Method for preparing cyclic olefin copolymer using continuous flow integrated microreactor

Abstract

The present application relates to the field of polymer preparation, and provides a method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor, wherein an inner cavity of the integrated microreactor is sequentially provided with a catalyst pre-activation section and a polymerization section along a material flow direction, an inlet of the integrated microreactor is connected to the catalyst pre-activation section, and an outlet of the integrated microreactor is connected to the polymerization section; starting material for the reaction includes ethylene, a cyclic olefin monomer solution, a main catalyst solution and a cocatalyst solution; the main catalyst solution and the cocatalyst solution are mixed in the catalyst pre-activation section, and then enter the polymerization section to react with the ethylene and the cyclic olefin monomer solution, and finally the cyclic olefin copolymer is discharged from the outlet of the integrated microreactor.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polymer preparation, in particular to a method for efficiently preparing cyclic olefin copolymer by using continuous flow integrated microreactor. BACKGROUND

[0002] Cyclic olefin copolymer (COC) is a kind of copolymer of cyclic olefin monomer and α-olefin. Due to the introduction of cyclic structure in the main chain, COC has high transparency, excellent heat resistance, chemical stability, melt flowability and dimensional stability, etc., and is widely used in the manufacture of various optical lenses, automobile headlamps, optical films for LCD, contact lenses, etc. In addition, COC also has very low dielectric constant, which can be used for the manufacture of 5G communication materials and electronic and electrical components. At the same time, COC also becomes a new emerging medical and food packaging material due to its good moisture barrier property and easy disinfection. At present, the mainstream process route for preparing COC is based on traditional stirred tank reactor and homogeneous solution polymerization process. It should be pointed out that the homogeneous solution polymerization here refers to that the catalyst can be dissolved in the reaction system, and there is no solid catalyst in the polymerization system.

[0003] Japanese Borealis Plastics Corporation patent CN106232641A discloses a method for preparing olefin copolymer by using titanium metallocene metal catalyst in a kettle type stirred reactor. Although 1 g of the above titanium metallocene catalyst can obtain more than 1 kg of copolymer, the polymerization temperature is low (40℃), the polymerization time is long (1-5h), and the activity per unit time is low. Japanese Mitsui Oil Industries Corporation patent CN1131162A also aims to obtain higher polymer yield, with 1.8-4.8 kg of copolymer produced per millimole of main catalyst, reaction time of 60 minutes, and reaction temperature of 70℃. Chinese patent CN108752526 uses metallocene catalyst, catalyst concentration of 1-6×10 -5 mol / L, reaction temperature of 40-80℃, reaction time of 30 minutes, and activity of 1-17×10 6 g / mol Zr.h, with 2.9-8.5 kg of copolymer produced per millimole of main catalyst.

[0004] Tecknica Limited patent CN1245506A also uses metallocene catalyst to prepare cyclic olefin copolymer (ethylene-norbornene copolymer) in an autoclave. The reactants are ethylene and norbornene, the norbornene concentration is 30-80wt%, the catalyst is metallocene catalyst, the cocatalyst is alkylaluminoxane, and the amount is 1:1-10000, the polymerization temperature is 70℃, the pressure is 3-58 bar, and the polymerization time is generally 8-30 minutes. The activity of the patent is only 2×10 6The COC obtained per unit mass of the main catalyst is only 400 g / gZr.h, and in order to improve the catalyst efficiency, the method of prolonging the reaction time (1 h) is adopted. It needs to be noted that the high activity can be obtained only under high pressure of ethylene, and ethylene is a flammable and explosive gas, which can bring huge safety hazards to the high-pressure stirred tank reaction process. The technical scheme has low activity, and further has the following defects: the polymerization temperature is low; in order to maintain a certain activity, ethylene needs to be continuously fed, and the reaction time is long.

[0005] The above patents all adopt the stirred tank reactor, and the gas ethylene needs to be continuously fed into the solution to dissolve and participate in the reaction, so that there is a serious mass transfer problem. The mass transfer of the gas in the liquid can seriously affect the actual monomer ratio (the monomer ratio of ethylene and cycloolefin) in the polymerization reaction main body (liquid phase), thereby affecting the stability of the product quality and the composition distribution of the copolymer, and further seriously affecting the polymerization rate. According to the literature (Macromol. Mater. Eng. 2004, 289, 475-479), the metallocene catalyst has a half-life at high temperature, and gradually deactivates with the prolongation of the reaction time. In order to prevent the catalyst from deactivating, the general polymerization temperature range is 20-90℃, the polymerization temperature is low, the mass transfer is poor, the polymerization rate is low, and in order to obtain high economic benefits (high polymer yield), the polymerization reaction time is prolonged. The low temperature of the polymerization reaction system increases the viscosity of the reaction system, and further deteriorates the mass transfer and heat transfer effect of the reaction system. SUMMARY

[0006] The problem to be solved by the present application is to provide a method for preparing a cycloolefin copolymer by using a continuous flow integrated micro-reactor.

