Long-chain branched poly-4-methyl-1-pentene and its preparation method and application

Abstract

This invention relates to the technical field of polymers, and more particularly to a long-chain branched poly(4-methyl-1-pentene), its preparation method, and its applications. The general structural formula of the long-chain branched poly(4-methyl-1-pentene) is shown in Formula I: where R is selected from C1-C8 alkyl groups, m is selected from natural numbers 2-10, and n is selected from natural numbers 0-50. A comonomer is obtained by reacting raw materials including α,ω-non-conjugated dienes and organosiloxane monomers; the comonomer is then polymerized with 4-methyl-1-pentene to obtain the long-chain branched poly(4-methyl-1-pentene). The preparation method is simple, the reaction is mild, the comonomer conversion rate is high, no complicated pretreatment or post-treatment processes are required, and conventional Ziegler-Natta catalysts can meet the requirements, showing broad prospects for industrial production. The selected raw materials are all commonly used in industry, and no special raw materials are required, ensuring cost-effectiveness and suitability for industrial applications.

Description

Technical Field

[0001] This invention relates to the technical field of polymers, and more particularly to a long-chain branched poly(4-methyl-1-pentene), its preparation method, and its applications. Background Technology

[0002] Poly(4-methyl-1-pentene) has an irreplaceable position in high-end fields such as electronic packaging, medical materials and optical materials due to its outstanding properties such as high melting point, low density, good transparency, high chemical stability and low dielectric constant.

[0003] Currently, commercially available poly(4-methyl-1-pentene) products are typically copolymers of 4-methyl-1-pentene and a small amount of α-olefins to improve the toughness of highly isotactic homopolymers. The same strategy is also common in polypropylene materials. However, while introducing comonomers can improve the toughness of polymer materials, when the comonomer content is too high, other excellent properties of the material, such as tensile strength and impact strength, are inevitably sacrificed. Introducing long-chain branched structures into polymers is another more efficient approach. Currently, the industry commonly uses post-modification and in-situ polymerization methods to prepare long-chain branched polyolefin materials. Post-modification uses free radical grafting to impart long-chain branched structures to polyolefins, but the free radical-involved reaction can cause degradation and cross-linking side reactions of polyolefins to varying degrees. In-situ polymerization directly obtains long-chain branched polyolefins through microscopic control of the chain structure during the polymerization reaction, but this places very strict requirements on the catalytic system, requiring catalysts with specific structures or multiple catalysts used in combination, resulting in high production costs. Furthermore, if an industrially mature catalytic system can be selected, long-chain branched poly(4-methyl-1-pentene) can be directly prepared by changing the process conditions during polymerization, which will have great advantages and application prospects. Summary of the Invention

[0004] To address the problems existing in current related technologies, this invention discloses a long-chain branched poly4-methyl-1-pentene and its preparation method. This method can directly copolymerize poly4-methyl-1-pentene with a long-chain branched structure by designing novel comonomers without increasing the difficulty of process operation.

[0005] The solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a long-chain branched poly(4-methyl-1-pentene), the general structural formula of which is shown in Formula I:

[0007]

[0008] In the formula, R is selected from C1-C8 alkyl groups, m is selected from natural numbers from 2 to 10, and n is selected from natural numbers from 0 to 50.

[0009] The structure shown in Formula I provides a rigid long carbon chain and a flexible siloxane segment, and this unique structure that combines rigidity and flexibility gives it excellent impact resistance.

[0010] Preferably, the alkyl group includes straight-chain alkyl groups and branched-chain alkyl groups.

[0011] In the structure shown in Equation I, both excessively high and excessively low values ​​of m will affect the copolymerization ability of the comonomer.

[0012] In some preferred embodiments, R is selected from C1-C6 alkyl groups;

[0013] And / or, m is a natural number selected from 4 to 10;

[0014] And / or, n is a natural number selected from l to 10.

[0015] Secondly, the present invention provides a method for preparing long-chain branched poly(4-methyl-1-pentene), the method comprising: reacting raw materials including α,ω-nonconjugated diene and organosiloxane monomer to obtain a comonomer; and polymerizing the comonomer with 4-methyl-1-pentene to obtain long-chain branched poly(4-methyl-1-pentene).

[0016] In this invention, a siloxane monomer with a carbon-carbon double bond structure at both ends is first prepared as a comonomer through a hydrosilylation reaction between a diene and a siloxane. Then, it is polymerized with 4-methyl-1-pentene to obtain long-chain branched poly4-methyl-1-pentene.

