Method for producing polyolefins

Abstract

The present invention provides a method for producing polyolefins. In this production method, a cycloolefin monomer is used as the gas phase, a catalyst as the solid phase, the catalyst is supported on a substrate, and the cycloolefin monomer is subjected to a gas-to-solid-phase polymerization reaction with the catalyst to obtain a polyolefin, with the amount of catalyst supported on the substrate being 0.1 to 1000 ppm. The method of the present invention overcomes the complicated operations of the prior art and can produce polyolefin products having ultra-high molecular weight and a narrow molecular weight distribution.

Description

Technical Field

[0001] Cross reference information This application claims the priority of a Chinese patent application filed with the China National Intellectual Property Administration on December 28, 2023, with an application number of 202311837594.7 and an invention title of "Method for Producing Polyolefin", and all its contents are incorporated herein by reference. Technical field The present invention belongs to the technical field of organic synthesis, and specifically relates to a method for producing polyolefin.

Background Art

[0002] Background technology Ring-opening metathesis polymerization (ROMP) is a living polymerization reaction that is widely applied in the synthesis of polyolefin materials. The polymerization reaction is often carried out in solution and is affected by chain transfer side reactions, and the maximum molecular weight that the obtained product can reach is limited. When the polymerization reaction is carried out in the gas phase, the movement of polymer chains is restricted, chain transfer side reactions are suppressed, and products with higher molecular weights can be obtained. By supporting a catalyst on a solid substrate and polymerizing a gaseous cycloolefin monomer, polycyclopentene having a number average molecular weight exceeding 1 million, which is more than three times the upper limit of the molecular weight by conventional solution polymerization, and maintaining a polydispersity coefficient of less than 1.5 can be obtained. By hydrogenating this, ultra-high molecular weight and unbranched polyethylene can be obtained. Such a polymerization method can be applied to many monomers that are often used in ring-opening metathesis polymerization reactions such as cyclopentene, cyclohexadiene, cycloheptene, norbornene, cyclooctene, 1,5-cyclooctadiene, cyclooctatetraene, 1,5,9-cyclododecatriene, etc. Also, in the reaction process, the use of a solvent is avoided, thereby reducing production costs and environmental pollution.

[0003] In conventional techniques, the amount of product obtained is insufficient for detecting molecular weight, and therefore, all methods are inadequate for characterizing the molecular weight or polydispersity coefficient of the product. [Overview of the Initiative] [Means for solving the problem]

[0004] Summary of the Invention To solve the above problems, the present invention provides a method for producing polyolefins. The method of the present invention overcomes the complicated operations of the prior art and allows for the production of polyolefin products having ultra-high molecular weight and a narrow molecular weight distribution by supporting a catalyst on a substrate in a reaction vessel and carrying out a gas-phase-solid-phase polymerization reaction.

[0005] The present invention involves using a cycloolefin monomer as the gas phase and a catalyst as the solid phase, with the catalyst supported on a substrate. The cycloolefin monomer is subjected to a gas-to-solid-phase polymerization reaction using the catalyst to obtain the polyolefin. The present invention provides a method for producing polyolefins, wherein the amount of catalyst supported on the substrate is 0.1 to 1000 ppm, preferably 0.5 to 1000 ppm, and more preferably 0.5 to 50 ppm.

[0006] By adding purified cycloolefin monomers that do not directly contact the substrate, the monomers volatilize into the gas phase and come into contact with the solid-phase catalyst, a gas-solid polymerization reaction occurs, yielding polyolefin products with ultra-high molecular weight and a narrow molecular weight distribution. The molecular weight of the product can be controlled by controlling the amount of catalyst supported. By employing an efficient ROMP catalyst, a reaction with the characteristics of living polymerization is enabled, and because the polymerization reaction occurs at the gas-solid interface, the content of non-cycloolefin impurities decreases after monomer purification, reducing chain transfer side reactions in the polymerization process, and ultimately yielding a polymerization product with a narrow molecular weight distribution.

[0007] After the reaction is complete, the product is obtained by peeling it off the substrate. In actual manufacturing, cycloolefin raw materials may contain linear olefin impurities. These impurities act as chain transfer agents, causing a decrease in the molecular weight and broadening of the molecular weight distribution of the product during polymerization. Therefore, it is very important to purify the monomers and remove the linear olefins. Methods for purifying monomers include rectification, hydroboration, or a combination of both. In hydroboration, a borane molecule is added to the monomer. Borane and linear olefins are highly reactive, and the hydroboration product obtained after the reaction has a high boiling point, is not highly volatile, and has no reactive activity, thus not affecting the polymerization process. The borane molecule is shown in formula 6, where R1 and R2 are the same or different C1-C20 hydrocarbon groups. R1 and R2 may be linked to form a monocyclic or polycyclic group. A preferred borane is 9-borabicyclo[3.3.1]nonane (9-BBN). The amount of borane added depends on the amount of linear olefin impurities in the monomer, but it is preferably 5 to 20 times the molar amount of the impurities. In the present invention, it is preferable to first purify the monomer by rectification, and then further reduce the impurity content by hydroboration.