[0007] In order to solve the above technical problems, the present application provides a method for preparing a cycloolefin copolymer by using a continuous flow integrated micro-reactor:

[0008] The inner cavity of the integrated micro-reactor is sequentially provided with a catalyst pre-activation section and a polymerization section (the structures of the catalyst pre-activation section and the polymerization section can be the same or different) along the material flow direction, the inlet of the integrated micro-reactor is in communication with the catalyst pre-activation section, and the outlet of the integrated micro-reactor is in communication with the polymerization section,

[0009] The starting material of the reaction includes ethylene, a cycloolefin monomer solution, a main catalyst solution and a cocatalyst solution;

[0010] The main catalyst solution and the cocatalyst solution are mixed in the catalyst pre-activation section, and then enter the polymerization section to react together with the ethylene and the cycloolefin monomer solution, and finally the cycloolefin copolymer is discharged from the outlet of the integrated micro-reactor;

[0011] The temperature of the catalyst pre-activation section is 0-150°C, the temperature of the polymerization section is 60-200°C, the reaction pressure of the catalyst pre-activation section and the polymerization section is 1-200 bar, and the total residence time of the material in the catalyst pre-activation section and the polymerization section is ≤300 s;

[0012] The main catalyst is a catalyst containing metal atoms;

[0013] The cocatalyst is any one of alkyl aluminoxane or a composition consisting of alkyl aluminum and a boron-containing compound (as a ligand);

[0014] The molar ratio of ethylene: cyclic olefin monomer = 0.1-10:1 (preferably 0.2-8:1);

[0015] The molar ratio of the cyclic olefin monomer to the main catalyst is 4×10 4 -5×10 5 :1;

[0016] When the cocatalyst is alkyl aluminoxane, the molar ratio of Al in the alkyl aluminoxane to the metal atoms in the main catalyst is 100-2000:1 (preferably 300-1000:1);

[0017] When the cocatalyst is a composition consisting of alkyl aluminum and a boron-containing compound (as a ligand), the molar ratio of aluminum atoms in the alkyl aluminum: metal atoms in the main catalyst: boron atoms in the boron-containing compound = 50-2000:1:1-100 (preferably 100-1000:1:3-50, more preferably 300-500:1:5-10).

[0018] Note:

[0019] When the cocatalyst is alkyl aluminoxane, no boron-containing compound needs to be added; when the cocatalyst is alkyl aluminum, a boron-containing compound needs to be added.

[0020] The main catalyst needs to be activated with the cocatalyst, and the catalyst can be active, and the time is the pre-activation time of the catalyst.

[0021] Improvements of the method for preparing a cyclic olefin copolymer using a continuous flow integrated microreactor according to the present application:

[0022] The yield of the cyclic olefin copolymer is not less than 10 kg with respect to 1 g of the main catalyst, the number average molecular weight is 20,000-200,000 g / mol, and the glass transition temperature Tg is -10-220°C.

[0023] Further improvements of the method for preparing a cyclic olefin copolymer using a continuous flow integrated microreactor according to the present application: the cyclic olefin monomer is at least one of the compounds represented by the following structural formula:

[0024]

[0025]

[0026] In formulae (1) to (29), R1to R 108 are each independently selected from H, aliphatic hydrocarbon group or aromatic hydrocarbon group;

[0027] The aliphatic hydrocarbon group includes C1to C 20 hydrocarbon group;

[0028] The aromatic hydrocarbon group includes C6to C 10 aryl group.

[0029] As a preference, in formulae (1) to (29), R1to R 108 are each independently selected from C1to C 20 aliphatic hydrocarbon group or C6to C 10 aromatic hydrocarbon group.

[0030] As a further improvement of the method for preparing a cyclic olefin copolymer using a continuous flow integrated microreactor according to the present application:

[0031] The main catalyst is:

[0032] methylene-bis(cyclopentadienyl)zirconium dichloride, diphenylmethylene-bis(cyclopentadienyl)zirconium dichloride, isopropylene-bis(cyclopentadienyl)zirconium dichloride, biscyclopentadienylzirconium dichloride, biscyclopentadienylzirconium methyl, biscyclopentadienylzirconium diphenyl, biscyclopentadienylzirconium dibenzyl, biscyclopentadienylzirconium bistrimethylsilyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(l,2-dimethylcyclopentadienyl)zirconium dichloride, bis(l,3-dimethylcyclopentadienyl)zirconium dichloride, bis(l,2,4-trimethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(propylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconium dichloride, bisfluorenylzirconium dichloride, bisindenylzirconium dichloride, diphenylmethylene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, diphenylmethylene(9-indenyl)(cyclopentadienyl)zirconium dichloride, dimethylsilyl-bis(cyclopentadienyl)zirconium dichloride, dimethylsilyl-(9-fluorenyl)zirconium dichloride, dimethylsilyl-(9-indenyl)zirconium dichloride, isopropylidene-(9-fluorenyl)zirconium dichloride, isopropylidene-(9-indenyl)zirconium dichloride, ethylene-bis(l-indenyl)zirconium dichloride, ethylene-bis(l-fluorenyl)zirconium dichloride, ethylene-bis-l-(4,5,6,7-tetrahydroindenyl)zirconium dichloride, isopropyl-(cyclopentadienyl)zirconium dichloride, isopropyl-(3-methylcyclopentadienyl)zirconium dichloride, methylethylene-bis(l-fluorenyl)zirconium dichloride, methylphenylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, diphenylmethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropyl(9-fluorenyl)(l-(3-methylcyclopentadienyl))zirconium dichloride, dimethylsilyl(9-fluorenyl)(l-(3-methylcyclopentadienyl))zirconium dichloride, isopropyl(9-fluorenyl)(l-indenyl)zirconium dichloride, dimethylsilyl(9-fluorenyl)(l-indenyl)zirconium dichloride, (tert-butylamide)dimethyl-9-fluorenylsilane titanium dichloride, cyclopentadienyl(di-tert-butylamido)titanium dichloride, indenyl(2,6-diisopropylphenolato)titanium dichloride, dichloro[(l,2,3,4,5-η)-l-(l,l-dimethylethyl)-2,4-cyclopentadien-l-yl](2,2,4,4-tetramethyl-3-pentanediamido)titanium, (isopropylamide)dimethyl-9-fluorenylsilane titanium dimethyl, (tert-butylamide)dimethyl-9-fluorenylsilane titanium dimethyl, dichloro[Η(5):Η(l)-N-dimethyl(tetramethylcyclopentadienyl)silyl(tert-butyl)amide] titanium.

