Trans-polycyclopentene rubber and continuous solution polymerization process thereof

Abstract

The present application relates to a kind of trans polycyclopentene rubber, it is characterized in that, the trans structure content is 70%~95%, number average molecular weight is 30000~1200000, molecular weight distribution is 1.2~3.5, gel content is less than 3.0% mass.The present application also discloses a kind of trans polycyclopentene rubber continuous solution polymerization method.The implementation of the present application not only can realize the continuous production of trans polycyclopentene rubber, but also can realize the efficient, sufficient mixing of various materials in reaction process, greatly improve catalyst activity, polymerization conversion rate and reaction efficiency, and the structure of polymer is stably controlled.

Description

Technical Field

[0001] This invention relates to a trans-polycyclopentene rubber and a continuous solution polymerization method thereof. Background Technology

[0002] Trans-polycyclopentene rubber is produced by ring-opening polymerization of cyclopentene as a monomer under the action of Ziegler-Natta catalyst. It has a low glass transition temperature, high raw rubber strength, no cold flow, excellent processing performance, crystallization after stretching, excellent resilience and wear resistance of vulcanized rubber, low heat generation, and low rolling resistance, making it very suitable for making heavy-duty vehicle tires and green energy-saving tires.

[0003] Cyclopentene can be obtained from the C5 fraction, a byproduct of ethylene production from cracked petroleum. Early development of trans-cyclopentene rubber was significantly limited by the shortage of the monomer cyclopentene. In recent years, with the abundance of C5 resources, the effective utilization of C5, including cyclopentadiene and cyclopentene, has attracted widespread attention. In 2020, China's domestic cracked C5 resources will reach over 3 million tons, of which cyclopentadiene will amount to 350,000-460,000 tons and cyclopentene to 70,000 tons. Cyclopentene sources include direct separation from C5 or hydrogenation of cyclopentadiene. Cyclopentadiene is abundant, and the selectivity for hydrogenation to cyclopentene can reach 90-95%, with a relatively short process flow, mild process conditions, and mature technology, thus solving the monomer source problem for cyclopentene rubber.

[0004] Early cyclopentene polymerization employed a WCl6-R3Al binary catalytic system, but the polymerization reproducibility was poor. Later, a ternary catalytic system was adopted, with phenols, alcohols, and peroxides being better activators. When the trans-structure content in trans-polycyclopentene rubber is too low, the rubber does not easily crystallize during stretching, resulting in lower strength. Conversely, when the trans-structure content is too high, the crystallization rate is too fast during stretching. A trans-structure content between 80% and 95% exhibits better overall performance, with a crystallization rate close to that of natural rubber and properties similar to natural rubber (NR). Currently, trans-polycyclopentene rubber polymerization primarily employs batch polymerization processes, which suffer from low reaction efficiency, high energy consumption, and unstable process control, leading to unstable product performance and low reaction efficiency. For example, CA843494, when using batch polymerization, exhibits low polymerization conversion and unstable product performance, failing to meet the requirements for industrial scale-up.

[0005] US Patent 4239874 from Goodyear Inc. discloses a process for preparing a copolymer rubber of cyclopentene and dicyclopentadiene. The catalysts used include (A) soluble tungsten halides or halide oxides, (B) organoaluminum compounds, (C) alcohols, and (D) polychlorinated phenols. The polymerization employs a single-stage continuous polymerization process. In the examples, the reactor used is a 1-gallon glass reactor with stirring and internal cooling. The reactor has a feed pipe and a discharge pipe. The feed pipe is connected to monomer and solvent storage tanks, a tungsten catalyst storage tank, and an organoaluminum storage tank, respectively. The discharge port has a regulating valve to adjust the discharge rate. The reaction process involves continuous feeding and discharging. The reaction temperature is 10-22°C, the reaction residence time is 47-69 minutes, the polymerization conversion rate is 53-66%, and the gel content is 1.4-64%. Although this process can effectively copolymerize cyclopentene and dicyclopentadiene, the reactor used is a small-scale conventional stirred reactor used in the laboratory. The reactor structure is not explained in detail, so it is not helpful for industrial scale-up. Moreover, the polymerization conversion rate is low (53-66%) and the gel content is high (1.4-64%).