[0017] In some embodiments, the raw materials further include solvent a and catalyst a;

[0018] Preferably, solvent a is selected from at least one of alkanes, cycloalkanes, and aromatic alkanes having 6-10 carbon atoms; further, the alkanes include straight-chain alkanes and branched-chain alkanes;

[0019] More preferably, solvent a is selected from at least one of n-hexane, cyclohexane, n-heptane, benzene, toluene, and xylene.

[0020] And / or, preferably, the catalyst a is selected from at least one of platinum, rhodium, palladium and nickel compounds commonly used in hydrosilylation reactions;

[0021] More preferably, the catalyst a is selected from at least one of the Karstedt catalyst and the Speier catalyst.

[0022] In some implementation schemes, the polymerization reaction system also includes solvent b and catalyst b;

[0023] Preferably, the solvent b is selected from at least one of alkanes, cycloalkanes, and aromatic alkanes having 4-10 carbon atoms; further, the alkanes include straight-chain alkanes and long-chain alkanes;

[0024] More preferably, the solvent b is selected from at least one of n-hexane, n-heptane, n-octane, cyclohexane, toluene, and xylene;

[0025] Preferably, catalyst b includes a main catalyst and a co-catalyst;

[0026] The main catalyst includes at least one of metallocene catalyst, Ziegler-Natta catalyst, post-metallocene catalyst, supported metallocene catalyst, and supported post-metallocene catalyst.

[0027] The cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, methylaluminoxane compound, modified methylaluminoxane compound, tri(pentafluorophenyl)boron compound, triphenylcarbium tetra(pentafluorophenyl)boron compound, and N,N-dimethylaniline tetra(pentafluorophenyl)boron compound.

[0028] In some preferred embodiments, the organosiloxane monomer comprises a linear organosiloxane having silane-hydrogen bonds at both ends;

[0029] And / or, the α,ω-nonconjugated diene includes at least one of 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene;

[0030] And / or, the molar ratio of the α,ω-nonconjugated diene to the organosiloxane monomer is 3-10:1;

[0031] And / or, the molar ratio of the 4-methyl-1-pentene to the comonomer is 100-500:1.

[0032] To prevent the two raw materials from reacting excessively to form oligomers and to ensure that the product has a structure with two terminal double bonds, it is necessary to limit the molar ratio of α,ω-nonconjugated diene to organosiloxane monomer.

[0033] In some preferred embodiments, the comonomer structure is as shown in the following formula:

[0034]

[0035] Where R is selected from C1-C6 alkyl groups, m is selected from natural numbers from 2 to 10, and n is selected from natural numbers from 0 to 10.

[0036] In some preferred embodiments, R is selected from C1-C8 alkyl groups, m is selected from natural numbers from 4 to 10, and n is selected from natural numbers from 0 to 50.

[0037] In some preferred embodiments, the reaction conditions for obtaining the comonomer include: a reaction temperature of 0-100°C and a reaction time of 6-18 hours;

[0038] Preferably, the reaction temperature is 20-80℃; the reaction time is 8-16h;

[0039] And / or, the conditions for the polymerization reaction include: a reaction temperature of 0-80℃; and a reaction time of 0.5-5h.

[0040] Thirdly, the present invention provides the application of the above-mentioned long-chain branched poly4-methyl-1-pentene or the long-chain branched poly4-methyl-1-pentene prepared by the above method in the preparation of materials in the field of electronic packaging.

[0041] In some preferred embodiments, the application is in the preparation of medical materials and / or optical materials.

[0042] The beneficial effects of this invention are:

[0043] 1. The present invention provides a long-chain branched poly4-methyl-1-pentene, which has an H-type long-chain branched structure.

[0044] 2. The preparation method of the present invention is simple, the reaction is mild, the comonomer conversion rate is high, no complicated pretreatment or post-treatment process is required, and conventional Ziegler-Natta catalysts can meet the requirements, which has broad prospects for industrial production.

[0045] 3. The selected raw materials are all common industrial materials, and no special materials are required, so the cost is guaranteed and they are suitable for industrial applications. Attached Figure Description

[0046] Figure 1 The NMR spectrum of the comonomer prepared in Example 1;

[0047] Figure 2 The NMR spectrum of the long-chain branched poly(4-methyl-1-pentene) prepared in Example 1 is shown. Detailed Implementation

[0048] To further clarify the purpose, technical solution, and advantages of the present invention, the present invention will be further described in detail below with reference to specific embodiments, but this does not limit the scope of protection of the present invention.

