Cycloolefin polymer, cycloolefin polymerization process and application

Abstract

The invention provides a cycloolefin polymer, a cycloolefin polymerization process and application. The cycloolefin polymerization process comprises a raw material preparation process, a polymerization process, a hydrogenation reaction process, a devolatilization process and a devolatilization extrusion granulation process. According to the process, cycloolefin is subjected to a polymerization reaction in a polymerization kettle to generate a polymer; the process comprises the following steps: feeding a material from a polymerization kettle into a hydrogenation reaction kettle, and carrying out hydrogenation reaction to generate a cycloolefin polymer; the process comprises the following steps: feeding a material from a hydrogenation reaction kettle into a devolatilization kettle to remove volatile matters; according to the process, the cycloolefin polymer discharged from a devolatilization kettle enters a screw extruder, the space between a feed port and an outlet of the screw extruder is at least divided into 2-3 sections, exhaust ports are formed in the at least 1-2 sections from the feed port and used for vacuumizing, volatile matter is further removed, and the cycloolefin polymer with the low volatile matter content is obtained. The cycloolefin polymer is not crosslinked, has stable structure and performance, does not turn yellow, and is easy to process.

Description

Technical Field

[0001] The present invention relates to polymer materials, polymer material synthesis methods, polymer material synthesis processes, and applications of polymer materials, polymer material synthesis methods, and polymer material synthesis processes, and specifically to cycloolefin polymer materials, cycloolefin polymer synthesis methods, cycloolefin polymer synthesis processes, and applications of cycloolefin polymer materials, cycloolefin polymer synthesis methods, and cycloolefin polymer synthesis processes. Background Art

[0002] Cyclic olefin polymer (COP) is a general term for cycloolefin homopolymers and copolymers, and is a product obtained by ring-opening metathesis polymerization (ROMP) of cycloolefins. Chauvin proposed the ROMP polymerization mechanism, Grubbs invented the ruthenium carbene catalyst, and Schrock invented the molybdenum carbene catalyst. These three people won the Nobel Prize in Chemistry in 2005 for their contributions to ROMP. Cyclic olefin polymer (COP) is a highly transparent, extremely pure non-crystalline resin with excellent optical properties, close to the high refractive index of glass, and comparable transparency to PMMA and PC, and can be used as a substitute for glass. It can also be used for optical data storage, optical discs, lenses, prisms, carriers, films, covers and focusing plates of solar cells, or for glass fibers, etc.; it has excellent water vapor barrier properties, which can extend the shelf life of drugs, and has excellent biocompatibility, low content of dissolved substances and impurities. It can be used in medical prefilled syringes and medical testing consumables, and can replace the high-cost quartz glass and polydimethylsiloxane; it has excellent chemical stability, excellent water resistance, acid resistance, alkali resistance, solvent resistance, low density and high temperature resistance, can be sterilized by steam and gamma rays, and can be used for blood storage, test tubes, high-temperature medical goggles, etc.; it has excellent thermal properties, a high glass transition temperature, and can increase Tg by controlling the cycloolefin content, has excellent high temperature resistance and antioxidant properties, can be prepared into films and substrates, has unchanged viscoelasticity, electrical properties, good adhesion, thermal stability, high elongation and low stress at high temperatures; it has excellent dielectric properties, easy molding and processing and good compatibility. Sartori et al. studied the addition polymerization of cycloolefins. Natta used W and Mo transition metal catalysts to study the ring-opening polymerization of cycloolefins, but its activity was low. Japan's JSR company used ring-opening metathesis polymerization (ROMP) polymerization to develop a cycloolefin copolymer with the trade name ARTON. Until now, the production technology is mostly in the hands of Japanese companies, mainly Zeon, JSR, TOPAS Advanced Polymers GmbH and Mitsui. There are still high technical barriers in my country, and it is still impossible to achieve localization. The ROMP principle is used to produce cycloolefin polymers. The unsaturated double bonds in the monomers are still retained in the generated polymer, that is, the number of unsaturated bonds in the main chain of the generated polymer molecule is equal to the degree of polymerization. The main chain of the cycloolefin polymer contains a large number of double bonds and is very easy to crosslink. For example, dicyclopentanediol undergoes crosslinking during the polymerization process, which is difficult to control. The ROMP principle is used to produce norbornene polymers. The polynorbornene quickly turns yellow and crosslinks. The current existing cycloolefin polymerization process is to send the material coming out of the cycloolefin polymerization reactor into the devolatilization reactor for post-treatment. During the post-treatment process, the double bonds in the main chain of the cycloolefin polymer molecule are very easy to undergo crosslinking reactions, causing the cycloolefin polymer to turn yellow in color and difficult to process after crosslinking.Therefore, how to produce qualified cycloolefin polymers is a key core technology that urgently needs to be solved.