[0033] As a further improvement of the process for the preparation of a cycloolefin copolymer using a continuous flow integrated microreactor according to the present invention:

[0034] The alkylaluminoxane is preferably at least one of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane (EAO), isobutylaluminoxane (i-BAO);

[0035] The alkylaluminum is at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-sec-butylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, and other trialkylaluminums; diethylmethylaluminum, dimethylethylaluminum, monochlorodimethylaluminum, dichloromonomethylaluminum, monochlorodiethylaluminum, dichloro-monoethylaluminum, monochlorodi-n-propylaluminum, dichloro-n-propylaluminum, monochlorodiisobutylaluminum, dichloro-isobutylaluminum, monochlorodi-n-butylaluminum, dichloro-n-butylaluminum, monochlorodi-pentylaluminum, dichloro-pentylaluminum, monochlorodi-n-hexylaluminum, dichloro-n-hexylaluminum, monochlorodiisohexylaluminum, or dichloro-isohexylaluminum, and other chlorinated aluminums; dimethylaluminummethoxide, and other dialkylaluminum alkoxides. The alkylaluminum is preferably a trialkylaluminum, and particularly preferably at least one of trimethylaluminum, triethylaluminum, and triisobutylaluminum. Preferably, the alkylaluminum is used in combination with the boron-containing compound;

[0036] The boron-containing compound is selected from the group consisting of tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-tetrafluorophenyl)borane, tris(2,3,4-tetrafluorophenyl)borane, phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-tetrafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, tetrakis(2,3,4-tetrafluorophenyl)borate, phenylbis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylammonium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, and tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate. Of these, at least one of N,N-dimethylammonium tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, and triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate is preferred. Of these, N,N-dimethylammonium tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, and triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are particularly preferred.

[0037] As a further improvement of the method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor according to the present application:

[0038] As a preferred:

[0039] The temperature of the catalyst pre-activation section is 30-130℃, and the temperature of the polymerization section is 70-180℃;

[0040] The reaction pressure of the catalyst pre-activation section and the polymerization section is 2-120 bar, and the total residence time is 5-300 s;

[0041] As a further preferred:

[0042] The temperature of the catalyst pre-activation section is 80-100℃; and the temperature of the polymerization section is 80-160℃;

[0043] The reaction pressure of the catalyst pre-activation section and the polymerization section is 4-60 bar, and the total residence time is 20-200 s;

[0044] More preferably, the total residence time of the catalyst pre-activation section and the polymerization section is 30-100 s.

[0045] As a further improvement of the method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor according to the present application:

[0046] The solvents used for the cyclic olefin monomer solution, the main catalyst solution and the cocatalyst solution are all inert organic solvents;

[0047] The inert organic solvent is at least one of a linear aliphatic hydrocarbon, a branched aliphatic hydrocarbon, a substituted cyclic aliphatic hydrocarbon, an unsubstituted cyclic aliphatic hydrocarbon, a substituted aromatic hydrocarbon, and an unsubstituted aromatic hydrocarbon.

[0048] As a further improvement of the method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor according to the present application:

[0049] The inert solvent is hexane, heptane, cyclohexane, cyclooctane, toluene, or xylene.

[0050] As a further improvement of the method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor according to the present application:

[0051] In the cyclic olefin monomer solution, the mass fraction of the cyclic olefin monomer is 5wt%-90wt%, and further preferably 10wt%-80wt%.

[0052] Note: The amount of the solvent in the main catalyst solution and the cocatalyst solution only needs to ensure that the main catalyst and the cocatalyst are dissolved.

[0053] As a further improvement of the method for preparing cycloolefin copolymer by using continuous flow integrated microreactor according to the application:

[0054] The catalyst feeding port is arranged in the catalyst pre-activation section, and the main catalyst solution and the cocatalyst solution enter the catalyst pre-activation section from the catalyst feeding port;

[0055] The raw material inlet is arranged at the joint of the catalyst pre-activation section and the polymerization section, and the ethylene and the cycloolefin monomer solution enter the polymerization section from the raw material inlet.

[0056] Description: There are two raw material inlets, and the ethylene and the cycloolefin monomer solution enter the polymerization section through the corresponding raw material inlet respectively;

[0057] The catalyst feeding port is at least one; when the catalyst feeding port is one, the main catalyst solution and the cocatalyst solution are pre-mixed and then enter through the same feeding port; otherwise, when the catalyst feeding port is multiple, the main catalyst solution and the cocatalyst solution enter the catalyst pre-activation section through the corresponding catalyst feeding port respectively.