[0008] [ka]

[0009] In a preferred embodiment of the present invention, the method for supporting the catalyst is as follows: The process includes preparing a catalyst solution by combining the catalyst and an organic solvent, distributing the catalyst solution onto the substrate, and then removing the organic solvent.

[0010] In a preferred embodiment of the present invention, the organic solvent is one or more combinations of linear aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and aromatic hydrocarbons. More preferably, the organic solvent is an aromatic hydrocarbon.

[0011] In a preferred embodiment of the present invention, the concentration of the catalyst solution is 1 to 2000 μmol / L. More preferably, the concentration of the catalyst solution is 5 to 600 μmol / L.

[0012] In a preferred embodiment of the present invention, the catalyst comprises one or more combinations of ruthenium-based ROMP catalysts, tungsten-based ROMP catalysts, molybdenum-based ROMP catalysts, and rhenium-based ROMP catalysts. More preferably, the catalyst is a Grubbs 1st generation catalyst and / or a Grubbs 2nd generation catalyst.

[0013] In a preferred embodiment of the present invention, the substrate includes one of glass, silicon wafer, paper, aluminum foil, stainless steel, and plastic. Preferably, the substrate is placed at the bottom of the reactor.

[0014] More preferably, the substrate is glass or paper. In a preferred embodiment of the present invention, the reaction temperature of the gas-solid-phase polymerization reaction is -80 to 200°C, and the reaction time is 30 min to 12 h. More preferably, the reaction temperature is 0°C to 30°C, and the reaction time is 1 h to 6 h.

[0015] The lower the reaction temperature, the higher the molecular weight of the polymer. In actual operation, the reaction temperature is preferably supplied from outside the reactor by a liquid medium.

[0016] By adjusting the reaction temperature, the molecular weight of the product obtained by the manufacturing method of the present invention can be controlled.

[0017] In a preferred embodiment of the present invention, the cycloolefin monomer comprises one or more combinations of cycloolefins represented by formulas 1, 2, 3, 4, and 5.

[0018] [ka]

[0019] In Equation 1, n is 1, 3, 4, or 8. In a preferred embodiment of the present invention, the method for removing the organic solvent includes drying the organic solvent with an inert gas.

[0020] Preferably, the temperature of the inert gas is 0 to 50°C. More preferably, the temperature of the inert gas is 20 to 30°C.

[0021] Preferably, the inert gas is selected from nitrogen gas and / or argon gas. In some embodiments of the present invention, the method for supporting the catalyst includes a spin coating method.

[0022] The present invention also provides two types of reactors suitable for the production method of the present invention. The structural schematic diagram of reactor A is shown in FIG. 1, and the structural schematic diagram of reactor B is shown in FIG. 2.

[0023] In reactor A, the outer bottle 5 is provided with a pad 1 at the top and is fixedly sealed by a lid 2 with a hole in the central part. The inner bottle 4 is suspended in the outer bottle 5 by tying the top with an iron wire 3 and then passing the iron wire 3 through the pad 1 for fixation.

[0024] In reactor B, the outer bottle 5 is provided with a pad 1 at the top and is hermetically fixed by a lid 2 with a hole in the central part. A hole is made in the substrate 7 to pass the iron wire 3, and further the iron wire 3 is passed through the pad 1 for fixation, so that the substrate 7 is suspended in the outer bottle 5. The paper 6 adheres to the inner wall of the outer bottle 5 and contacts the bottom, and when impregnated with the monomer liquid, it speeds up the evaporation rate.

[0025] The main materials of reactors A and B are glass. The above reactors A and reactor B are merely examples and are not intended to further limit the production method of the present invention.

[0026] The manufacturing method of the present invention can yield ultra-high molecular weight polyolefins. If a product with a lower molecular weight is desired, a certain amount of linear olefin can be added to the reaction monomer. The structural formula of the linear olefin is shown in formula 7, where R3 and R4 are the same or different C1-C10 hydrocarbon groups or hydrogen. Those skilled in the art can select specific linear olefins and determine their addition amounts based on common knowledge of the art and a finite number of experiments.