[0006] Therefore, designing a novel reactor with practical value and proposing a completely new polymerization process is of great significance for improving catalyst activity and polymerization efficiency, stabilizing product structure and performance, and reducing reaction energy consumption. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a trans-polycyclopentene rubber and its continuous solution polymerization method. The implementation of this invention not only enables the continuous production of trans-polycyclopentene rubber, but also significantly improves catalyst activity, polymerization conversion rate, and polymerization reaction efficiency, stably controls the polymerization reaction temperature, stably controls the polymer structure, reduces energy and material consumption in the reaction process, and yields low-gel trans-polycyclopentene rubber.

[0008] To achieve the above objectives, the present invention provides a trans polycyclopentene rubber, wherein the trans structure content is 70% to 95%, the number average molecular weight is 30,000 to 1,200,000, the molecular weight distribution is 1.2 to 3.5, and the gel content is less than 3.0% by mass.

[0009] This invention also provides a method for continuous solution polymerization of trans-polycyclopentene rubber, the specific implementation of which is as follows:

[0010] (1) Under an inert atmosphere, the polymerization solvent, cyclopentene monomer, main catalyst solution, oxygen- or halogenated activator solution, or aged liquid of main catalyst solution and oxygen- or halogenated activator solution are continuously fed into the premix reactor. The premix reactor is a loop reactor equipped with a circulation pump and a cooling jacket. The circulation pump is used for premixing and circulating the material, and the cooling medium in the jacket is used for precooling the material in the premix reactor.

[0011] (2) Under an inert atmosphere, the premixed liquid, molecular weight regulator solution and organoaluminum compound solution from step (1) are continuously fed into the first polymerization reactor, wherein the first polymerization reactor is an adiabatic fully mixed reactor with stirring. In order to fully mix and disperse the molecular weight regulator solution and organoaluminum compound solution with the premixed liquid from step (1), the molecular weight regulator solution and aluminum compound solution are inserted into the vicinity of the bottom stirring paddle through two or more tubes.

[0012] (3) Under an inert atmosphere, the material from the first reactor in step (2) continuously enters from the bottom of the second reactor and subsequent reactors and flows out from the top, wherein the second reactor and subsequent polymerization reactors are adiabatic fully mixed flow reactors with stirring.

[0013] In the method of the present invention, the aging temperature of the main catalyst solution and the oxygen- or halogen-containing activator solution in step (1) is -20 to 80°C, and the aging reaction time is 5 to 180 min.

[0014] In the method of the present invention, the aspect ratio of the premixed loop reactor in step (1) is 5 to 150:1, preferably 10 to 100:1; the circulation ratio of the circulating pump is 2 to 80:1, preferably 5 to 30:1; the temperature of the circulating material is -50 to 40°C, preferably -30 to 20°C; the residence time of the material in the reactor is 3 to 60 min, preferably 5 to 30 min; and the system pressure is 0.01 to 1 MPa, preferably 0.05 to 0.5 MPa.

[0015] In the method of the present invention, the first reactor in step (2) has a height-to-diameter ratio of 2 to 30:1, preferably 5 to 20:1, the residence time of the material in the reactor is 10 to 240 min, preferably 30 to 120 min, the temperature of the circulating material is -50 to 50°C, preferably -10 to 20°C, and the system pressure is 0.01 to 1 MPa, preferably 0.05 to 0.5 MPa.

[0016] In the method of the present invention, the height-to-diameter ratio of the second reactor and the subsequent reactor in step (3) is 2 to 50:1, preferably 5 to 30:1, the residence time of the material in the reactor is 10 to 240 min, preferably 30 to 120 min, the temperature of the circulating material is -30 to 50°C, preferably -5 to 30°C, and the system pressure is 0.01 to 1 MPa, preferably 0.05 to 0.5 MPa.

[0017] In the method of the present invention, the stirring paddle in the upper layer of the first reactor and the stirring paddle in the second reactor can be any type of stirring paddle, and they can be the same or different.

[0018] In the method of the present invention, the main catalyst component is characterized in that, in step (1), the main catalyst component is selected from one or more of tungsten halides, tungsten oxyhalides, tungsten alkoxyhalides, molybdenum halides, molybdenum oxyhalides, and molybdenum alkoxyhalides; preferably, the main catalyst component is selected from one or more of WCl6, WBr6, WCl2, WBr2, WOCl4, WOBr4, MoCl5, and MoBr5;

[0019] In the method of the present invention, the oxygen- or halogen-containing activator in step (1) is selected from one or more of polyhalogenated phenols, benzoyl peroxide and epichlorohydrin; preferably, the polyhalogenated phenol is selected from one or more of trichlorophenol, tetrachlorophenol, pentachlorophenol, dichlorophenol, dibromophenol, tribromophenol, diiodophenol and triiodophenol.