[0058] The present application provides a method for efficiently preparing cycloolefin copolymer by using continuous flow integrated microreactor, which realizes the efficient preparation of cycloolefin copolymer by microreactor, and the catalyst is not easy to be deactivated even at high temperature, has high catalytic efficiency, can obtain high polymer yield in a very short time, is safe, fast, composition controllable, efficient, flexible, stable and easy to mass production.

[0059] In the present application, the cycloolefin monomer is preferably as follows:

[0060] The cyclic olefin monomer can be one or more of the following: bicyclo[2,2,1]hept-2-ene, 5-methylbicyclo[2,2,1]hept-2-ene, 5-ethylbicyclo[2,2,1]hept-2-ene, 5- propylbicyclo[2,2,1]hept-2-ene, 5-butylbicyclo[2,2,1]hept-2-ene, 5-hexylbicyclo[2,2,1]hept-2- ene, 5-decylbicyclo[2,2,1]hept-2-ene, 5-methyl-5-ethylbicyclo[2,2,1]hept-2-ene, 5- fluorobicyclo[2,2,1]hept-2-ene, 5-chlorobicyclo[2,2,1]hept-2-ene, 5,6-dimethylbicyclo[2,2,1]hept- 2-ene, 5-phenylbicyclo[2,2,1]hept-2-ene, 5-cyclohexylbicyclo[2,2,1]hept-2-ene, 5-cycloethyl- bicyclo[2,2,1]hept-2-ene, 5-cyclooctylbicyclo[2,2,1]hept-2-ene, 5-indenylbicyclo[2,2,1]hept-2- ene, tetracyclo[4,4,0,1,1]dodec-4-ene, 8-methyltetracyclo[4,4,0,1,1]dodec-3-ene, 8- ethyltetracyclo[4,4,0,1,1]dodec-3-ene, bicyclo[2,2,1]hepta-2,5-diene, 5-methylbicyclo[2,2,1]hepta- 2,5-diene, 5-ethylbicyclo[2,2,1]hepta-2,5-diene, 5-propylbicyclo[2,2,1]hepta-2,5-diene, 5- butylbicyclo[2,2,1]hepta-2,5-diene, 5-hexylbicyclo[2,2,1]hepta-2,5-diene, 5-decylbicyclo[2,2,1]hepta- 2,5-diene, 5-methyl-5-ethylbicyclo[2,2,1]hepta-2,5-diene, 5-fluorobicyclo[2,2,1]hepta-2,5- diene, 5-chlorobicyclo[2,2,1]hepta-2,5-diene, 5,6-dimethylbicyclo[2,2,1]hepta-2,5-diene, 5- phenylbicyclo[2,2,1]hepta-2,5-diene, 5-cyclohexylbicyclo[2,2,1]hepta-2,5-diene, 5-cyclohexyl- bicyclo[2,2,1]hepta-2,5-diene, 5-cyclooctylbicyclo[2,2,1]hepta-2,5-diene, 5-indenylbicyclo[2,2,1]hepta- 2,5-diene, tetracyclo[4,4,0,1,1]dodeca-2,5-diene, 8-methyltetracyclo[4,4,0,1,1]dodeca-2,5- diene, 8-ethyltetracyclo[4,4,0,1,1]dodeca-2,5-diene, tricyclo[4,3,0,1]dec-3-ene, 1-1] dec-3-ene, 9-ethyltricyclo[4,3,0,1]dec-3-ene, 10-methyltricyclo[4,3,0,1]dec-3-ene, 10- ethyltricyclo[4,3,0,1]dec-3-ene, 10-phenyltricyclo[4,3,0,1]dec-3-ene, 10-cyclohexyltricyclo[4,3,0,1]dec-3-ene, tricyclo[4,2,0,1]non-3-ene, 2-methyltricyclo[4,2,0,1]non-3-ene, 7-methyltricyclo[4,2,0,1]non-3-ene, tricyclo[4,4,0,1]undec-3-ene, 1-methyltricyclo[4,4,0,1]undec-3-ene, 2-methyltricyclo[4,4,0,1]undec-3-ene, 2-ethyltricyclo[4,4,0,1]undec-3-ene, 8-methyltricyclo[4,4,0,1]undec-3-ene, tricyclo[6,4,0,1]tridec-3-ene, 2-methyltricyclo[6,4,0,1]tridec-3-ene, 8-methyltricyclo[6,4,0,1]tridec-3-ene, tricyclo[4,3,0,1]dec-3,7-diene, 1-methyltricyclo[4,3,0,1]dec-3,7-diene, 2-methyltricyclo[4,3,0,1]dec-3,7-diene, 2-ethyltricyclo[4,3,0,1]dec-3,7-diene, 5-methyltricyclo[4,3,0,1]dec-3,7-diene, 6-methyltricyclo[4,3,0,1]dec-3,7-diene, 6-ethyltricyclo[4,3,0,1]dec-3,7-diene, 10-methyltricyclo[4,3,0,1]dec-3,7-diene, 10-ethyltricyclo[4,3,0,1]dec-3,7-diene, 10-phenyltricyclo[4,3,0,1]dec-3,7-diene, 10-cyclohexyltricyclo[4,3,0,1]dec-3,7-diene, tricyclo[4,4,0,1]undec-3,7-diene, 1-methyltricyclo[4,4,0,1]undec-3,7-diene, 2-methyltricyclo[4,4,0,1]undec-3,7-diene, 2-ethyltricyclo[4,4,0,1]undec-3,7-diene, 7-chlorotricyclo[4,4,0,1]undec-3,7-diene, 7-fluorotricyclo[4,4,0,1]undec-3,7-diene, 8-methyltricyclo[4,4,0,1]undec-3,7-diene, tricyclo[4,4,0,1]undec-3,8-diene, 1-methyltricyclo[4,4,0,1]undec-3,8-diene, 2-methyltricyclo[4,4,0,1]undec-3,8-diene, 2-ethyltricyclo[4,4,0,1]undec-3,8-diene, 8-methyltricyclo[4,4,0,1]undec-3,8-diene, tricyclo[6,4,0,1]tridec-3,11-diene, 2-methyltricyclo[6,4,0,1]tridec-3,11-diene, 8-methyltricyclo[6,4,0,1]tridec-3,11-diene,1] trideca-3,10-diene, 2-methyltricyclo[6,4,0,1]trideca-3,10-diene, 8-methyltricyclo[6,4,0,1]trideca-3,10-diene, tricyclo[6,4,0,1]trideca-3,9-diene, 2-methyltricyclo[6,4,0,1]trideca-3,9-diene, 9-methyltricyclo[6,4,0,1]trideca-3,9-diene, 3a,4,4a,5,8,8a,9,9a-octahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 1-methyl-3a,4,4a,5,8,8a,9,9a-octahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 2-methyl-3a,4,4a,5,8,8a,9,9a-octahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 3-methyl-3a,4,4a,5,8,8a,9,9a-octahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 2,3,3a,4,4a,5,8,8a,9,9a-decahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 1-methyl-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 2-methyl-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-4,9:5,8-dimethano-1H-benzo[F]indene, 3-methyl-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-4,9:5,8-dimethano-1H-benzo[F]indene, (12R)-10,11,12,13,14,17-hexahydro-9H-9,10-[2]bicyclophenanthrene, (12R)-1-methyl-10,11,12,13,14,17-hexahydro-9H-9,10-[2]bicyclophenanthrene, (12R)-2-methyl-10,11,12,13,14,17-hexahydro-9H-9,10-[2]bicyclophenanthrene, (12R)-3-methyl-10,11,12,13,14,17-hexahydro-9H-9,10-[2]bicyclophenanthrene, (12R)-4-methyl-10,11,12,13,14,17-hexahydro-9H-9,10-[2]bicyclophenanthrene, 1,4,4a,5,8,8a,9,9a,10,10a-hexahydro-1,4:5,8-dimethylbridgedanthracene, 2-methyl-1,4,4a,5,8,8a,9,9a,10,10a-hexahydro-1,4:5,8-dimethylbridgedanthracene, 9-methyl-1,4,4a,5,8,8a,9,9a,10,10a-hexahydro-1,4:5,8-dimethylbridgedanthracene, 2-methyl-1,2,3,4,4a,5,8,8a,9,9a,10,10a-hexahydro-1,4:5,8-dimethylbridgedanthracene, 9-methyl-1,2,3,4,4a,5,8,8a,9,9a,10,10a-hexahydro-1,4:5,8-dimethyl bridged anthracene, 1,4-dihydro-1,4-methylnaphthalene, 1,2,3,4,4a,4b,5,8,8a,8b-decahydro-1,4:5,8-dimethyl biphenyl, 1,4,4a,8b-tetrahydro-1,4-dimethyl biphenyl, 2',3'-dibispiro[bi[2.2.1]hept[5]ene-2,1'-indene], 2',3,3',4,4a,5,8,8a-octahydro-1H-spiro[1,4:5,8-dimethyl bridged naphthalene-2,1'-indene].