[0027] [ka]

[0028] Compared to the prior art, the present invention has the advantageous effect of being relatively easy to operate in the manufacturing process and being able to obtain polyolefin products having ultra-high molecular weight and a narrow molecular weight distribution in high yield. [Brief explanation of the drawing]

[0029] [Figure 1] A schematic diagram of reactor A is shown. [Figure 2] A schematic diagram of reactor B is shown. [Figure 3] The carbon spectrum of the product obtained in Synthesis Example 1, measured by solid-state nuclear magnetic resonance, is shown. [Modes for carrying out the invention]

[0030] The symbols in the diagram are as follows: 1-Pad, 2-Lid, 3-Wire, 4-Inner bottle, 5-Outer bottle, 6-Paper, 7-Circuit board. Modes for carrying out the invention The following describes in detail the proposed technical features, objectives, and beneficial effects of the present invention in order to provide a clearer understanding of them, but this should not be understood as limiting the scope of the invention's applicability.

[0031] In the following examples, the number-average molecular weight, weight-average molecular weight, and molecular weight distribution coefficient are measured by size exclusion gel chromatography. The apparatus consists of an Agilent 1260 liquid pump, two Agilent PLgel MIXED-B 300×7.5 mm chromatography columns connected in series, a Wyatt DAWN HELEOS 18-angle light scattering detector, and a Wyatt Optilab rEX differential refractive detector. Tetrahydrofuran is used as the solvent and mobile phase, with a concentration of 1 g / L and a flow rate of 1 mL / min.

[0032] In the following examples and comparative examples, reactor A has the structure shown in Figure 1, and reactor B has the structure shown in Figure 2.

[0033] In reactor A, the outer bottle 5 is secured and sealed by a lid 2 with a pad 1 on top and a hole in the center. The inner bottle 4 is suspended inside the outer bottle 5 by tying its top with an iron wire 3 and then passing the iron wire 3 through the pad 1 to secure it.

[0034] In reactor B, the outer bottle 5 is sealed and secured by a lid 2 with a pad 1 at its top and a hole in the center. The substrate 7 is suspended inside the outer bottle 5 by making a hole in the substrate 7, passing an iron wire 3 through it, and then passing the iron wire 3 through the pad 1 to secure it. The paper 6 is in close contact with the inner wall of the outer bottle 5 and also in contact with the bottom. [Examples]

[0035] Example 1 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0036] Example 2 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 50 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0037] Example 3 In this example, reactor A was used. 0.92 mg of Grubbs 1st catalyst was weighed and dissolved in 200 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0038] Example 4 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 30°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 30°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 30°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0039] Example 5 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 50 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 30°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 30°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 30°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0040] Example 6 In this example, reactor A was used. 0.92 mg of Grubbs 1st catalyst was weighed and dissolved in 200 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 30°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 30°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 30°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0041] Example 7 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an ice bath at 0°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an ice bath at 0°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an ice bath at 0°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0042] Example 8 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 50 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an ice bath at 0°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an ice bath at 0°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an ice bath at 0°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0043] Example 9 In this example, reactor A was used. 0.92 mg of Grubbs 1st catalyst was weighed and dissolved in 200 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an ice bath at 0°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an ice bath at 0°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an ice bath at 0°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0044] Example 10 In this example, reactor A was used. 2.4 mg of Grubbs 2nd catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0045] Example 11 In this example, reactor A was used. 2.4 mg of Grubbs 2nd catalyst was weighed and dissolved in 50 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0046] Example 12 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 30°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cycloheptene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 30°C for 30 minutes, and 2.6 mL was taken with a syringe and added to the bottom of inner bottle 4. The reactor was placed in an oil bath at 30°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0047] Example 13 In this example, reactor B was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and placed in a glass dish. Paper 6 was immersed in the catalyst solution, and all of the solution was absorbed into the paper 6. The material of paper 6 was filter paper. After purging the filter paper with argon gas for 30 minutes until the solvent had completely evaporated, paper 6 was fixed to a silicone pad 1 with iron wire 3 and suspended in an outer bottle 5. 50 mL of distilled and purified cycloheptene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in a 30°C oil bath for 30 minutes, and 2.6 mL was taken with a syringe and added to the bottom of the outer bottle 5. The reactor was placed in a 30°C oil bath and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0048] Example 14 In this example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of unpurified cyclopentene was placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of inner bottle 5. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0049] Comparative Example 1 In this comparative example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 5 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of outer bottle 5. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0050] Comparative Example 2 In this comparative example, reactor A was used. 2.3 mg of Grubbs 1st catalyst was weighed and dissolved in 50 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of outer bottle 5. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0051] Comparative Example 3 In this comparative example, reactor A was used. 0.92 mg of Grubbs 1st catalyst was weighed and dissolved in 200 mL of toluene to obtain a catalyst solution. 2 mL of the catalyst solution was taken with a syringe and added to the bottom of outer bottle 5, and the reactor was placed in an oil bath at 20°C. The reactor was purged with argon gas for 30 minutes until the solvent had completely evaporated. 50 mL of distilled and purified cyclopentene and 50 mg of 9-BBN were mixed and stirred in a sealed glass bottle for 12 hours. The glass bottle was then placed in an oil bath at 20°C for 30 minutes, and 2 mL was taken with a syringe and added to the bottom of outer bottle 5. The reactor was placed in an oil bath at 20°C and reacted for 6 hours to obtain the polymer. The properties and yield of the polymer are shown in Table 1.