[0003] Based on the profound understanding of the ROMP principle and the structure of cycloolefin polymers by the inventors Huang Sihuang and others, cycloolefin polymers and cycloolefin polymerization processes and applications were invented. The cycloolefin polymerization process is mainly composed of a raw material preparation process, a polymerization process, a hydrogenation reaction process, a devolatilization process and a devolatilization extrusion granulation process; the system used in the cycloolefin polymerization process includes a raw material storage tank, a meter, a catalyst preparation kettle, a catalyst injection pump, a cycloolefin polymerization kettle, a hydrogenation reactor, a devolatilization kettle, a screw extruder, a pelletizer, and drying and packaging equipment; wherein the raw material storage tank is a solvent storage tank, a cycloolefin storage tank, a metal carbene catalyst storage tank, a hydrogenation catalyst storage tank, and a hydrogen storage tank; the ROMP principle is adopted to produce cycloolefin polymers, and the materials coming out of the polymerization kettle directly enter the hydrogenation reactor for hydrogenation reaction, and the ROMP reaction is terminated in the hydrogenation reactor, and the molecular weight of the cycloolefin polymer can be adjusted, and the materials coming out of the hydrogenation reactor are subjected to post-treatment processes such as devolatilization to obtain qualified cycloolefin polymers. By adopting the cycloolefin polymerization process disclosed in the present patent, the material coming out of the polymerization kettle directly enters the hydrogenation reactor for hydrogenation reaction, and the double bonds in the main chain of the cycloolefin polymer molecule are converted into saturated bonds through the hydrogenation reaction, so the cycloolefin polymer has a stable structure, stable performance, and does not change to yellow; the characteristic effect of the cycloolefin polymer and the cycloolefin polymerization process and application is to obtain high-quality cycloolefin polymer, and the cycloolefin polymer is a cycloolefin homopolymer or a cycloolefin copolymer; wherein, the cycloolefin polymer is a non-crystalline resin with high transparency and high purity, has excellent optical properties, can be used as a substitute for glass, and can be used for optical data storage, optical disks, lenses, prisms, carriers, films, cover plates and focusing plates of solar cells or for glass fibers, etc.; has excellent water vapor The vapor barrier property can extend the shelf life of the drug, has excellent biocompatibility, low content of dissolution and impurities, can be used in medical prefilled syringes and medical testing consumables, and can replace the high-cost quartz glass and polydimethylsiloxane; it has excellent chemical stability, excellent water resistance, acid resistance, alkali resistance, solvent resistance, low density and high temperature resistance, can be sterilized by steam and gamma rays, and can be used for blood storage, test tubes, high-temperature medical goggles, etc.; it has excellent thermal properties, a high glass transition temperature, excellent high temperature resistance and anti-oxidation properties, can be prepared into films and substrates, and has constant viscoelasticity, electrical properties, good adhesion, thermal stability, high elongation and low stress at high temperatures; it has excellent dielectric properties, easy molding and processing and good compatibility. The cycloolefin polymer and cycloolefin polymerization process disclosed in the present invention are pioneering technologies. The present invention discloses to the world that my country has achieved a high level of scientific and technological self-reliance in the field of cycloolefin polymer synthesis. Summary of the invention

[0004] The first object of the present invention is to provide a cycloolefin polymer, wherein the olefin polymer is prepared by ROMP principle using a metal carbene catalyst in the presence of an inert organic solvent to catalyze the reaction of C5-C 30 Cycloolefin polymerization to obtain cycloolefin polymer, wherein the C5-C 30 Cycloolefins are cycloolefin molecules containing one double bond, two double bonds or more than two double bonds, wherein the C5-C 30 Cycloolefins are cyclic olefins containing one double bond and one triple bond, wherein the C5-C 30 The cycloolefin is a cycloolefin molecule containing one or two or more heteroatoms; wherein the heteroatoms are nitrogen, oxygen, halogen, selenium, sulfur, phosphorus, iron, copper, silver, gold, ruthenium, molybdenum, palladium or rhodium; wherein the metal carbene catalyst is a ruthenium carbene catalyst, a rhodium carbene catalyst, a molybdenum carbene catalyst, a palladium carbene catalyst, a vanadium carbene catalyst, a nickel carbene catalyst, a platinum carbene catalyst, a titanium carbene catalyst or a cobalt carbene catalyst; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof; wherein the cycloolefin polymerization temperature is 0-180° C., the polymerization pressure is 0.1-10 MPa, and the molar ratio of the cycloolefin to the metal carbene catalyst is (50-100000):1.

[0005] The second object of the present invention is to provide a cycloolefin polymerization process, which is mainly composed of a raw material preparation process, a polymerization process, a hydrogenation reaction process, a devolatilization process and a devolatilization extrusion granulation process; the system used in the cycloolefin polymerization process includes a raw material storage tank, a meter, a catalyst preparation kettle, a catalyst injection pump, a cycloolefin polymerization kettle, a hydrogenation reactor, a devolatilization kettle, a screw extruder, a pelletizer, and a drying and packaging device; wherein the raw material storage tank is a solvent storage tank, a cycloolefin storage tank, a metal carbene catalyst storage tank, a hydrogenation catalyst catalyst storage tank, and a hydrogen storage tank; wherein the cycloolefin polymerization process uses a metal carbene catalyst to produce cycloolefin polymers, the material coming out of the polymerization kettle directly enters the hydrogenation reactor for hydrogenation reaction, the ROMP reaction is terminated in the hydrogenation reactor, the molecular weight of the cycloolefin polymer can be adjusted, and the material coming out of the hydrogenation reactor enters the devolatilization kettle, after devolatilization, is sent to a screw extruder with an exhaust port for extrusion, pelletization, centrifugal drying, and drying , packaging and other post-treatment processes to obtain qualified cycloolefin polymer pellets; the double bonds in the cycloolefin polymer molecules are converted into saturated bonds through hydrogenation reaction, so the cycloolefin polymer has a stable structure, stable performance, and the color does not turn yellow, and the cycloolefin polymer is easy to process; wherein the hydrogenation reaction temperature is 50-180°C, the reaction pressure is 3-10MPa, the mass content of the cycloolefin polymer in the material is 3-40%, and the hydrogenation catalyst is a precious metal or metal carbene catalyst such as Pd, Rh, Ru, Ni, Mo, Ir, Pt, etc.; in particular, the special feature of the cycloolefin polymerization process disclosed in the present invention is that the material coming out of the polymerization kettle enters the hydrogenation reactor for hydrogenation reaction, and the double bonds in the cycloolefin polymer molecules are converted into saturated bonds through hydrogenation reaction, and cross-linking reaction is not easy to occur during the hydrogenation reaction process, the devolatilization process or the devolatilization extrusion granulation process, the cycloolefin polymer has a stable structure, stable performance, and the color does not turn yellow, and the cycloolefin polymer is easy to process.