[0049] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or a process variable such as temperature or time, is stated as 0-100, in this specification it means specifically listing values ​​such as 0-99, 1-98, ..., and 49-51. For non-integer values, it may be appropriate to consider a unit of 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0050] Example 1:

[0051] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0052] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 11.0 g of 1,7-octadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration 2%) were added sequentially. The temperature was controlled at 80 °C and the reaction was stirred for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was continued with stirring for 8 h. The catalyst was removed by silica gel adsorption, followed by vacuum distillation to obtain 6.5 g of a colorless oily liquid product, with a yield of 92%. NMR analysis of the product is shown below. Figure 1 As can be seen, 1,7-octadiene undergoes a hydrosilylation reaction with tetramethyldihydrodisiloxane, and the product has a well-defined structure with two terminal carbon-carbon double bonds.

[0053] (2) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 20 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst, and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added sequentially. The reaction temperature was controlled at 40 °C. After reacting for 180 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, thoroughly stirred, washed, filtered, and vacuum dried at 80 °C for 12 h to obtain the polymerization product. The NMR analysis of the product is shown in [reference needed]. Figure 2 This shows that the comonomer with two terminal carbon-carbon double bonds successfully polymerized with 4-methyl-1-pentene, the positions of each characteristic peak were clear, and the product had an H-type long-chain branched structure.

[0054] Example 2:

[0055] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0056] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 8.2 g of 1,5-hexadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration of 2%) were added sequentially, and the reaction was stirred at 50 °C for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was stirred for another 8 h. The catalyst was removed by silica gel adsorption, and the product was then distilled under reduced pressure to obtain 5.6 g of a colorless oily liquid product, with a yield of 93%.

[0057] (2) A 50 mL reactor with a magnetic stirrer was evacuated and purged with nitrogen three times to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 14 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added in sequence. The reaction temperature was controlled at 40 °C. After reacting for 180 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, stirred and washed thoroughly, filtered, and dried under vacuum at 80 °C for 12 h to obtain the polymer product.

[0058] Example 3:

[0059] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0060] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 11.0 g of 1,7-octadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration of 2%) were added sequentially, and the reaction was carried out at 80 °C with stirring for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was continued with stirring for 8 h. The catalyst was removed by silica gel adsorption, and the product was then distilled under reduced pressure to obtain 6.5 g of colorless oily liquid product, with a yield of 92%.

[0061] (2) A 50 mL reactor with a magnetic stirrer was evacuated and purged with nitrogen three times to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 40 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added in sequence. The reaction temperature was controlled at 40 °C. After reacting for 180 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, stirred and washed thoroughly, filtered, and dried under vacuum at 80 °C for 12 h to obtain the polymer product.

[0062] Example 4:

[0063] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0064] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 11.0 g of 1,7-octadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration of 2%) were added sequentially, and the reaction was stirred at 80 °C for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was stirred for another 8 h. The catalyst was removed by silica gel adsorption, and the product was then distilled under reduced pressure to obtain 6.5 g of a colorless oily liquid product, with a yield of 92%.

[0065] (2) A 50 mL reactor with a magnetic stirrer was evacuated and purged with nitrogen three times to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 80 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added in sequence. The reaction temperature was controlled at 40 °C. After reacting for 180 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, stirred and washed thoroughly, filtered, and dried under vacuum at 80 °C for 12 h to obtain the polymer product.

[0066] Example 5:

[0067] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0068] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 11.0 g of 1,7-octadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration of 2%) were added sequentially, and the reaction was stirred at 80 °C for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was stirred for another 8 h. The catalyst was removed by silica gel adsorption, and the product was then distilled under reduced pressure to obtain 6.5 g of a colorless oily liquid product, with a yield of 92%.

[0069] (2) A 50 mL reactor with a magnetic stirrer was evacuated and purged with nitrogen three times to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 20 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added in sequence. The reaction temperature was controlled at 50 °C. After reacting for 180 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, stirred and washed thoroughly, filtered, and dried under vacuum at 80 °C for 12 h to obtain the polymer product.

[0070] Example 6:

[0071] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0072] (1) A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 25 mL of toluene, 11.0 g of 1,7-octadiene, and 50 ppm of Karstedt catalyst solution (platinum concentration of 2%) were added sequentially, and the reaction was stirred at 80 °C for 1 h. Subsequently, 2.7 g of tetramethyldihydrodisiloxane was added dropwise, and the reaction was stirred for another 8 h. The catalyst was removed by silica gel adsorption, and the product was then distilled under reduced pressure to obtain 6.5 g of a colorless oily liquid product, with a yield of 92%.