[0061] The main catalyst is preferably at least one of diphenyl methylene-bis(cyclopentadienyl) zirconium dichloride, isopropylene-bis(cyclopentadienyl) zirconium dichloride, ethylene-bis(1-indenyl) zirconium dichloride, (dichloro[Η(5):Η(1)-N-dimethyl(tetramethylcyclopentadienyl) silyl(t-butyl) amide] titanium.

[0062] Different cyclic olefin monomers have structural differences, which will cause the physical and chemical properties of the main catalyst, cocatalyst, solvent and product required for synthesis to be different. In order to take into account the differences in physical properties and reaction activity of the materials involved in the preparation of different cyclic olefin copolymers, the present application designs a set of continuous flow integrated microreactors. Using the reactor to synthesize different cyclic olefin copolymers, only the process conditions and parameters need to be adjusted, including the division and setting of the temperature of each section, the concentration of the material, the ratio of the material, the flow rate of the material, the reaction pressure, so that they can work in coordination, that is, the integrated microreactor has flexible applicability for different cyclic olefin monomer copolymerization reactions.

[0063] The microreactor of the present application not only includes the narrow sense of microreactor (a kind of reaction material continuously flows in the micro channel, reacts, and at the same time realizes heat exchange. The equipment is generally biased to the limited area of the size of 1mm and below to realize the characteristics of short intermolecular diffusion distance, high mass transfer efficiency, large specific surface area and high heat transfer efficiency. The most typical form of such limited area is a micro-sized channel), but also includes all tubular reactors that can realize high-efficiency heat exchange and mass transfer. The size of the pipe diameter channel can be up to 50mm (for example, tubular reactors with static mixers, etc.). The microreactor can use single or multiple, or be connected in series or parallel. Preferably, the channel size of the continuous flow integrated microreactor is 0.5-50mm.