[0020] In the method of the present invention, the molecular weight regulator is characterized in that, in step (2), the molecular weight regulator is selected from one or more linear monoolefins having 2 to 10 carbon atoms; preferably, the molecular weight regulator is selected from one or more of 1-butene, 2-butene, 1-hexene and 1-octene.

[0021] In the method of the present invention, the organoaluminum compound is characterized in that, in step (2), the organoaluminum compound is an alkylaluminum and / or an alkylaluminum halide; preferably, the alkylaluminum is selected from one or more of triisobutylaluminum and triethylaluminum; the alkylaluminum halide is selected from one or more of diethylaluminum chloride, dichloroethylaluminum, dibutylaluminum chloride, dichlorobutylaluminum, dibromodiethylaluminum, dibromoethylaluminum, dibromodibutylaluminum, and dibromobutylaluminum.

[0022] In the method of the present invention, the amount of the oxygen- or halogen-containing activator relative to 1 mole of the main catalyst component is 0.2 to 10 moles, preferably 0.5 to 3 moles; the amount of the molecular weight regulator is 0.1 to 10 moles, preferably 0.5 to 5 moles; and the amount of the organoaluminum is 0.2 to 10 moles, preferably 1 to 6 moles.

[0023] In the method of the present invention, in step (2), the amount of the main catalyst component is 1 × 10⁻⁶ per g of the polymerization monomer. -6 ~3×10 -5 mol, preferably 1.5 × 10⁻⁶ -6 ~1.0×10 -5 mol;

[0024] In the method of the present invention, in step (2), the concentration of the monomer in the reaction mixture is 10-70% by weight; preferably, the concentration of the monomer in the reaction mixture is 15-50% by weight.

[0025] In the method of the present invention, the main catalyst and activator solvent are selected from one or more of toluene, xylene and benzene; the polymerization solvent is selected from one or more of n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, xylene, benzene and toluene.

[0026] In the method of the present invention, the trans-polycyclopentene rubber has a trans structure content of 75% to 92%, a number average molecular weight of 50,000 to 600,000, a molecular weight distribution of 1.5 to 2.5, and a gel content of less than 2.0% by mass.

[0027] Beneficial effects of the present invention

[0028] The purpose of this invention is to overcome the shortcomings of existing technologies, such as low polymerization conversion rate, unstable polymerization temperature control, unstable product performance, and high energy consumption, and to provide a trans-polycyclopentene rubber and its continuous solution polymerization method. The implementation of this invention not only enables continuous production of trans-polycyclopentene rubber, but also achieves efficient and thorough mixing of various materials during the reaction process, greatly improving catalyst activity, polymerization conversion rate, and reaction efficiency, and stabilizing the polymer structure. By premixing and precooling the materials in the early stages and controlling the residence time of the materials in the reactor, the polymerization reaction temperature can be stably controlled. During the reaction, there is no need for temperature control of the reactor through jackets or cooling coils, thereby greatly reducing energy and material consumption in the reaction process, resulting in low-gel trans-polycyclopentene rubber suitable for industrial production, with significant economic value and practical importance.

[0029] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0030] Figure 1 Schematic diagram of the process for producing trans-polycyclopentene rubber. Detailed Implementation

[0031] The specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the invention. It should also be understood that the technical solutions described in this invention require implementation by those skilled in the art with prior knowledge of conventional technical operations.

[0032] The testing method involved in this invention is as follows:

[0033] 1. The microstructure of the polymer was determined using a commercially available Bruker AVANCE400 superconducting nuclear magnetic resonance spectrometer (NMR spectrometer). 1The determination was performed by ¹H-NMR using deuterated chloroform (CDCl₃) as the solvent at 25°C, and calibrated by TMS.

[0034] 2. The number-average molecular weight and molecular weight distribution index of the polymer were determined using a Shimadzu LC-10AVP gel permeation chromatography (GPC) system at 25°C, with tetrahydrofuran as the mobile phase and a flow rate of 1.0 ml / min.