[0006] The third object of the present invention is the application of the cycloolefin polymerization process, wherein the application of the cycloolefin polymerization process is to catalyze C5-C 20Cycloolefin polymerization is carried out to obtain cycloolefin polymers. The materials discharged from the polymerization kettle are directly fed into a hydrogenation reactor for hydrogenation reaction. The ROMP reaction is terminated in the hydrogenation reactor, and the molecular weight of the cycloolefin polymer can be regulated. The materials discharged from the hydrogenation reactor are sent to a screw extruder with an exhaust port for extrusion, pelletizing, centrifugal drying, drying, packaging and other post-treatment processes after devolatilization to obtain qualified cycloolefin polymer pellets. In particular, the cycloolefin polymerization process disclosed in the present invention is special in that the cycloolefin polymer discharged from the devolatilization reactor is fed into the feed port of the screw extruder, and the cycloolefin polymer pellets are obtained in the screw extruder. The extruder is divided into at least 2-3 sections from the feed inlet to the outlet, and exhaust ports are provided in at least 1-2 sections in front of the feed inlet for vacuuming to further remove volatiles in the material melt and obtain a product with low volatile content; an additive is added to the front section of the screw extruder, wherein the additive is an anti-aging agent or a flame retardant, and the mass ratio of the additive to the cycloolefin polymer is (1-3): (100-10000); the screw extruder is divided into at least 2-3 sections from the feed inlet to the outlet, and the operating temperature of each section is different or the same, and the operating temperature is 150-350°C.

[0007] The fourth object of the present invention is the application of cycloolefin polymers, wherein the application of cycloolefin polymers is that cycloolefin polymers are highly transparent, high-purity non-crystalline resins with excellent optical properties, and can be used for optical data storage, AI think tanks, AI equipment, quantum communications, quantum computing, optical disks, lenses, prisms, carriers, films, covers and focusing plates of solar cells or for glass fibers, etc.; have excellent water vapor barrier properties, can extend the shelf life of drugs, and have excellent biocompatibility, low content of dissolved substances and impurities, and can be used in medical prefilled syringes and medical detection Consumables; it has excellent chemical stability, excellent water resistance, acid resistance, alkali resistance, solvent resistance, low density and high temperature resistance, can be sterilized by steam and gamma rays, and can be used for blood storage, test tubes, high temperature resistant medical goggles, etc.; it has excellent thermal properties, a high glass transition temperature, and the Tg can be increased by controlling the cyclic olefin content. It has excellent high temperature resistance and antioxidant properties, can be prepared into films and substrates, and has unchanged viscoelasticity, electrical properties, good adhesion, thermal stability, high elongation and low stress at high temperatures; it has excellent dielectric properties, easy molding and processing and good compatibility.

[0008] Cycloolefin polymer and cycloolefin polymerization process and application, characterized in that the cycloolefin polymer is catalyzed by metal carbene catalyst in the presence of inert organic solvent in a polymerization reactor through ROMP principle to produce C5-C 30 Cycloolefin polymerization is carried out to obtain a cycloolefin polymer containing an unsaturated bond in the main chain; double bonds in the polymer main chain are converted into saturated bonds by hydrogenation reaction in a hydrogenation reactor to obtain a cycloolefin polymer; wherein the C5-C 30Cycloolefins are cycloolefin molecules containing one double bond, two double bonds or more than two double bonds, wherein the C5-C 30 Cycloolefins are cyclic olefins containing one double bond and one triple bond, wherein the C5-C 30 Cycloolefins are cycloolefins containing one or two or more heteroatoms in the molecule; wherein the heteroatoms are nitrogen, oxygen, halogen, selenium, sulfur, phosphorus, iron, copper, silver, gold, ruthenium, platinum, palladium or rhodium, etc.; wherein the metal carbene catalyst is a ruthenium carbene catalyst, a rhodium carbene catalyst, a platinum carbene catalyst, a palladium carbene catalyst, a vanadium carbene catalyst, a nickel carbene catalyst, a platinum carbene catalyst, a titanium carbene catalyst or a cobalt carbene catalyst, etc.; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof; wherein The cycloolefin polymerization temperature is 0-180° C., the polymerization pressure is 0.1-10 MPa, the polymerization time is 5 min-300 min, and the molar ratio of cycloolefin to metal carbene catalyst is (50-100000): 1; the mass content of the cycloolefin in the polymerization kettle is 10-70%; the hydrogenation reaction temperature is 50-180° C., the reaction pressure is 3-10 MPa, the reaction time is 0.5-15 hours, the mass content of the cycloolefin polymer in the material is 3-40%, and the hydrogenation catalyst is a precious metal such as Pd, Rh, Ru, Ni, Mo, Ir, Pt or a metal carbene catalyst.

[0009] The invention discloses a cycloolefin polymer and a cycloolefin polymerization process and application, characterized in that the cycloolefin polymerization process mainly consists of a raw material preparation process, a polymerization process, a hydrogenation reaction process, a devolatilization process and a devolatilization extrusion granulation process; the system used in the cycloolefin polymerization process comprises a raw material storage tank, a meter, a catalyst preparation kettle, a catalyst injection pump, a cycloolefin polymerization kettle, a hydrogenation reactor, a devolatilization kettle, a screw extruder, a pelletizer, and drying and packaging equipment; wherein the raw material storage tank is a solvent storage tank, a cycloolefin storage tank, a metal carbene catalyst storage tank, a hydrogenation catalyst catalyst storage tank, and a hydrogen storage tank; wherein the cycloolefin polymerization process adopts a metal carbene catalyst to produce cycloolefin polymers, the material coming out of the polymerization kettle directly enters the hydrogenation reactor for hydrogenation reaction, the ROMP reaction is terminated in the hydrogenation reactor, the molecular weight of the cycloolefin polymer can be adjusted, and the material coming out of the hydrogenation reactor is sent to a screw extruder with an exhaust port for extrusion, pelletization, centrifugal drying, drying, packaging and other post-treatment processes after devolatilization to obtain a qualified cycloolefin polymer; the cycloolefin polymer is separated and separated. The double bonds in the main chain are converted into saturated bonds through hydrogenation reaction, so the cycloolefin polymer has stable structure, stable performance, and color does not turn yellow, and the cycloolefin polymer is easy to process; wherein the hydrogenation reaction temperature is 50-180°C, the reaction pressure is 3-10MPa, the reaction time is 0.5-15 hours, the mass content of the cycloolefin polymer in the material is 3-40%, and the hydrogenation catalyst is a precious metal or metal carbene catalyst such as Pd, Rh, Ru, Ni, Mo, Ir, Pt, etc.; wherein the raw material preparation process is metal carbene catalyst preparation, hydrogenation catalyst preparation, solvent preparation and cycloolefin monomer preparation; in particular, the cycloolefin polymerization process disclosed by the present invention is special in that the material coming out of the polymerization kettle enters the hydrogenation reactor for hydrogenation reaction, and the double bonds in the cycloolefin polymer molecules are converted into saturated bonds through hydrogenation reaction, and crosslinking reaction is not easy to occur in the hydrogenation reaction process, the devolatilization process or the devolatilization extrusion granulation process, the cycloolefin polymer has stable structure, stable performance, and color does not turn yellow, and the cycloolefin polymer is easy to process.

