4 was then added... 0.71 g (2.2 mmol) of toluene suspension was added to the reaction flask, and the mixture was heated to 120 °C and reacted for 6 hours. The mixture was then allowed to cool naturally to room temperature and then placed in a low-temperature bath to cool to -40 °C. MeMgBr (2.5 mL, 3 M) was then slowly added dropwise to the reaction system. After the addition was complete, the mixture was allowed to cool naturally to room temperature and stirred for 6 hours. The precipitate was removed by filtration and then washed three times with toluene. The filtrates were combined and the solvent in the filtrate was removed by vacuum distillation to obtain a solid. The solid was washed three times with n-hexane and dried to obtain the main catalyst P1, a yellow solid with a yield of 64%.

[0058] The characterization data of the main catalyst P1 are as follows:

[0059] 1 H 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).

[0060] MS-EI (m / z): 684.3 (M + ).

[0061] 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.

[0062] 2) Preparation of catalyst C1-3

[0063] Using compound P1 as the main catalyst and a combination of triphenylcarbamonite tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio 1:67) as the activator, and labeling the activator as A3, the main catalyst P1 and the activator A3 were compounded in a molar ratio of 1:1.5 to obtain catalyst C1-3.

[0064] 3) Preparation of poly(4-methyl-1-pentene)

[0065] The specific steps include: continuously evacuating a Schlenk flask equipped with a magnetic stirrer and drying it with an infrared lamp for two hours; after natural cooling, replacing the nitrogen gas three times to atmospheric pressure; then adding 7 mL of toluene and 3 mL of 4-methyl-1-pentene monomer sequentially to the Schlenk flask; and stirring at 40°C in a water bath for half an hour. Subsequently, 1 μmol of catalyst C1-3 (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 24000:1) was added to the system to initiate polymerization. After polymerization reached 5 min, the polymerization was terminated by adding a 10% hydrochloric acid-acidified ethanol solution. The polymerization system was filtered, washed three times with ethanol, and dried under vacuum to constant weight to obtain poly(4-methyl-1-pentene).

[0066] Calculations show that the catalytic activity of catalyst C1-3 in the above homopolymerization reaction is 14.5 kg polymer / (mmolHf·h).

[0067] The poly(4-methyl-1-pentene) prepared in Example 1 was characterized using data. Figure 1 The poly(4-methyl-1-pentene) prepared in Example 1 13 C NMR spectrum; Figure 2 The image shows the DSC curve of poly(4-methyl-1-pentene) prepared in Example 1. Figure 3 The image shows the GPC curve of poly(4-methyl-1-pentene) prepared in Example 1. Figures 1 to 3 As can be seen from the analysis,

[0068] 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%.

[0069] Example 2

[0070] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0071] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization temperature is changed from 40°C to 20°C.

[0072] In this embodiment, the catalytic activity of catalyst C1-3 is 3.1 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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 of >99%.

[0073] Example 3

[0074] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0075] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization temperature is changed from 40°C to 60°C.

[0076] In this embodiment, the catalytic activity of catalyst C1-3 is 6.5 kg polymer / (mmol Hf·h), and the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) is 821 kg / mol, the molecular weight distribution index is 2.0, the melting temperature is 237 °C, and the isotacticity is 97%.

[0077] Example 4

[0078] The main catalyst and catalyst preparation methods in this example are the same as in Example 1;

[0079] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1. The difference is that the amount of 4-methyl-1-pentene monomer added in the homopolymerization reaction is 0.0125 mL (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 100:1).

[0080] In this embodiment, the catalytic activity of catalyst C1-3 is 4.8 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0081] Example 5

[0082] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0083] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1. The difference is that the amount of 4-methyl-1-pentene monomer added in the homopolymerization reaction is 0.125 mL (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 1000:1).

[0084] In this embodiment, the catalytic activity of catalyst C1-3 is 13.8 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0085] Example 6

[0086] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0087] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those 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).