[0035] 3. The glass transition temperature was determined using a TA Instruments MDSC2910 differential scanning calorimeter (DSC) with a modulation period of 60 seconds, a modulation amplitude of ±1.5℃, a heating rate of 10℃ / min, nitrogen protection, and a flow rate of 50mL / min.

[0036] 4. The polymerization conversion rate is calculated from the weight of the obtained polymer. The calculation formula is (W1-W2) / W1×100%, where W1 is the weight of the polymerized monomer and W2 is the weight of the obtained polymer.

[0037] 5. The method for testing the gel content is to place the polymer in a stainless steel mesh, immerse it in toluene for a certain period of time, and measure the percentage of the portion that is insoluble in toluene, which is the gel content.

[0038] Example 1

[0039] The continuous production method of trans-polycyclopentene rubber adopts Figure 1 The diagram shows the apparatus and process flow.

[0040] Under a nitrogen atmosphere, purified hexane (polymer solvent), cyclopentene (polymer monomer), a 0.03M tungsten hexachloride toluene solution, and a 0.05M tetrachlorophenol toluene solution were continuously added to a 30L premixing reactor with an aspect ratio of 50:1. The flow rates of hexane, cyclopentene, hexachloride, and tetrachlorophenol were 1.55L / min, 0.4L / min, 0.03L / min, and 0.035L / min, respectively. A circulation pump was started to mix the premixed reactants in the premixing reactor and continuously supply the mixture to the first reactor. The material temperature in the premixing reactor was controlled by adjusting the circulation ratio of the circulation pump, the material residence time, and the temperature and flow rate of the cooling medium. The material circulation ratio was 15:1, the material temperature in the premixing reactor was -5 to -3℃, the material residence time in the premixing reactor was 15 min, and the system pressure was 0.1 MPa.

[0041] Under a nitrogen atmosphere, a mixture from a premixed reactor, a 0.05M hexane solution of the molecular weight regulator butene-1, and a 0.1M hexane solution of triisobutylaluminum were continuously added to a 100L reactor with a height-to-diameter ratio of 10:1. The flow rates of the butene-1 solution and the triisobutylaluminum solution were 0.031L / min and 0.03L / min respectively. The first reactor had a ribbon-type agitator on the upper layer and a straight-blade turbine-type agitator on the lower layer. The hexane solutions of the molecular weight regulator butene-1 and triisobutylaluminum were introduced into the vicinity of the lower agitator blades through three 8mm diameter pipes. The agitator in the first reactor was turned on, and the stirring speed was adjusted to 200rpm. The material temperature in the first reactor was controlled at 0-2℃, the residence time of the material in the first reactor was 50min, and the system pressure was 0.1MPa. The concentration of cyclopentene monomer was controlled at 22% by mass, and the catalyst was prepared at a concentration of 3.0×10⁻⁶. -6 The amount of cyclopentene added was molW / g, the molar ratio of phenol to tungsten was 2:1, the molar ratio of aluminum to tungsten was 3.5:1, and the molar ratio of butene-1 to tungsten was 1.8:1.

[0042] Under a nitrogen atmosphere, material from the first reactor was continuously added to a second reactor with a volume of 120 L and an aspect ratio of 15:1. The agitator in the second reactor was an inclined blade impeller. The temperature of the second reactor was 2.0–3.0 °C, the material residence time was 60 min, and the system pressure was 0.1 MPa. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 200,000, a molecular weight distribution (Mw / Mn) of 1.80, a conversion rate of 81.5%, a trans-structure content of 85.2%, a glass transition temperature (Tg) of -94.4 °C, and a gel content of 0.1%.

[0043] Example 2

[0044] The process was essentially a repeat of Example 1, except that a 0.05 M trichlorophenol toluene solution was used instead of a 0.05 M tetrachlorophenol toluene solution. The catalyst was aged before use. The aging conditions were: a mixture of 0.03 M tungsten hexachloride toluene solution and 0.05 M trichlorophenol toluene solution was aged at 25°C for 1 hour, with a molar ratio of trichlorophenol to tungsten hexachloride of 0.5:1. The catalyst dosage was 8 × 10⁻⁶. -6 The molar ratio of triisobutylaluminum to tungsten hexachloride was 6:1, and the molar ratio of butene-1 to tungsten hexachloride was 0.5:1. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 316,000, a Mw / Mn ratio of 1.80, a conversion rate of 77%, a trans structure content of 86.5%, a glass transition temperature (Tg) of -94.2℃, and a gel content of 0.2%.