[0064] In the process of the present application, the following problems are fully considered:

[0065] When the heterogeneous reaction is carried out in the traditional stirred tank reactor for industrial scale-up, although the feeding mode and feeding sequence can be kept the same as the small test, in the microcosmic state, due to the great difference in mass transfer and heat transfer from the small test, the local concentration and temperature are difficult to reach the same as the small test, which causes distortion in the industrial scale-up, which is called scale-up effect in industry. In the microreactor, because the mass transfer and heat transfer are good enough, the mass transfer and heat transfer can be kept the same as the small test in the scale-up, so as to realize the direct scale-up from the laboratory to the industrialization.

[0066] For the traditional stirred tank reactor, due to the low polymerization activity, in order to maximize the economic benefit (i.e. more polymer per unit mass of catalyst), the reaction time will be relatively long. On the other hand, it is also found that when the traditional stirred tank reactor is used for high-temperature polymerization, gelation caused by local over-high temperature and local over-fast reaction will occur, which seriously affects the quality of the polymer.

[0067] The solution of the present application does not have the scale-up effect, greatly reduces the difficulty of industrial application, and can be scaled up to the required production scale at one time without the complicated and complex multiple step-by-step scale-up and adjustment and optimization of process conditions and parameters, greatly saving the cost and project development time; in the industrial production, multi-species cyclic olefin copolymer can be prepared in the same reactor according to the market, the product quality is stable, and the safety is good. The production process of the present application not only can carry out the reaction at a temperature much higher than that of the tank reactor, but also can ensure a very high production efficiency. It can be seen that the production process of the present application breaks through the limitation of the prior art, successfully realizes the high efficiency (high activity and high yield) and multi-species synthesis of cyclic olefin copolymer, and is very suitable for industrial production.

[0068] For the preparation of the cyclic olefin copolymer described in the present application, there is also an important factor of viscosity effect, especially for the gas-liquid two-phase polymerization reaction in the present application, the viscosity not only seriously hinders the efficiency of the monomer entering the catalyst active center, reduces the reaction rate, but also greatly reduces the heat transfer efficiency, and seriously causes the generation of reaction "hot spot", which seriously affects the product quality stability. Higher temperature can effectively reduce the viscosity of the reaction system. However, for the traditional tank reactor, the reaction temperature is not only limited by the boiling point of the solvent used in the reaction (the reaction temperature is generally lower than the boiling point of the solvent), but also limited by the gradual deactivation of the catalyst at high temperature. Therefore, limited by the viscosity of the reaction system, the content of the polymer in the single tank of the traditional tank reactor is limited in the actual industrial production.

[0069] The application innovatively proposes a novel micro-reactor preparation process of cyclic olefin copolymer, which can prepare cyclic olefin copolymers with different structures and properties according to different cyclic olefin monomers by flexibly adopting the same or different process parameters, is flexible in operation and has a wide application range. Moreover, the ultra-high activity (the activity can reach 1×10 9 g mol -1 M -1 h -1 above) of the catalyst can be maintained for various cyclic olefin monomers, the reaction time is short (not more than 300 s), and the amount of the obtained cyclic olefin copolymer is more than 10 kg relative to 1 g of the metal catalyst, the number average molecular weight of the copolymer is 20000-200000 g / mol, and the Tg of the polymer is-10-220℃.

[0070] Compared with the prior art, the application mainly has the following technical advantages:

[0071] 1) The application innovatively realizes controllable and efficient preparation of cyclic olefin copolymer in a micro-reactor. With the precise regulation of reaction temperature, pressure and residence time by the micro-reactor, not only the copolymerization of different types of cyclic olefin monomers is realized, but also the composition and performance of the copolymer are widely regulated; meanwhile, by virtue of the excellent mass and heat transfer characteristics of the micro-channel reactor, the reaction rate can be greatly accelerated, and the efficiency of the process is greatly improved, and the total residence time of the reaction is not more than 300 s.

[0072] 2) The application adopts a micro-reactor, greatly improves the gas-liquid mass transfer efficiency, and greatly improves the activity of the catalyst by adding ethylene at one time, and in a short time, not only a very high activity (the activity can reach 1×10 9 g mol - 1 M -1 h -1 above) is obtained, but also more than 10 kg of copolymer per unit mass (1 g) of catalyst is obtained, and the molecular weight of the polymer can be ensured to be 20000-200000 g / mol.

[0073] 3) The safety of the process is greatly improved, the good heat transfer efficiency of the micro-reactor can timely remove the heat released during polymerization, so that the process is safer. In addition, the reaction can be carried out at a higher reaction temperature than the traditional kettle process, which greatly accelerates the reaction rate and shortens the reaction time, avoids the catalyst deactivation caused by sudden local temperature rise and other adverse phenomena, and also solves the product stability problem caused by the deactivation of the catalyst exposed to high temperature for a long time.

[0074] 4) The present application develops a highly integrated one-piece micro-reactor with flexible applicability for different cyclic olefin monomers. With the one-piece micro-reactor, the synthesis process of cyclic olefin copolymer containing different cyclic olefin monomers can be realized by making targeted adjustments to the process conditions and parameters, including the settings of temperature, pressure, material concentration, material ratio and material flow rate, so that they work in coordination and match the reaction.