[0073] (2) A 50 mL reactor with a magnetic stirrer was evacuated and purged with nitrogen three times to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 20 mg of the product from step (1), 0.3 mL of triethylaluminum co-catalyst and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added in sequence. The reaction temperature was controlled at 40 °C. After reacting for 120 min, anhydrous ethanol was added to terminate the reaction. The product was then transferred to a beaker containing 50 mL of tetrahydrofuran, stirred and washed thoroughly, filtered, and dried under vacuum at 80 °C for 12 h to obtain the polymer product.

[0074] Comparative Example 1:

[0075] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0076] A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 0.3 mL of triethylaluminum co-catalyst, and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added sequentially. The reaction temperature was controlled at 40 °C. After reacting for 120 min, anhydrous ethanol was added to terminate the reaction. The mixture was then transferred to a beaker containing 50 mL of tetrahydrofuran, thoroughly stirred, washed, and filtered. After vacuum drying at 80 °C for 12 h, the polymerization product was obtained.

[0077] Comparative Example 2:

[0078] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0079] A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 11 mg of tetramethyldivinyldisiloxane, 0.3 mL of triethylaluminum co-catalyst, and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added sequentially. The reaction temperature was controlled at 40 °C. After reacting for 120 min, anhydrous ethanol was added to terminate the reaction. The mixture was then transferred to a beaker containing 50 mL of tetrahydrofuran, thoroughly stirred, washed, filtered, and vacuum dried at 80 °C for 12 h to obtain the polymerization product.

[0080] Comparative Example 3:

[0081] A method for preparing long-chain branched poly(4-methyl-1-pentene) includes the following steps:

[0082] A 50 mL reactor with a magnetic stirrer was subjected to three evacuation-nitrogen purging operations to fill it with an inert atmosphere. Then, 15 mL of n-heptane, 2.0 g of 4-methyl-1-pentene, 6 mg of 1,7-octadiene, 0.3 mL of triethylaluminum co-catalyst, and 6 mg of Ziegler-Natta main catalyst (Al / Ti = 100) were added sequentially. The reaction temperature was controlled at 40 °C. After reacting for 120 min, anhydrous ethanol was added to terminate the reaction. The mixture was then transferred to a beaker containing 50 mL of tetrahydrofuran, thoroughly stirred, washed, filtered, and vacuum dried at 80 °C for 12 h to obtain the polymerization product.

[0083] The polymerization experimental results of Examples 1-6 and Comparative Examples 1-3 are shown in the table.

[0084] Test case

[0085] The properties of the polymer products prepared in Examples 1-6 and Comparative Examples 1-3 were tested, and the results are shown in Table 1.

[0086] The polymerization activity of the polymer is the ratio of the product mass to the catalyst mass (calculated based on the mass of Ti in the catalyst).

[0087] The comonomer content in the polymerization product was determined by high-temperature NMR spectroscopy.

[0088] The tensile strength and impact strength of the polymer products were measured in accordance with national standards.

[0089] Table 1. Properties of the polymer products prepared in Examples 1-6 and Comparative Examples 1-3

[0090]

[0091]

[0092] The results in the table lead to the following conclusions: When the comonomer content is low, the polymer crystallizes well, resulting in a harder and more brittle material with slightly lower impact strength. As the comonomer content increases, the polymer crystallization is gradually disrupted, and the material's properties gradually shift towards softer and tougher materials. Therefore, increasing the comonomer content increases the impact strength. Thus, the comonomer content in this application is adjustable, making it suitable for a wider range of applications.

[0093] In addition, the polymerization activity remained at a high level throughout the preparation process of this impact-resistant poly(4-methyl-1-pentene) polymer.

[0094] By comparing Example 1 with Comparative Example 1, the product of Example 1 exhibits excellent impact strength. This is because the insertion of the comonomer introduces a long-chain branched structure into the polymer, which has both rigid long carbon chains and soft siloxane segments. This unique structure, which combines rigidity and flexibility, endows it with excellent impact resistance.

[0095] Comparing Example 1 and Comparative Example 2, the product of Example 1 exhibited excellent impact strength, while the product of Comparative Example 2 performed poorly. This is because the comonomer used in Example 1 lacked a long carbon chain structure, relying solely on siloxane segments to form a cross-linked structure. This structure cannot effectively form long-chain branching. More importantly, this comonomer structure exhibited poor polymerization ability, significant loss of polymerization activity, and a very low comonomer insertion rate.