[0045] Example 3

[0046] The process was essentially a repeat of Example 1, except that the catalyst dosage was 1.5 × 10⁻⁶. -6 The molar ratio of triisobutylaluminum to tungsten hexachloride was 1:1, and the molar ratio of butene-1 to tungsten hexachloride was 5:1. The catalyst aging temperature was 60℃, the aging time was 10 min, and the molar ratio of tetrachlorophenol to tungsten hexachloride was 3.0:1. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 75,000, a Mw / Mn ratio of 1.95, a conversion rate of 79.6%, a trans-structure content of 84.2%, a glass transition temperature (Tg) of -94.4℃, and a gel content of 0.1%.

[0047] Example 4

[0048] The process was essentially a repeat of Example 1, except that the aspect ratio of the premixed loop reactor was 10:1, the material circulation ratio was 5:1, the material residence time was 5 min, and the material temperature was -30℃. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 225,000, a Mw / Mn ratio of 1.81, a conversion rate of 77.0%, a trans-structure content of 80.5%, a glass transition temperature (Tg) of -96.3℃, and a gel content of 0.1%.

[0049] Example 5

[0050] The process was essentially a repeat of Example 1, except that the aspect ratio of the premixing reactor was 100:1, the material circulation ratio in the premixing reactor was 30:1, the material residence time was 30 min, and the material temperature was 20°C. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 203,000, a Mw / Mn ratio of 1.98, a conversion rate of 76.0%, a trans-structure content of 91.5%, a glass transition temperature (Tg) of -92.9°C, and a gel content of 0.2%.

[0051] Example 6

[0052] The process was essentially a repeat of Example 1, except that the aspect ratio of the first reactor was 5:1, the material residence time in the first reactor was 30 min, and the material temperature was -10°C; the aspect ratio of the second reactor was 5:1, the material residence time in the second reactor was 30 min, and the material temperature was -5°C. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 227,000, a Mw / Mn ratio of 1.75, a conversion rate of 79.1%, a trans-structure content of 81%, a glass transition temperature (Tg) of -95.8°C, and a gel content of 0.1%.

[0053] Example 7

[0054] The process was essentially a repeat of Example 1, except that the aspect ratio of the first reactor was 20:1, the material residence time in the first reactor was 120 min, and the material temperature was 20°C; and the aspect ratio of the second reactor was 30:1, the material residence time in the second reactor was 120 min, and the material temperature was 30°C. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 202,000, a Mw / Mn ratio of 2.05, a conversion rate of 78.5%, a trans-structure content of 91.8%, a glass transition temperature (Tg) of -92.8°C, and a gel content of 0.1%.

[0055] Example 8

[0056] The process was essentially a repeat of Example 1, except that the main catalyst was WOCl4, the activator was trichlorophenol, the molecular weight regulator was 1-octene, the organoaluminum compound was dibutylaluminum chloride, and the polymerization solvent was cyclohexane. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 213,000, a Mw / Mn ratio of 1.98, a conversion rate of 80.8%, a trans-structure content of 86.6%, a glass transition temperature (Tg) of -94.7°C, and a gel content of 0.1%.

[0057] Example 10

[0058] The process was essentially a repeat of Example 1, except that the monomer concentration was 15%. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 187,000, a Mw / Mn ratio of 1.89, a conversion rate of 73.5%, a trans-structure content of 87.2%, a glass transition temperature (Tg) of -94.3°C, and a gel content of 0.1%.

[0059] Example 11

[0060] The process was essentially a repeat of Example 1, except that the molar ratio of butene-1 to tungsten was 5:1 and the monomer concentration was 50%. The resulting trans-polycyclopentene rubber had a number-average molecular weight (Mn) of 78,000, a Mw / Mn ratio of 2.21, a conversion rate of 84.2%, a trans-structure content of 85.9%, a glass transition temperature (Tg) of -94.3°C, and a gel content of 0.3%.

[0061] Comparative Example 1

[0062] The process was essentially a repeat of Example 1, except that the polymerization solvent, cyclopentene monomer, and aging catalyst were introduced directly into the first reactor instead of the premixed reactor. This resulted in the inability to properly dissipate the heat of reaction in the first reactor, making it impossible to stably control the reaction temperature. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 353,000, a Mw / Mn ratio of 2.88, a polymerization conversion rate of 45%, a trans-structure content of 97%, a glass transition temperature (Tg) of -90.2°C, and a gel content of 8.0%.