[0075] 5) No amplification effect, i.e. the process is completed in a short time on an industrial scale, and the activity of the catalyst, the composition and properties of the polymer are basically the same as in the laboratory scale.

[0076] 6) The integrated micro-reactor provided by the present application is simple to operate and has good stability.

[0077] 7) The catalyst of the method of the present application is not easy to deactivate, has high utilization rate, is safe, fast, controllable in composition, efficient, flexible, stable and easy to mass-produce.

[0078] In summary, the present application innovatively realizes the preparation of COC at high temperature and high activity in a micro-reactor. The main difference between the present application and the prior art is that:

[0079] 1. The preparation of COC at high temperature and high activity is realized, and the limitation of low solid content (polymer content) in traditional processes is broken (in traditional reactors, high-temperature polymerization cannot be realized due to the limitation of catalyst, resulting in low solid content);

[0080] 2. The Tg of the polymer can be easily controlled in a large range;

[0081] 3. In order to prevent the safety problems caused by too fast reaction and too large heat release, the traditional stirred tank process adopts continuous feeding of ethylene. A large amount of ethylene gas is difficult to mix uniformly with the reaction liquid in a short time, which affects the composition of the polymer;

[0082] 4. Suitable for a variety of different monomers. BRIEF DESCRIPTION OF DRAWINGS

[0083] Figure 1 is a process flow diagram for the continuous synthesis process in the embodiments of the present application;

[0084] Figure 2 is a schematic diagram of the continuous flow one-piece micro-reactor. DETAILED DESCRIPTION

[0085] The following detailed description of the embodiments of the present application is given on the premise of the technical solutions of the present application, and detailed implementation manners and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0086] Embodiment 1: A method for preparing a cyclic olefin copolymer by using a continuous flow integrated microreactor, the integrated microreactor comprising a catalyst pre-activation section (pre-heating section) and a polymerization section arranged in sequence along the material flow direction, ethylene, a cyclic olefin monomer solution, a main catalyst solution and a co-catalyst solution continuously flow through the catalyst pre-activation section and the polymerization section of the continuous flow integrated microreactor at constant flow rates, the catalyst is pre-activated in the pre-activation section, the polymerization section is reacted, the discharge is obtained, the reaction liquid obtained by the discharge is precipitated in acidified ethanol, and then filtered and dried to obtain the cyclic olefin copolymer.

[0087] The specific structure of the integrated microreactor is as follows:

[0088] Three feed inlets are arranged on the side wall of the catalyst pre-activation section (pre-heating section) for continuously feeding the main catalyst solution, the co-catalyst 1 solution and the co-catalyst 2 solution, respectively, and the ethylene and the cyclic olefin monomer solution enter the integrated microreactor from the connection between the catalyst pre-activation section (pre-heating section) and the polymerization section.

[0089] The mass flow rate of ethylene is set to 0.6 g / min, the concentration of the cyclic olefin monomer solution is 40 wt%, toluene is used as the solvent, the mass flow rate is 5.0 g / min, and the cyclic olefin monomer is ① described in Table 1; therefore, the molar ratio of ethylene / cyclic olefin monomer is 1.0.

[0090] The main catalyst solution is a toluene solution of ethylene-bis(1-indenyl)zirconium dichloride (code c) with a concentration of 4×10 -5 mol / L, the co-catalyst 1 is a toluene solution of triisobutylaluminum with a concentration of 1.2×10 -2 mol / L, and the co-catalyst 2 is a toluene solution of triphenylmethyl tetra(pentafluorophenyl)borate with a concentration of 1.2×10 -4 mol / L, the molar ratio of the ethylene-bis(1-indenyl)zirconium dichloride (code c), the triisobutylaluminum and the triphenylmethyl tetra(pentafluorophenyl)borate is 1:300:3, and the mass flow rate of the main catalyst solution, the mass flow rate of the co-catalyst 1 solution and the mass flow rate of the co-catalyst 2 solution are all 2.5 g / min.

[0091] The temperature of the pre-activation section is 70°C, the temperature of the polymerization section is 90°C, the reaction pressure is 6 bar, and the total reaction time is 60 s. The total reaction time is the total time of the pre-activation section and the polymerization section, and specifically, the pre-activation time (residence time) of the catalyst in the pre-activation section is 20 s.

[0092] The reaction liquid flowing out from the end of the polymerization section undergoes conventional post-processing to obtain a cyclic olefin copolymer.

[0093] Post-treatment could be as follows: Collect the reaction solution from the outlet for 5 minutes and precipitate it in 0.5 L of 5% (v / v) hydrochloric acid-acidified ethanol with stirring (precipitating while stirring), then filter, and dry the resulting filter cake (drying at 80°C to constant weight) to obtain the cyclic olefin copolymer. The final cyclic olefin copolymer is named ethylene-norbornene copolymer; the yield is 59.0%, and the activity (10) 6 gmol -1 M -1 h -1 The value is 989.

[0094] Note: Yield = Polymer [g] as product / (Mass of metallocene as main catalyst [g])

[0095] Activity = Polymer [g] / (Time [h] × Mass of main catalyst metallocene [g])

[0096] Examples 2 to 10, Comparative Examples 1 to 2:

[0097] Change the reaction parameters (including the ratio of raw materials), and refer to Example 1 for the rest.