[0088] In this embodiment, the catalytic activity of catalyst C1-3 is 9.2 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0089] Example 7

[0090] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0091] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1. The difference is 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).

[0092] In this embodiment, the catalytic activity of catalyst C1-3 is 29.6 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0093] Example 8

[0094] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0095] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced with benzene instead of toluene.

[0096] In this embodiment, the catalytic activity of catalyst C1-3 is 8.3 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0097] Example 9

[0098] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0099] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced with xylene instead of toluene.

[0100] In this embodiment, the catalytic activity of catalyst C1-3 is 10.5 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0101] Example 10

[0102] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0103] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced with 1,2-dichloroethane instead of toluene.

[0104] In this embodiment, the catalytic activity of catalyst C1-3 is 12.1 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0105] Example 11

[0106] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0107] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced with chloroform instead of toluene.

[0108] In this embodiment, the catalytic activity of catalyst C1-3 is 9.8 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0109] Example 12

[0110] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0111] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced with chlorobenzene instead of toluene.

[0112] In this embodiment, the catalytic activity of catalyst C1-3 is 10.9 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0113] Example 13

[0114] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0115] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced by a mixture of toluene and benzene in a volume ratio of 1:1.

[0116] In this embodiment, the catalytic activity of catalyst C1-3 is 7.8 kg polymer / (mmol Hf·h), and the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) is 778 kg / mol, the molecular weight distribution index is 2.7, the melting temperature is 238 °C, and the isotacticity is 98%.

[0117] Example 14

[0118] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0119] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced by a mixture of toluene and xylene in a volume ratio of 1:1.

[0120] In this embodiment, the catalytic activity of catalyst C1-3 in the homopolymerization reaction is 8.7 kg polymer / (mmol Hf·h), and the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) is 749 kg / mol, the molecular weight distribution index is 2.7, the melting temperature is 238℃, and the isotacticity is 98%.

[0121] Example 15

[0122] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0123] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced by a mixture of 1,2-dichloroethane and chloroform in a volume ratio of 1:1.

[0124] In this embodiment, the catalytic activity of catalyst C1-3 is 7.1 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0125] Example 16

[0126] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0127] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the polymerization solvent is replaced by a mixture of chlorobenzene and benzene in a volume ratio of 1:1.

[0128] In this embodiment, the catalytic activity of catalyst C1-3 is 8.1 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0129] Example 17

[0130] The main catalyst in this embodiment is the same as that in Example 1;

[0131] The catalyst in this embodiment was obtained by compounding the main catalyst P1 and the activator A3 in a molar ratio of 1:1, and the resulting catalyst was labeled as catalyst C1-7.

[0132] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-7.

[0133] In this embodiment, the catalytic activity of catalyst C1-7 is 6.8 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0134] Example 18

[0135] The main catalyst in this embodiment is the same as that in Example 1;

[0136] The catalyst in this embodiment was obtained by compounding the main catalyst P1 and the activator A3 in a molar ratio of 1:3, and the resulting catalyst was labeled as catalyst C1-8.

[0137] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-8.

[0138] In this embodiment, the catalytic activity of catalyst C1-8 is 7.2 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0139] Example 19

[0140] The main catalyst in this embodiment is the same as that in Example 1;

[0141] The catalyst in this embodiment was obtained by compounding the main catalyst P1 and the activator A3 in a molar ratio of 1:5, and the resulting catalyst is labeled as catalyst C1-9.

[0142] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-9.

[0143] In this embodiment, the catalytic activity of catalyst C1-9 is 8.8 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0144] Example 20

[0145] The main catalyst in this embodiment is the same as that in Example 1;

[0146] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamate tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio of 1:50) as the activator, labeled A4. The main catalyst P1 and the activator A4 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-4.

[0147] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-4.

[0148] In this embodiment, the catalytic activity of catalyst C1-4 is 8.3 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0149] Example 21

[0150] The main catalyst in this embodiment is the same as that in Example 1;

[0151] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamate tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio of 1:150) as the activator, labeled A5. The main catalyst P1 and the activator A5 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-5.