[0010] Cycloolefin polymer and cycloolefin polymerization process and application, characterized in that the cycloolefin polymerization process is applied by ROMP principle, using metal carbene catalyst to catalyze C5-C 20Cycloolefin polymerization is carried out to obtain cycloolefin polymers. The materials discharged from the polymerization kettle are directly fed into a hydrogenation reactor for hydrogenation reaction. The ROMP reaction is terminated in the hydrogenation reactor, and the molecular weight of the cycloolefin polymer can be regulated. The materials discharged from the hydrogenation reactor are fed into a devolatilization reactor for devolatilization, and then fed into a screw extruder with an exhaust port for extrusion, pelletization, centrifugal drying, drying, packaging and other post-treatment processes to obtain qualified cycloolefin polymer pellets. In particular, the cycloolefin polymerization process disclosed in the present invention is special in that the cycloolefin polymer discharged from the devolatilization reactor is fed into the feed port of the screw extruder, and the cycloolefin polymer pellets are obtained by feeding the cycloolefin polymer discharged from the devolatilization reactor into the feed port of the screw extruder. The screw extruder is divided into at least 2-3 sections from the feed inlet to the outlet. Starting from the feed inlet, at least 1-2 sections in front are equipped with exhaust ports for vacuuming to further remove volatile components in the material melt and obtain a product with low volatile component content. Additives are added to the front section of the screw extruder, wherein the additives are anti-aging agents or flame retardants, and the mass ratio of the additive amount to the cycloolefin polymer is (1-3): (100-10000). The screw extruder is divided into at least 2-3 sections from the feed inlet to the outlet, and the operating temperature of each section is different or the same, and the operating temperature is 150-350°C.

[0011] Cycloolefin polymer and cycloolefin polymerization process and application, characterized in that, in the cycloolefin polymerization process, the material after hydrogenation reaction is subjected to a devolatilization process to remove solvent, unreacted monomer and other volatile components, extruded pelletized, dried and packaged; wherein the devolatilization is carried out by using a static film devolatilizer, a vertical or horizontal dynamic devolatilization kettle to remove solvent, unreacted monomer and other volatile components; wherein the devolatilization operation temperature is 90-350°C, the average residence time is 15-300min; the volume of the devolatilization kettle is 3L-100m 3 , preferably 3L-5m 3 , and preferably 5L-500L, stainless steel material; wherein the vertical or horizontal dynamic devolatilization reactor is equipped with a high-efficiency agitator, wherein the high-efficiency agitator is an agitator suitable for high-viscosity fluids, preferably an anchor agitator, a frame agitator, a ribbon agitator, a multi-zone reaction agitator or a surface renewal agitator, etc., the agitator speed is 5-60 rpm, which improves the removal effect of the solvent and the residual monomer, and obtains high-quality cycloolefin polymers; wherein the screw extrusion temperature of the extrusion pelletizing, drying and packaging process is 150-350°C, the extrusion time is 5-30min, cold water cooling, room temperature pelletizing, centrifugal drying, and the cycloolefin polymer pellets are sent to the silo, packaged, and sent to the warehouse through the air delivery pipeline.

[0012] Cyclic olefin polymers and cycloolefin polymerization processes and applications, characterized in that the cycloolefin polymers are used for optical data storage, AI think tanks, AI equipment, quantum communications, quantum computing, optical discs, lenses, prisms, carriers, films, covers and focusing plates of solar cells or for glass fibers, etc.; used for medical prefilled syringes and medical testing consumables; have excellent chemical stability and are used for blood storage, test tubes, high-temperature resistant medical goggles, etc.; prepare films and substrates; cycloolefin polymers have unchanged viscoelasticity, electrical properties, good adhesion, thermal stability, high elongation and low stress at high temperatures; cycloolefin polymers have excellent dielectric properties, are easy to mold and process, and have good compatibility.

[0013] Cycloolefin polymer and cycloolefin polymerization process and application, characterized in that the process of the cycloolefin polymer and cycloolefin polymerization process is as follows:

[0014] (1) Raw material storage and preparation process: The main raw materials are stored in storage tanks at room temperature. The raw material storage tanks include solvent storage tanks, monomer cycloolefin storage tanks, metal carbene catalyst storage tanks, hydrogenation catalyst storage tanks and hydrogen storage tanks. The volume of the raw material storage tanks is 3L-200m 3 , preferably 5L-5m 3 , preferably 5L-500L, made of stainless steel; wherein the metal carbene catalyst is fed into the polymerization kettle by an injection pump; wherein the monomer cycloolefin is fed into the polymerization kettle by a delivery pump, and the volume of the polymerization kettle is 1L-200m 3 , preferably 1L-500L, more preferably 1L-100L, made of stainless steel, the polymerization temperature is 0-180°C, the agitator speed is 10-80rpm, and the average residence time is 5-60min; wherein the hydrogenation catalyst is fed into the hydrogenation reactor by an injection pump, and the volume of the hydrogenation reactor is 1L-100m 3 , preferably 1L-500L, more preferably 1L-100L, made of stainless steel, the hydrogenation reaction temperature is 50-180°C, the reaction pressure is 3-10MPa, the agitator speed is 10-80rpm, the average residence time is 3-15 hours, and the mass content of cycloolefin polymer in the material is 3-40%; wherein the solvent is fed into the metal carbene catalyst preparation kettle, the hydrogenation catalyst preparation kettle or the solvent preparation kettle by a delivery pump; wherein the solvent preparation kettle is used to prepare the solvent, and the solvent is fed into the polymerization kettle by a delivery pump.