[0063] Comparative Example 2

[0064] The process was essentially a repeat of Example 1, except that the bottom of the agitator in the first reactor did not have a straight-bladed turbine. The hexane solution of molecular weight regulator butene-1, the hexane solution of triisobutylaluminum, and the premixed liquid from the premixing reactor were introduced into the first reactor from the bottom together, resulting in polycyclopentene rubber with a number-average molecular weight Mn of 230,000, a molecular weight distribution Mw / Mn of 2.52, a conversion rate of 65.1%, a trans structure content of 88.6%, a glass transition temperature Tg of -93.4℃, and a gel content of 3.5%.

[0065] Comparative Example 3

[0066] The process was essentially a repeat of Example 1, except that the aspect ratio of the premixed reactor was 1:1, the circulation ratio of the circulating pump was 1:1, the residence time was 2 min, the temperature in the premixed reactor was 60°C, and the resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 312,000, a Mw / Mn ratio of 2.85, a polymerization conversion rate of 45%, a trans-structure content of 97.2%, a glass transition temperature (Tg) of -91.0°C, and a gel content of 4.0%.

[0067] Comparative Example 4

[0068] The process was essentially a repeat of Example 1, except that the temperature of the premixed reactor and the first and second reactors was controlled at -60°C. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 386,000, a Mw / Mn ratio of 2.95, a polymerization conversion rate of 50%, a trans structure content of 33.6%, a glass transition temperature (Tg) of -107.5°C, and a gel content of 5.2%.

[0069] Comparative Example 5

[0070] The process was essentially a repeat of Example 1, except that the temperature of the premixed reactor and the first and second reactors was controlled at 60°C. The resulting polycyclopentene rubber had a number-average molecular weight (Mn) of 393,000, a Mw / Mn ratio of 2.89, a polymerization conversion rate of 22%, a trans structure content of 97.3%, a glass transition temperature (Tg) of -90.2°C, and a gel content of 5.5%.

[0071] As can be seen from the above examples and comparative examples, the polycyclopentene rubber prepared by the method of the present invention has a high polymerization conversion rate, a suitable molecular weight and its distribution, and the trans structure content can be controlled within a better range. It also has a low glass transition temperature and low gel content. In particular, the product obtained by the continuous polymerization method has stable performance and low energy and material consumption in the production process.

Claims

1. A continuous solution polymerization method for trans-polycyclopentene rubber, characterized in that, Includes the following steps: (1) Under an inert atmosphere, the polymerization solvent, cyclopentene monomer, main catalyst solution, oxygen- or halogenated activator solution or the aged liquid of main catalyst solution and oxygen- or halogenated activator solution are continuously fed into the premix reactor. The premix reactor is a loop reactor equipped with a circulation pump and a cooling jacket. The circulation pump is used for premixing and circulating the material, and the cooling medium in the jacket is used for precooling the material in the premix reactor. (2) Under an inert atmosphere, the premixed liquid, molecular weight regulator solution and organoaluminum compound solution from step (1) are continuously fed into the first reactor, wherein the first reactor is an adiabatic fully mixed reactor with stirring, the bottommost stirring blade is a straight blade turbine, and the molecular weight regulator solution and aluminum compound solution are inserted into the vicinity of the bottom stirring blade through two or more pipes. (3) Under an inert atmosphere, the material from the first reactor in step (2) continuously enters from the bottom of the second reactor and subsequent reactors and flows out from the top, wherein the second reactor and subsequent polymerization reactors are adiabatic fully mixed reactors with stirring. In step (1), the length-to-diameter ratio of the loop reactor is 5 to 150:1, the circulation ratio of the circulating pump is 2 to 80:1, the temperature of the circulating material is -50 to 40°C, the residence time of the material in the reactor is 3 to 60 min, and the system pressure is 0.01 to 1 MPa. In step (2), the height-to-diameter ratio of the first reactor is 2~30:1, the residence time of the material in the reactor is 10~240 min, the temperature of the circulating material is -50~50℃, and the system pressure is 0.01~1MPa; In step (3), the height-to-diameter ratio of the second reactor and the subsequent reactor is 2~50:1, the residence time of the material in the reactor is 10~240 min, the temperature of the circulating material is -30~50℃, and the system pressure is 0.01~1MPa.