[0152] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-5.

[0153] In this embodiment, the catalytic activity of catalyst C1-5 is 8.9 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0154] Example 22

[0155] The main catalyst in this embodiment is the same as that in Example 1;

[0156] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamate tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio of 1:300) as the activator, labeled A6. The main catalyst P1 and the activator A6 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-6.

[0157] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-6.

[0158] In this embodiment, the catalytic activity of catalyst C1-6 is 7.4 kg polymer / (mmol Hf·h), and the prepared 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%.

[0159] Example 23

[0160] The main catalyst in this embodiment is the same as that in Example 1;

[0161] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamonite tetra(pentafluorobenzene)borate and trimethylaluminum (molar ratio of 1:67) as the activator, labeled A1. The main catalyst P1 and the activator A1 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-1.

[0162] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-1.

[0163] In this embodiment, the catalytic activity of catalyst C1-1 is 7.8 kg polymer / (mmol Hf·h), and the prepared 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%.

[0164] Example 24

[0165] The main catalyst in this embodiment is the same as that in Example 1;

[0166] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamonite tetra(pentafluorobenzene)borate and triethylaluminum (molar ratio of 1:67) as the activator, labeled A2. The main catalyst P1 and the activator A2 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-2.

[0167] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-2.

[0168] In this embodiment, the catalytic activity of catalyst C1-2 is 9.4 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0169] Example 25

[0170] The preparation process of the main catalyst, the catalyst itself, and poly(4-methyl-1-pentene) in this embodiment is as follows:

[0171] 1) Preparation of main catalyst P2

[0172] The structural formula of the main catalyst P2 is as follows:

[0173]

[0174] The preparation steps of the main catalyst P2 are basically the same as those of the main catalyst P1 described in Example 1. The difference is 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%.

[0175] The structural formula of ligand L2 is as follows:

[0176]

[0177] The characterization data for ligand L2 are as follows:

[0178] 1 H 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).1.78(d,6H,CH(CH3)2),1.19(d,6H,CH(CH3)2),1.01(d,3H,CH(CH3)2).

[0179] 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.

[0180] The characterization data of the main catalyst P2 are as follows:

[0181] 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, 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).

[0182] MS-EI (m / z): 656.27 (M + ).

[0183] 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,4.25.

[0184] 2) Preparation of catalyst C2-3

[0185] Using compound P2 as the main catalyst, catalyst C2-3 was obtained by compounding the main catalyst P2 and the activator A3 in a molar ratio of 1:1.5.

[0186] 3) Preparation of poly(4-methyl-1-pentene)

[0187] The specific steps are basically the same as in Example 1, except that catalyst C1-3 is replaced with catalyst C2-3.

[0188] In this embodiment, the catalytic activity of catalyst C2-3 is 0.6 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0189] Example 26

[0190] The preparation process of the main catalyst, the catalyst itself, and poly(4-methyl-1-pentene) in this embodiment is as follows:

[0191] 1) Preparation of main catalyst P3

[0192] The structural formula of the main catalyst P3 is as follows:

[0193]

[0194] The preparation steps of the main catalyst P3 are basically the same as those of the main catalyst P1 described in Example 1, except that naphthylamine in step b is replaced with anthraceneamine.

[0195] The ligand obtained in step c is L3, and the yield of step c is 87%, while the yield of step d is 59%.

[0196] The structural formula of ligand L3 is as follows:

[0197]

[0198] The characterization data for ligand L3 are as follows:

[0199] 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).

[0200] 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.

[0201] The characterization data of the main catalyst P3 are as follows:

[0202] 1H 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).

[0203] MS-EI (m / z): 732.31 (M + ).

[0204] 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.

[0205] 2) Preparation of catalyst C3-3

[0206] Using compound P3 as the main catalyst, the catalyst system C3-3 was obtained by compounding the main catalyst P3 and the activator A3 in a molar ratio of 1:1.5.