[0015] Catalyst preparation process: the catalyst is mixed with a metal carbene catalyst and an inert organic solvent in a catalyst preparation kettle at room temperature to 50°C, and stirred for 5-30 minutes; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof.

[0016] The hydrogenation catalyst preparation process is as follows: the hydrogenation catalyst is mixed with an inert organic solvent in a hydrogenation catalyst preparation kettle at room temperature to 50° C., and stirred for 5-30 minutes; the hydrogenation catalyst is a noble metal such as Pd, Rh, Ru, Ni, Mo, Ir, Pt, or a metal carbene catalyst; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane, or hexadecane, or a mixed solvent thereof; wherein the mass ratio of the inert organic solvent to the hydrogenation catalyst is (10-100000):1.

[0017] (2) Cycloolefin polymerization process: Cycloolefin is polymerized in a polymerization kettle, the polymerization temperature of cycloolefin is 0-180°C, the polymerization pressure is 0.1-10 MPa, the polymerization time is 5 min-60 min, the mass content of cycloolefin in the polymerization kettle is 10-70%, the molar ratio of cycloolefin to metal carbene catalyst is (50-1000000): 1, the agitator speed is 5-60 rpm, and the mass content of cycloolefin polymer in the material is controlled at 3-40%.

[0018] (3) Hydrogenation reaction process: the material coming out from the bottom of the polymerization reactor is sent to the hydrogenation reactor. The hydrogenation reaction temperature is 50-180°C, the hydrogenation reaction pressure is 3-10MPa, and the hydrogenation reaction time is 0.5-10 hours. There is one, two or more hydrogenation reactors.

[0019] (4) Devolatilization process: the material coming out of the bottom of the hydrogenation reactor is sent to the devolatilization reactor from the upper part of the devolatilization reactor; wherein the devolatilization adopts a static film devolatilizer, a vertical or horizontal dynamic devolatilizer to remove volatile components such as solvent and unreacted monomer; wherein the devolatilization operation temperature is 90-350°C, and the average residence time is 10-300min; wherein the vertical or horizontal dynamic devolatilizer is equipped with a high-efficiency agitator, wherein the high-efficiency agitator is an agitator suitable for high-viscosity fluids, preferably an anchor agitator, a frame agitator, a screw ribbon agitator, a multi-zone reaction agitator or a surface renewal agitator, etc., and the agitator speed is 5-60rpm, thereby improving the removal effect of the solvent and the residual monomer, and obtaining a high-quality cycloolefin polymer.

[0020] (7) Devolatilization extrusion granulation process: the cycloolefin polymer coming out from the bottom of the devolatilization reactor is fed into the feed port of the screw extruder, and the feed port to the outlet of the screw extruder is divided into at least 2-3 sections. Starting from the feed port, at least 1-2 sections in front are equipped with exhaust ports for vacuuming to further remove the volatile matter in the material melt and obtain a product with a volatile matter of less than 0.1%; additives are added to the front section of the screw extruder, wherein the additives are anti-aging agents, flame retardants, etc., and the mass ratio of the additive added to the cycloolefin polymer is (1-3): (100-10000); the screw extruder is divided into at least 2-3 sections between the feed port and the outlet, and the operating temperature of each section is different or the same, the operating temperature is 150-350° C., the extrusion time is 5-30 min, cold water cooling, pelletizing, drying, and the cycloolefin polymer pellets are sent to the silo through the air conveying pipeline, packaged, and sent to the warehouse by conveyor belt. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Cyclic olefin polymerization process flow chart

[0022] 1 hydrogenation catalyst storage tank, 2 metal carbene catalyst storage tank, 3 solvent storage tank, 4 cycloolefin monomer storage tank, 5 hydrogenation catalyst preparation kettle, 6 metal carbene catalyst preparation kettle, 7 solvent preparation kettle, 8 cycloolefin monomer preparation kettle, 9 polymerization kettle, 10 hydrogenation reactor, 11 devolatilization kettle, 12 screw extruder, 13 agitator, 14 delivery pump, 15 injection pump, 16 meter, 17 hydrogen storage tank, 18 separation tower, 19 jacket heat exchanger, 20 safety valve, 21 exhaust port devolatilization. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with specific implementation modes, but the protection scope of the present invention is not limited to the following embodiments.

[0024] Embodiment 1:

[0025] Use attached Figure 1Cycloolefin polymerization process, the organic solvent added to the polymerization kettle is 10 tons of toluene, the metal carbene catalyst is ruthenium carbene, the amount of ruthenium carbene catalyst added is 0.8 kg, the cycloolefin is 5 tons of norbornene, the polymerization temperature is 60 ° C, the stirring speed is 25 rpm, the polymerization time is 30 min; the material is sent from the bottom of the polymerization kettle to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 4.5 MPa, 0.1 kg of ruthenium carbene hydrogenation catalyst is added, the reaction temperature is 75 ° C, the average residence time is 8 hours, and the stirrer speed is 20 rpm; the material is sent from the hydrogenation reactor The cycloolefin polymer is sent to the devolatilizer from the bottom. The mass content of the cycloolefin polymer in the material is 15%. The temperature of the devolatilizer is 260℃, the speed of the agitator is 20rpm, and the average residence time is 50min. The cycloolefin polymer is sent to the screw extruder from the bottom of the devolatilizer. The temperature of the first section of the screw extruder is 260℃ and the air is exhausted. The temperature of the second section of the screw extruder is 270℃ and the air is exhausted. 5kg of 1010 antioxidant is added. The temperature of the third section of the screw extrusion is 275℃. The extrusion time is 5min. The product is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 16.3×10 4 g / mol, density 1.09 g / cm 3 .