[0096] Comparing Example 1 and Comparative Example 3, the impact strength of the product in Comparative Example 3 showed only a slight improvement. The difference lies in the fact that the comonomer is 1,7-octadiene, which lacks siloxane segments. This demonstrates the crucial role of flexible siloxane segments in improving impact resistance.

[0097] The above embodiments and application examples are intended to help understand the method and key points of the present invention. This specification should not be construed as limiting the invention.

Claims

1. A long-chain branched poly(4-methyl-1-pentene), characterized in that, The structural formula of the long-chain branched poly(4-methyl-1-pentene) is shown in Formula I: In the formula, R is selected from C1-C8 alkyl groups, m is selected from natural numbers from 2 to 10, and n is selected from natural numbers from 0 to 50.

2. The long-chain branched poly-4-methyl-1-pentene according to claim 1, characterized in that, R is selected from C1-C6 alkyl groups; And / or, m is a natural number selected from 4 to 10; And / or, n is a natural number selected from 1 to 10.

3. The method for preparing long-chain branched poly(4-methyl-1-pentene) according to claim 1 or 2, characterized in that, The preparation method includes: reacting raw materials including α,ω-nonconjugated dienes and organosiloxane monomers to obtain a comonomer; and polymerizing the comonomer with 4-methyl-1-pentene to obtain long-chain branched poly4-methyl-1-pentene.

4. The preparation method according to claim 3, characterized in that, The raw materials also include solvent a and catalyst a; Preferably, solvent a is selected from at least one of alkanes, cycloalkanes, and aromatic alkanes having 6-10 carbon atoms; More preferably, solvent a is selected from at least one of n-hexane, cyclohexane, n-heptane, benzene, toluene, and xylene; Preferably, the catalyst a is selected from at least one compound of platinum, rhodium, palladium, and nickel; More preferably, the catalyst a is selected from at least one of the Karstedt catalyst and the Speier catalyst.

5. The preparation method according to claim 3 or 4, characterized in that, The polymerization reaction system also includes solvent b and catalyst b; Preferably, the solvent b is selected from at least one of alkanes, cycloalkanes, and aromatic alkanes having 4-10 carbon atoms; More preferably, the solvent b is selected from at least one of n-hexane, n-heptane, n-octane, cyclohexane, toluene, and xylene; Preferably, catalyst b includes a main catalyst and a co-catalyst; The main catalyst includes at least one of metallocene catalyst, Ziegler-Natta catalyst, post-metallocene catalyst, supported metallocene catalyst, and supported post-metallocene catalyst. The cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, methylaluminoxane compound, modified methylaluminoxane compound, tri(pentafluorophenyl)boron compound, triphenylcarbium tetra(pentafluorophenyl)boron compound, and N,N-dimethylaniline tetra(pentafluorophenyl)boron compound.

6. The preparation method according to any one of claims 3-5, characterized in that, The organosiloxane monomers include linear organosiloxanes with silane-hydrogen bonds at both ends; And / or, the α,ω-nonconjugated diene includes at least one of 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene; And / or, the molar ratio of the α,ω-nonconjugated diene to the organosiloxane monomer is 3-10:1; And / or, the molar ratio of the 4-methyl-1-pentene to the comonomer is 100-500:

1.

7. The preparation method according to any one of claims 3-6, characterized in that, The structure of the comonomer is shown in Formula II: In formula II, R is selected from C1-C6 alkyl groups, m is selected from natural numbers from 2 to 10, and n is selected from natural numbers from 0 to 10.

8. The preparation method according to claim 7, characterized in that, R is selected from C1-C8 alkyl groups, m is selected from natural numbers from 4 to 10, and n is selected from natural numbers from 0 to 50.

9. The preparation method according to any one of claims 3-8, characterized in that, The reaction conditions for obtaining the comonomer include: a reaction temperature of 0-100℃; a reaction time of 6-18h; preferably, a reaction temperature of 20-80℃; and a reaction time of 8-16h. And / or, the conditions for the polymerization reaction include: a reaction temperature of 0-80℃; and a reaction time of 0.5-5h.

10. A material prepared using long-chain branched poly(4-methyl-1-pentene) according to claim 1 or 2, or long-chain branched poly(4-methyl-1-pentene) prepared by any one of claims 3-9, characterized in that, Preferably, the material includes at least one of electronic packaging materials, medical materials, and optical materials.

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