[0207] 3) Preparation of poly(4-methyl-1-pentene)

[0208] The specific steps are basically the same as in Example 1, except that catalyst C1-3 is replaced with catalyst C3-3.

[0209] In this embodiment, the catalytic activity of catalyst C3-3 is 8.3 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0210] Example 27

[0211] The preparation process of the main catalyst, the catalyst itself, and poly(4-methyl-1-pentene) in this embodiment is as follows:

[0212] 1) Preparation of main catalyst P4

[0213] The structural formula of the main catalyst P4 is as follows:

[0214]

[0215] The preparation steps of the main catalyst P4 are basically the same as those of the main catalyst P3 described in Example 26. The difference is 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%.

[0216] The structural formula of ligand L4 is as follows:

[0217]

[0218] The characterization data for ligand L4 are as follows:

[0219] 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).

[0220] 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.

[0221] The characterization data of the main catalyst P4 are as follows:

[0222] 1H 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).

[0223] MS-EI (m / z): 706.28 (M + ).

[0224] 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.

[0225] 2) Preparation of catalyst C4-3

[0226] Using compound P4 as the main catalyst, the catalyst system C4-3 was obtained by compounding the main catalyst P4 and the activator A3 in a molar ratio of 1:1.5.

[0227] 3) Preparation of poly(4-methyl-1-pentene)

[0228] The specific steps are basically the same as in Example 1, except that catalyst C1-3 is replaced with catalyst C4-3.

[0229] In this embodiment, the catalytic activity of C4-3 is 0.4 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0230] Example 28

[0231] The main catalyst in this embodiment is the same as that in Example 1;

[0232] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamate tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio of 1:25) as the activator, labeled A4. The main catalyst P1 and the activator A4 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-10.

[0233] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-10.

[0234] In this embodiment, the catalyst C1-10 has a catalytic activity of 9.5 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) 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%.

[0235] Example 29

[0236] The main catalyst in this embodiment is the same as that in Example 1;

[0237] In this embodiment, the catalyst uses compound P1 as the main catalyst and a combination of triphenylcarbamate tetra(pentafluorobenzene)borate and triisobutylaluminum (molar ratio of 1:450) as the activator, labeled A6. The main catalyst P1 and the activator A6 are compounded in a mass ratio of 1:1.5 to obtain catalyst C1-11.

[0238] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-11.

[0239] In this embodiment, the catalytic activity of catalyst C1-11 is 6.9 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0240] Example 30

[0241] The main catalyst in this embodiment is the same as that in Example 1;

[0242] The catalyst in this embodiment was obtained by compounding the main catalyst P1 and the activator A3 in a molar ratio of 2:1, and the resulting catalyst was labeled as catalyst C1-12.

[0243] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-12.

[0244] In this embodiment, the catalytic activity of catalyst C1-12 is 2.9 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0245] Example 31

[0246] The main catalyst in this embodiment is the same as that in Example 1;

[0247] The catalyst in this embodiment was obtained by compounding the main catalyst P1 and the activator A3 in a molar ratio of 1:7, and the resulting catalyst was labeled as catalyst C1-13.

[0248] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that catalyst C1-3 is replaced with catalyst C1-13.

[0249] In this embodiment, the catalytic activity of catalyst C1-13 is 9.9 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0250] Example 32

[0251] The main catalyst and catalyst preparation methods in this example are the same as in Example 1;

[0252] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1, except that the amount of 4-methyl-1-pentene monomer added in the homopolymerization reaction is 0.025 mL (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 200:1).

[0253] In this embodiment, the catalytic activity of catalyst C1-3 is 0.6 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0254] Example 33

[0255] The main catalyst and catalyst preparation in this embodiment are the same as in Example 1;

[0256] The preparation steps of poly(4-methyl-1-pentene) in this embodiment are basically the same as those in Example 1. The difference is that 7.5 mL of 4-methyl-1-pentene monomer was added in the homopolymerization reaction (the molar ratio of 4-methyl-1-pentene monomer to catalyst C1-3 is 60000:1).