[0026] Embodiment 2:

[0027] Use attached Figure 1 Cycloolefin polymerization process, the organic solvent added to the polymerization kettle is 15 tons of hexane, the metal carbene catalyst is ruthenium carbene, the amount of ruthenium carbene catalyst added is 0.6 kg, the cycloolefin is 3.5 tons of norbornene, the polymerization temperature is 50 ° C, the stirring speed is 25 rpm, the polymerization time is 25 min; the material is sent from the bottom of the polymerization kettle to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 5.5 MPa, 0.05 kg of precious metal Pd hydrogenation catalyst is added, the reaction temperature is 65 ° C, the average residence time is 6 hours, and the stirrer speed is 20 rpm; the material is sent from the bottom of the polymerization kettle to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 5.5 MPa, 0.05 kg of precious metal Pd hydrogenation catalyst is added, the reaction temperature is 65 ° C, the average residence time is 6 hours, and the stirrer speed is 20 rpm; The cycloolefin polymer comes out from the bottom of the reactor and is sent to the devolatilizer. The mass content of the cycloolefin polymer in the material is 7%. The temperature of the devolatilizer is 190°C, the speed of the agitator is 20rpm, and the average residence time is 50min. The cycloolefin polymer comes out from the bottom of the devolatilizer and is sent to the screw extruder. The temperature of the first section of the screw extruder is 180°C and the air is exhausted. The temperature of the second section of the screw extruder is 175°C and the air is exhausted. 1kg of 1010 antioxidant is added. The temperature of the third section of the screw extrusion is 175°C. The extrusion time is 6min. The product is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 21.5×10 4 g / mol, density 1.18 g / cm 3 .

[0028] Embodiment 3:

[0029] Use attached Figure 1 Cycloolefin polymerization process, the organic solvent added to the polymerization kettle is 15 tons of toluene, the metal carbene catalyst is ruthenium carbene, the amount of ruthenium carbene catalyst added is 0.8 kg, the cycloolefin is 4 tons of dicyclopentadiene, the polymerization temperature is 50°C, the stirring speed is 25 rpm, and the polymerization time is 25 min; the material is sent from the bottom of the polymerization kettle to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 5.5 MPa, 0.1 kg of metal Pd hydrogenation catalyst is added, the reaction temperature is 95°C, the average residence time is 7 hours, and the stirrer speed is 20 rpm; the material is sent from the bottom of the hydrogenation reactor to the devolatilization reactor The mass content of cycloolefin polymer in the material is 7.4%, the temperature of the devolatilizer is 210℃, the speed of the agitator is 20rpm, and the average residence time is 50min; the cycloolefin polymer comes out from the bottom of the devolatilizer and is sent to the screw extruder. The temperature of the first section of the screw extruder is 210℃ and air is exhausted. The temperature of the second section of the screw extruder is 205℃ and air is exhausted. The temperature of the third section of the screw extruder is 205℃ and air is exhausted. 2kg of 1010 antioxidant is added. The temperature of the fourth section of the screw extrusion is 205℃. The extrusion time is 6min. The product is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 24.6×10 4 g / mol, density 1.11 g / cm 3 .

[0030] Embodiment 4:

[0031] Use attached Figure 1 Cycloolefin polymerization process, the organic solvent added to the polymerization kettle is 15 tons of toluene, the metal carbene catalyst is ruthenium carbene, the amount of ruthenium carbene catalyst added is 0.8 kg, the cycloolefin is 4.5 tons of cyclooctene, the polymerization temperature is 50 ° C, the stirring speed is 25 rpm, the polymerization time is 40 min; the material comes out from the bottom of the polymerization kettle and is sent to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 3.5 MPa, 0.01 kg of ruthenium carbene hydrogenation catalyst is added, the reaction temperature is 80 ° C, the average residence time is 6 hours, and the stirrer speed is 20 rpm; the material comes out from the hydrogenation reactor The cycloolefin polymer is sent to the devolatilizer from the bottom. The mass content of the cycloolefin polymer in the material is 16%. The temperature of the devolatilizer is 210℃, the speed of the agitator is 20rpm, and the average residence time is 50min. The cycloolefin polymer is sent to the screw extruder from the bottom of the devolatilizer. The temperature of the first section of the screw extruder is 210℃ and the air is exhausted. The temperature of the second section of the screw extruder is 205℃ and the air is exhausted. 1.2kg of 1010 antioxidant is added. The temperature of the third section of the screw extrusion is 205℃. The extrusion time is 6min. The product is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 24.6×10 4 g / mol, density 1.10 g / cm 3 .

[0032] Embodiment 5:

[0033] Use attached Figure 1 The cycloolefin polymerization process comprises the following steps: the organic solvent added to the polymerization kettle is 15 tons of toluene, the metal carbene catalyst is ruthenium carbene, the amount of the ruthenium carbene catalyst added is 1 kg, the cycloolefins are 3.5 tons of norbornene and 1.5 tons of dicyclopentadiene, the polymerization temperature is 60°C, the stirring speed is 25 rpm, and the polymerization time is 30 min; the material is sent out from the bottom of the polymerization kettle to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 4.5 MPa, 0.01 kg of ruthenium carbene hydrogenation catalyst is added, the reaction temperature is 80°C, the average residence time is 6 hours, and the stirrer speed is 20 rpm; the material The cycloolefin polymer is sent to the devolatilizer from the bottom of the hydrogenation reactor. The mass content of the cycloolefin polymer in the material is 13%. The temperature of the devolatilizer is 250°C, the speed of the agitator is 20rpm, and the average residence time is 50min. The cycloolefin polymer is sent to the screw extruder from the bottom of the devolatilizer. The temperature of the first section of the screw extruder is 250°C and the air is exhausted. The temperature of the second section of the screw extruder is 255°C and the air is exhausted. 3kg of 1010 antioxidant is added. The temperature of the third section of the screw extrusion is 255°C. The extrusion time is 5min. It is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 18.2×10 4 g / mol, density 1.15 g / cm 3 .