2. The method according to claim 1, characterized in that, In step (1), the aging temperature of the main catalyst solution and the oxygen- or halogen-containing activator solution is -20 to 80°C, and the aging reaction time is 5 to 180 min.

3. The method according to claim 1, characterized in that, The length-to-diameter ratio of the loop reactor in step (1) is 10-100:1, the circulation ratio of the circulating pump is 5-30:1, the temperature of the circulating material is -30-20℃, the residence time of the material in the reactor is 5-30 min, and the system pressure is 0.05-0.5 MPa.

4. The method according to claim 1, characterized in that, In step (2), the height-to-diameter ratio of the first reactor is 5~20:1, the residence time of the material in the reactor is 30~120 min, the temperature of the circulating material is -10~20℃, and the system pressure is 0.05~0.5MPa.

5. The method according to claim 1, characterized in that, In step (3), the height-to-diameter ratio of the second reactor and the subsequent reactor is 5~30:1, the residence time of the material in the reactor is 30~120min, the temperature of the circulating material is -5~30℃, and the system pressure is 0.05~0.5MPa.

6. The method according to claim 1, characterized in that, In step (1), the main catalyst is selected from one or more of tungsten halides, tungsten oxyhalides, tungsten alkoxy compounds, molybdenum halides, molybdenum oxyhalides and molybdenum alkoxy compounds.

7. The method according to claim 6, characterized in that, In step (1), the main catalyst is selected from one or more of WCl6, WBr6, WCl2, WBr2, WOCl4, WOBr4, MoCl5 and MoBr5.

8. The method according to claim 1, characterized in that, In step (1), the oxygen- or halogenated activator is selected from one or more of polyhalogenated phenols, benzoyl peroxide and epichlorohydrin; the polyhalogenated phenol is selected from one or more of trichlorophenol, tetrachlorophenol, pentachlorophenol, dichlorophenol, dibromophenol, tribromophenol, diiodophenol and triiodophenol.

9. The method according to claim 1, characterized in that, In step (2), the molecular weight regulator is selected from one or more linear monoolefins having 2 to 10 carbon atoms.

10. The method according to claim 9, characterized in that, In step (2), the molecular weight regulator is selected from one or more of 1-butene, 2-butene, 1-hexene and 1-octene.

11. The method according to claim 1, characterized in that, In step (2), the organoaluminum compound is an alkylaluminum and / or an alkylaluminum halide; the alkylaluminum is selected from one or more of triisobutylaluminum and triethylaluminum; the alkylaluminum halide is selected from one or more of diethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromodiethylaluminum, diethylaluminum bromodibutylaluminum, dibutylaluminum bromodibutylaluminum, and dibutylaluminum bromodibutylaluminum.

12. The method according to claim 1, characterized in that, The aging reaction temperature is 10~60℃, and the aging reaction time is 20~120min.

13. The method according to claim 1, characterized in that, Relative to 1 mole of the main catalyst, the amount of the oxygen- or halogen-containing activator is 0.2 to 10 moles, the amount of the molecular weight regulator is 0.1 to 10 moles, and the amount of the organoaluminum is 0.2 to 10 moles.

14. The method according to claim 13, characterized in that, Relative to 1 mole of the main catalyst, the amount of the oxygen- or halogen-containing activator is 0.5 to 3 moles, the amount of the molecular weight regulator is 0.5 to 5 moles, and the amount of the organoaluminum is 1 to 6 moles.

15. The method according to claim 1, characterized in that, In step (2), the amount of the main catalyst used is 1 × 10⁻⁶ per gram of the cyclopentene monomer. -6 ~3×10 -5 mol.

16. The method according to claim 15, characterized in that, In step (2), the amount of the main catalyst is 1.5 × 10⁻⁶ per gram of the cyclopentene monomer. -6 ~1.0×10 -5 mol.

17. The method according to claim 1, characterized in that, In step (2), the concentration of cyclopentene monomer in the reaction mixture is 10-70% by weight.

18. The method according to claim 17, characterized in that, In step (2), the concentration of cyclopentene monomer in the reaction mixture is 15-50% by weight.

19. The method according to claim 1, characterized in that, The solvents for the main catalyst and activator are selected from one or more of toluene, xylene, and benzene; the polymerization solvents are selected from one or more of n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, xylene, benzene, and toluene.

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