[0257] In this embodiment, the catalytic activity of catalyst C1-3 is 27.4 kg polymer / (mmol Hf·h), and the prepared poly(4-methyl-1-pentene) has 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%.

[0258] Comparative Example 1

[0259] This comparative example uses a Ziegler-Natta catalyst (commercially available, product code CS-2) to catalyze the homopolymerization of 4-methyl-1-pentene. The specific steps are as follows:

[0260] A Schlenk flask equipped with a magnetic stirrer was continuously evacuated and dried under an infrared lamp for two hours. After natural cooling, the nitrogen gas was purged three times to atmospheric pressure. Then, 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 500 μmol of triethylaluminum were added sequentially, and the mixture was stirred and kept at a constant temperature of 40°C for half an hour in a water bath. 20 mg of Ziegler-Natta catalyst was added to the reaction system and the time was started. After 2 hours of polymerization, the reaction flask was opened, and a 10% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. After stirring for 3 hours, the mixture was filtered, washed three times with ethanol, and dried under vacuum to constant weight to obtain poly(4-methyl-1-pentene).

[0261] In this comparative example, the catalytic activity of the Ziegler-Natta catalyst was 275 g polymer / (mmol Ti·h), and the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) was 1004 kg / mol, the molecular weight distribution index was 13.7, the melting temperature was 237 °C, and the isotacticity was 96%.

[0262] Comparative Example 2

[0263] This comparative example uses a zirconocene catalyst to catalyze the homopolymerization of 4-methyl-1-pentene. The structural formula of the zirconocene catalyst is as follows:

[0264]

[0265] The above catalyst can be prepared by referring to the method described in the literature J.Mol.Catal.A 1996,112:37.

[0266] The specific steps of the homopolymerization reaction in this comparative example were as follows: A Schlenk flask equipped with a magnetic stirrer was continuously evacuated and dried with an infrared lamp for two hours. After natural cooling, nitrogen gas was purged three times to atmospheric pressure. Then, 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 20 mmol of methylaluminoxane (MAO) were added sequentially, and the mixture was stirred and kept at a constant temperature of 40°C for half an hour in a water bath. 10 μmol of zirconium monoxide catalyst was added to the reaction system and the time was started. After 7 hours of polymerization, the reaction flask was opened, and ethanol solution acidified with 10% hydrochloric acid was added to terminate the polymerization. After stirring for 3 hours, the mixture was filtered, washed three times with ethanol, and dried under vacuum to constant weight to obtain poly(4-methyl-1-pentene).

[0267] In this comparative example, the catalytic activity of the zirconium cadmium catalyst was 10.9 g polymer / (mmol Zr·h), and the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) was 17 kg / mol, the molecular weight distribution index was 2.9, the melting temperature was 214 °C, and the isotacticity was 90%.

[0268] Comparative Example 3

[0269] This comparative example uses a post-transition metal nickel catalyst to catalyze the homopolymerization of 4-methyl-1-pentene. The structural formula of the catalyst is as follows:

[0270]

[0271] The catalyst described above can be prepared by referring to the method described in Macromolecules 2000, 33, 2320.

[0272] The specific steps of the homopolymerization reaction in this comparative example were as follows: A Schlenk flask equipped with a magnetic stirrer was continuously evacuated and dried with an infrared lamp for two hours. After natural cooling, nitrogen was purged three times to atmospheric pressure. Then, 7 mL of toluene, 3 mL of 4-methyl-1-pentene, and 2.5 mmol of diethylaluminum chloride were added sequentially. The mixture was stirred and kept at a constant temperature of 40°C for half an hour in a water bath. 10 μmol of a nickel catalyst (a later transition metal) was added to the reaction system and the time was started. After 1 hour of polymerization, the reaction flask was opened, and ethanol solution acidified with 10% hydrochloric acid was added to terminate the polymerization. After stirring for 3 hours, the mixture was filtered, washed three times with ethanol, and dried under vacuum to constant weight to obtain poly(4-methyl-1-pentene).