[0034] Embodiment 6:

[0035] Use attached Figure 1 Cycloolefin polymerization process, the organic solvent added to the polymerization kettle is 10kg of toluene, the metal carbene catalyst is ruthenium carbene, the amount of ruthenium carbene catalyst added is 0.5g, the cycloolefin is 1.5kg of ethylidene norbornene and 0.5kg of carboxyl norbornene, the polymerization temperature is 60°C, the stirring speed is 25rpm, and the polymerization time is 30min; the material comes out from the bottom of the polymerization kettle and is sent to the hydrogenation reactor, hydrogen is added to increase the pressure in the reactor to 6.5MPa, 0.1g of ruthenium carbene hydrogenation catalyst is added, the reaction temperature is 90°C, the average residence time is 5 hours, and the stirrer speed is 20 rpm ; The material comes out from the bottom of the hydrogenation reactor and is sent to the devolatilizer. The mass content of cycloolefin polymer in the material is 16%. The temperature of the devolatilizer is 265℃, the speed of the agitator is 20rpm, and the average residence time is 50min; the cycloolefin polymer comes out from the bottom of the devolatilizer and is sent to the screw extruder. The temperature of the first section of the screw extruder is 260℃ and the air is exhausted. The temperature of the second section of the screw extruder is 255℃ and the air is exhausted. 3g of 1010 antioxidant is added. The temperature of the third section of the screw extrusion is 255℃. The extrusion time is 5min. The product is cooled with cold water, pelletized, dried, packaged, and sent to the warehouse by conveyor belt. Weight average molecular weight 15.6×10 4 g / mol, density 1.16 g / cm3 。

Claims

1. A cycloolefin polymerization process, characterized in that: The cycloolefin polymerization process comprises a raw material preparation process, a polymerization process, a hydrogenation reaction process, a devolatilization process and a devolatilization extrusion granulation process; the system used in the cycloolefin polymerization process comprises a raw material storage tank, a meter, a catalyst preparation kettle, a catalyst injection pump, a cycloolefin polymerization kettle, a hydrogenation reaction kettle, a devolatilization kettle, a screw extruder, a pelletizer, and drying and packaging equipment; wherein the raw material storage tank is a solvent storage tank, a cycloolefin storage tank, a metal carbene catalyst storage tank, a hydrogenation catalyst storage tank, and a hydrogen storage tank; the cycloolefin polymerization process is that the mass content of the cycloolefin in the polymerization kettle is 10-70%, and the cycloolefin undergoes a polymerization reaction in the polymerization kettle to generate a polymer ; The cycloolefin polymerization process is that the material from the polymerization kettle enters the hydrogenation reactor for hydrogenation reaction to generate cycloolefin polymer; the material from the hydrogenation reactor enters the devolatilization reactor to remove the solvent and unreacted monomer volatiles; the cycloolefin polymer from the devolatilization reactor enters the screw extruder, and the screw extruder is divided into at least 2-3 sections between the feed inlet and the outlet of the screw extruder, starting from the feed inlet, at least 1-2 sections in front are equipped with exhaust ports for vacuuming, further removing volatiles, and obtaining cycloolefin polymer; the raw material preparation process is the preparation of metal carbene catalyst, hydrogenation catalyst, solvent and cycloolefin monomer; The process is as follows: (1) Raw material preparation process: the raw materials are stored in storage tanks at room temperature, and the raw material storage tanks include a solvent storage tank, a monomer cycloolefin storage tank, a metal carbene catalyst storage tank, a hydrogenation catalyst storage tank and a hydrogen storage tank; the metal carbene catalyst is fed into the polymerization kettle by an injection pump; the monomer cycloolefin is fed into the polymerization kettle by a delivery pump, the polymerization temperature is 0-180° C., the stirrer speed is 10-80 rpm, and the average residence time is 5-60 min; the hydrogenation catalyst is fed into the hydrogenation reactor by an injection pump, the hydrogenation reaction temperature is 50-180° C., the reaction pressure is 3-10 MPa, the stirrer speed is 10-80 rpm, the average residence time is 3-15 hours, and the mass content of the cycloolefin polymer in the material is 3-40%; the solvent is fed into the metal carbene catalyst preparation kettle, the hydrogenation catalyst preparation kettle or the solvent preparation kettle by a delivery pump; the solvent preparation kettle prepares the solvent, and the delivery pump is used to feed the solvent into the polymerization kettle; Catalyst preparation: The catalyst is mixed with a metal carbene catalyst and an inert organic solvent in a catalyst preparation kettle at room temperature to 50° C., and stirred for 5-30 minutes; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof; Preparation of hydrogenation catalyst: The hydrogenation catalyst is mixed with an inert organic solvent in a hydrogenation catalyst preparation kettle at room temperature to 50° C., and stirred for 5-30 minutes; the hydrogenation catalyst is a Pd, Rh, Ru, Ni, Mo, Ir or Pt noble metal or metal carbene catalyst; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof; (2) Cycloolefin polymerization process: in a polymerization reactor, cycloolefin polymerization is catalyzed by a metal carbene catalyst, the cycloolefin polymerization temperature is 0-180° C., the polymerization pressure is 0.1-10 MPa, the polymerization time is 5 min-60 min, the molar ratio of cycloolefin to metal carbene catalyst is (50-1000000): 1, and the agitator speed is 5-60 rpm; (3) Hydrogenation reaction process: the material discharged from the polymerization reactor is fed into a hydrogenation reactor, and a hydrogenation reaction is carried out in the presence of a hydrogenation catalyst. The hydrogenation reaction temperature is 50-180° C., the hydrogenation reaction pressure is 3-10 MPa, and the hydrogenation reaction time is 0.5-10 hours. There are one, two or more hydrogenation reactors. (4) Devolatilization step: the material coming out of the hydrogenation reactor is fed into a devolatilization reactor; wherein the devolatilization is carried out by using a static film devolatilizer, a vertical or horizontal dynamic devolatilizer to remove the solvent and unreacted monomer volatiles; wherein the devolatilization operation temperature is 90-350°C, and the average residence time is 10-300 min; wherein the vertical or horizontal dynamic devolatilizer is equipped with a high-efficiency agitator, wherein the high-efficiency agitator is an agitator suitable for high-viscosity fluids, preferably an anchor agitator, a frame agitator, a ribbon agitator, a multi-zone reaction agitator or a surface renewal agitator, and the agitator speed is 5-60 rpm, thereby improving the removal effect of the solvent and the residual monomers to obtain a cycloolefin polymer; (5) Devolatilization extrusion granulation process: the cycloolefin polymer from the devolatilization reactor is fed into the feed port of the screw extruder, and the section between the feed port and the outlet of the screw extruder is divided into at least 2-3 sections. Starting from the feed port, at least 1-2 sections in front are equipped with exhaust ports for vacuuming to further remove volatile components in the material melt; additives are added to the front section of the screw extruder, wherein the additives are anti-aging agents or flame retardants, and the mass ratio of the additives to the cycloolefin polymer is (1-3): (100-10000); the screw extruder is divided into at least 2-3 sections between the feed port and the outlet, and the operating temperature of each section is different or the same, the operating temperature is 150-350° C., the extrusion time is 5-30 min, cold water cooling, pelletizing, drying, and the cycloolefin polymer pellets are sent to a silo through an air conveying pipeline, packaged, and sent to a warehouse by a conveyor belt.