[0052] The results from the examples and comparative examples show that the molecular weight of polymers obtained by gas-solid-phase polymerization is higher than that obtained by solution polymerization. The lower the reaction temperature, the higher the molecular weight of the polymer. Due to limitations of the analytical equipment, only polymer samples soluble at room temperature could be measured, but since some polymers may be partially insoluble at room temperature, it is presumed that the actual polymer molecular weight is higher than the measured result.

[0053] Synthesis Example 1 In Example 7, 1 g of the polymer was added to a 100 mL round-bottom flask, 5 mg of 2,6-di-tert-butyl-4-methylphenol and 70 mL of xylene were added, and the mixture was heated under reflux at 140°C until the polymer dissolved. Then, 12.5 mL of tributylamine and 9 g of p-toluenesulfonyl hydrazide were added, and the mixture was stirred for 12 hours. The hot solution was poured into 500 mL of cold methanol to allow sedimentation, and the resulting solid was vacuum-dried to obtain 1.03 g of a white solid. As shown in Figure 3, the carbon spectrum CP / MAS was obtained by solid-state nuclear magnetic resonance. 13 When measured by 13C NMR, the obtained product showed a peak only at 35 ppm, with no peaks in the 100-150 ppm range. This indicates that the double bonds in the starting material were completely hydrogenated, resulting in unbranched polyethylene as the product.

[0054] [Table 1]

[0055] As can be seen from Table 1, according to the technical proposal of the present invention, it is possible to obtain polyolefin products having an ultra-high molecular weight and a narrow molecular weight distribution.

Claims

1. A cycloolefin monomer is used as the gas phase, a catalyst as the solid phase, and the catalyst is supported on a substrate. The cycloolefin monomer is subjected to a gas-to-solid-phase polymerization reaction using the catalyst to obtain the polyolefin. A method for producing polyolefins, characterized in that the amount of catalyst supported on the substrate is 0.1 to 1000 ppm.

2. The manufacturing method according to claim 1, wherein the amount of catalyst supported on the substrate is 0.5 to 1000 ppm.

3. The manufacturing method according to claim 1, wherein the catalyst and an organic solvent are prepared as a catalyst solution, the catalyst solution is distributed on the substrate, and then the organic solvent is removed to support the catalyst.

4. The production method according to claim 3, wherein the organic solvent is one or a combination of two or more linear aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and aromatic hydrocarbons.

5. The manufacturing method according to claim 3, wherein the concentration of the catalyst solution is 1 to 2000 μmol / L.

6. The manufacturing method according to claim 1, wherein the catalyst comprises one or more combinations of a ruthenium-based ROMP catalyst, a tungsten-based ROMP catalyst, a molybdenum-based ROMP catalyst, and a rhenium-based ROMP catalyst.

7. The manufacturing method according to claim 1, wherein the substrate includes one of glass, silicon wafer, paper, aluminum foil, stainless steel, and plastic.

8. The manufacturing method according to claim 1 or 7, wherein the substrate is placed at the bottom of the reactor.

9. The manufacturing method according to claim 1, wherein the reaction temperature of the gas-phase-solid-phase polymerization reaction is -80 to 200°C and the reaction time is 30 min to 12 h.

10. The production method according to claim 1, wherein the cycloolefin monomer comprises one or a combination of two or more cycloolefins represented by formulas 1, 2, 3, 4, and 5. 【Chemistry 1】 n is 1, 3, 4, or 8.

11. The manufacturing method according to claim 3, wherein the organic solvent is removed by drying the organic solvent with an inert gas.

12. The manufacturing method according to claim 11, wherein the temperature of the inert gas is 0 to 50°C.

13. The production method according to claim 1, further comprising purifying the cycloolefin monomer before the gas-phase-solid-phase polymerization reaction.

14. The manufacturing method according to claim 13, wherein the cycloolefin monomer is purified by rectification and / or hydroboration.

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