[0273] In this comparative example, the catalytic activity of the post-transition metal nickel catalyst was 105 g polymer / (mmol Ni·h), the weight-average molecular weight of the prepared poly(4-methyl-1-pentene) was 175 kg / mol, the molecular weight distribution index was 1.5, there was no melting temperature, the product was a random polymer, and the isotacticity was less than 10%.

[0274] For ease of comparison, the catalytic activity of the catalysts prepared in the above examples and comparative examples, as well as the weight-average molecular weight, molecular weight distribution index, melting temperature, and isotacticity of the prepared poly(4-methyl-1-pentene), are listed in Table 1.

[0275] In Table 1, M in the catalyst activity unit of Examples 1 to 33 is Hf, M is Ti in Comparative Example 1, M is Zr in Comparative Example 2, and M is Ni in Comparative Example 3.

[0276] Table 1

[0277]

[0278]

[0279]

[0280] As shown in Table 1, the imine-amine hafnium catalyst of the present invention exhibits higher catalytic activity and narrower molecular weight distribution than the Ziegler-Natta catalyst, and higher catalytic activity than the zirconium catalyst. The prepared poly(4-methyl-1-pentene) has higher molecular weight and isotacticity, and exhibits higher catalytic activity than the post-transition metal nickel catalyst. Furthermore, the prepared polymer (4-methyl-1-pentene) has higher isotacticity.

[0281] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A procatalyst for the preparation of poly(4-methyl-l-pentene) characterized in that, The procatalyst has a structure shown in formula I: Formula I In formula I, R1 is selected from hydrogen or phenyl, and when R1 is selected from phenyl, R1 is fused with the naphthalene ring in formula I to form an anthracene ring; R2 is selected from methyl or isopropyl.

2. A process for the preparation of the procatalyst for the preparation of poly(4-methyl-1-pentene) according to claim 1, characterized in that The preparation method comprises the following steps: 1) reacting methylglyoxal with 2,6-diisopropylaniline to obtain intermediate A; 2) reacting the intermediate A with an α-naphthylamine or an α-anthracene amine to obtain an intermediate B: 3) reacting the intermediate B with a phenyllithium compound substituted with R2 at the 2-position to obtain an intermediate C; 4) sequentially reacting the intermediate C with an alkyl lithium and hafnium tetrahalide to obtain an intermediate D; 5) reacting the intermediate D with methyl magnesium halide to obtain the procatalyst shown in formula I.

3. A catalyst for the preparation of poly(4-methyl-l-pentene) characterized in that, The catalyst comprises an activator and the procatalyst according to claim 1.

4. The catalyst of claim 3, wherein The activator is selected from a combination of triphenylcarbenium tetra(pentafluorophenyl)borate and an alkyl aluminum.

5. The catalyst of claim 4, wherein The molar ratio of triphenylcarbenium tetra(pentafluorophenyl)borate to the alkyl aluminum in the combination is 1: (50-300).

6. Catalyst according to any one of claims 3-5, characterised in that The molar ratio of the procatalyst to the activator is 1: (1-5).

7. A process for the preparation of poly(4-methyl-l-pentene) characterized in that, The preparation method comprises: using the catalyst according to any one of claims 4-6 to catalyze a homopolymerization reaction of 4-methyl-1-pentene monomers to obtain poly(4-methyl-1-pentene).

8. The preparation method according to claim 7, characterized in that, The molar ratio of the 4-methyl-1-pentene monomers to the catalyst is (100-400000):

1.

9. The preparation method according to claim 7, characterized in that, The homopolymerization reaction is carried out at a temperature of 20-60 ℃.

10. The preparation method according to claim 7, characterized in that, The poly(4-methyl-1-pentene) has a weight average molecular weight of ≥500,000, a molecular weight distribution index of ≤4, an isotacticity of ≥95%, and a melting temperature of ≥230 ℃.

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