2. The cycloolefin polymerization process according to claim 1, characterized in that: Metal carbene catalysts are used in polymerization reactors to catalyze the polymerization of C5-C 30 Cyclic olefin polymerization; wherein the C5-C 30 Cycloolefins are cycloolefin molecules containing one double bond, two double bonds or more than two double bonds, wherein the C5-C 30 Cycloolefins are cyclic olefins containing one double bond and one triple bond, wherein the C5-C 30 The cycloolefin is a cycloolefin molecule containing one or two or more heteroatoms; wherein the heteroatom is nitrogen, oxygen, halogen, selenium, sulfur, phosphorus, iron, copper, silver, gold, ruthenium, platinum, palladium or rhodium; wherein the metal carbene catalyst is a ruthenium carbene catalyst, a rhodium carbene catalyst, a platinum carbene catalyst, a palladium carbene catalyst, a vanadium carbene catalyst, a nickel carbene catalyst, a platinum carbene catalyst, a titanium carbene catalyst or a cobalt carbene catalyst; wherein the inert organic solvent is toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof.

3. The cycloolefin polymer and cycloolefin polymerization process and application according to claim 1, characterized in that: The material coming out of the polymerization kettle enters the hydrogenation reactor and undergoes a hydrogenation reaction under the action of a hydrogenation catalyst. The double bonds in the cycloolefin polymer molecules are converted into saturated bonds through the hydrogenation reaction. The hydrogenation catalyst is a precious metal or metal carbene catalyst such as Pd, Rh, Ru, Ni, Mo, Ir or Pt.

4. The cycloolefin polymer and cycloolefin polymerization process and application according to claim 1, characterized in that: The devolatilization process described in the period is to use a static film devolatilizer, a vertical or horizontal dynamic devolatilizer to remove the solvent and the unreacted monomer volatiles; wherein the devolatilization operation temperature is 90-350°C, the average residence time is 15-300min; the volume of the devolatilizer is 3L-100m 3 , preferably 3L-5m 3 , and preferably 5L-500L, stainless steel; wherein the vertical or horizontal dynamic devolatilization reactor is equipped with a high-efficiency agitator, wherein the high-efficiency agitator is an agitator suitable for high-viscosity fluids, preferably an anchor agitator, a frame agitator, a ribbon agitator, a multi-zone reaction agitator or a surface renewal agitator, and the agitator speed is 5-60 rpm.

5. The cycloolefin polymer and cycloolefin polymerization process and application according to claim 1, characterized in that: The devolatilization extrusion granulation process described in the present invention is to feed the cycloolefin polymer from the devolatilization kettle into the feed port of the screw extruder, and the area between the feed port and the outlet of the screw extruder is divided into at least 2-3 sections. Starting from the feed port, at least 1-2 sections in front are equipped with exhaust ports for vacuuming to further remove the volatile components in the material melt and obtain a product with low volatile content; an additive is added to the front section of the screw extruder, wherein the additive is an anti-aging agent or a flame retardant, and the mass ratio of the additive added to the cycloolefin polymer is (1-3): (100-10000); the screw extruder is divided into at least 2-3 sections between the feed port and the outlet, the operating temperature of each section is different or the same, the operating temperature is 150-350°C, the extrusion time is 5-30min, cold water cooling, room temperature pelletizing, centrifugal drying, and the cycloolefin polymer pellets are sent to the silo through the air delivery pipeline, packaged, and sent to the warehouse.

6. The cycloolefin polymerization process according to claim 1, characterized in that: Metal carbene catalyst was used to catalyze the polymerization of C5-C 20 Cycloolefin polymerization is carried out to obtain cycloolefin polymers with unsaturated bonds in the main chain; the material coming out of the polymerization kettle directly enters the hydrogenation reactor for hydrogenation reaction to obtain cycloolefin polymers, and the ROMP reaction is terminated in the hydrogenation reactor to regulate the molecular weight of the cycloolefin polymer.

7. Cycloolefin polymer and cycloolefin polymerization process and application, characterized in that: The applications of the cycloolefin polymers are for optical data storage, AI think tanks, AI devices, quantum communications, quantum computing, optical discs, lenses, prisms, carriers, films, covers and focusing plates of solar cells or for glass fibers; for medical prefilled syringes and medical testing consumables.

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