[0098] The cyclic olefin monomers are listed in Table 1. The raw material ratios, reaction parameters and results, and polymer structures and characteristics are shown in Tables 2 to 4, respectively. The main catalysts in Table 2 refer to the following: a) methylphenylsilyl(9-indenyl)(cyclopentadienyl)zirconia; b) isopropene-bis(cyclopentadienyl)zirconia; c) ethylene-bis(1-indenyl)zirconia; d) dichloro[H(5):H(1)-N-dimethyl(tetramethylcyclopentadienyl)silyl(tert-butyl)amide]titanium.

[0099] Table 1

[0100]

[0101] Table 2. Raw Material Ratio

[0102]

[0103]

[0104]

[0105] Table 3 Reaction parameters and results

[0106]

[0107] Table 4 Polymer Structure and Characteristics

[0108]

[0109]

[0110] According to the comparison of Comparative Examples 1-2 and Inventive Examples 1 and 2, it is shown that the low polymerization section temperature leads to the following disadvantages:

[0111] The Tg variation (ΔTg) of the polymer is wide, the composition distribution is wide, the melting point can occur, and the transparency of the polymer is poor.

[0112] Comparative Example 1, compared to Inventive Example 1, the microreactor is replaced by a traditional stirred tank reactor; the details are as follows:

[0113] A 100 mL stirred tank reactor is used. 25.2 mL of dry norbornene toluene solution with a concentration of 5 mol / L is added to 50.8 mL of refined toluene, and the solution is added to the reactor which is previously flushed with nitrogen. The solution is saturated with ethylene by multiple punches (6 bar). At a temperature of 90°C, 6 bar and stirring (300 r / min) (under the conditions, E / NB = 1:1), triisobutyl aluminum toluene solution, Ph3CB(C6F5)4hexane solution and main catalyst ethylene-bis(1-indenyl)zirconium dichloride solution are sequentially added to start the polymerization, wherein Al:Zr:B (mol / mol / mol) = 300:1:3; the polymerization process is controlled by supplementing the metering of inert gas nitrogen to control the pressure at 6 bar.

[0114] After 60 seconds of reaction, the reaction solution is precipitated in acidified ethanol, then filtered and dried to obtain a cyclic olefin copolymer, 0.63 g of polymer is obtained, the catalyst activity is 1.2 x 10 7 g / (mol Zr·h), the polymer mass per unit mass of main catalyst is 0.9 kg.P / cat.g, the weight average molecular weight is 122500 g / mol, the molecular weight distribution is 3.8, the cyclic olefin monomer content in the polymer is 38.7%, the polymer Tg is 104.6°C and the ΔTg is 21.7°C, and the light transmittance is 74%.

[0115] The defects of this Comparative Example 1 relative to Inventive Example 1 are that the catalyst activity is greatly reduced after the continuous flow microreactor is replaced by a tank reactor, the molecular weight distribution is widened, the glass transition temperature range of the copolymer is widened, the composition drift is serious, and the light transmittance of the film prepared from the obtained copolymer is low.

[0116] Comparative Example 2, compared to Inventive Example 2, the microreactor is replaced by a traditional stirred tank reactor; the details are as follows:

[0117] A 100 ml stirred tank reactor was used. 6.4 ml of dry norbornene toluene solution with a concentration of 5 mol / L was added to 69.6 ml of refined toluene, and the solution was added to the reactor which was previously flushed with nitrogen, and the solution was saturated with ethylene by multiple punches (10 bar). At a temperature of 100℃, 10 bar and stirring (300 r / min), E / NB = 6:1, triisobutyl aluminum toluene solution, Ph3CB(C6F5)4hexane solution and main catalyst ethylene-bis(1-indenyl)zirconium dichloride solution were sequentially added to start polymerization, wherein Al:Zr:B (mol / mol / mol) = 100:1:5; the polymerization process was controlled by supplementing the metering of inert gas nitrogen, and the pressure was 10 bar.

[0118] After 20 seconds of reaction, the reaction solution was precipitated in acidified ethanol, and then filtered and dried to obtain a cyclic olefin copolymer, 0.52 g of polymer was obtained, and the catalyst activity was 2.8 x 10 7 g / (mol Zr·h), the polymer mass per unit mass of main catalyst was 0.35 kg.P / cat.g, the weight average molecular weight was 75700 g / mol, the molecular weight distribution was 2.8, the cyclic olefin monomer content in the polymer was 15.8%, the polymer Tg was 8.2℃ and △Tg was 15.8℃, the melting point Tm was 122.6℃, and the light transmittance was 62%.

[0119] This comparative example 2 has the defects that the catalyst activity is greatly reduced, the molecular weight distribution is widened, and the copolymer has a melting point after the continuous flow microreactor is replaced by a tank reactor, so that the transparency of the copolymer film is seriously reduced.

[0120] It can be seen that the microreactor described in the present application has a wide range of applications, and is suitable for different types of cyclic olefin monomers, and can maintain high catalytic activity and yield at a higher temperature and a short reaction time, and the copolymer composition and structure can be widely regulated.

[0121] Finally, it should be noted that the above enumeration is only a few specific embodiments of the present application. Obviously, the present application is not limited to the above embodiments, and many modifications can be made. All modifications that can be directly derived or inferred by those of ordinary skill in the art from the disclosure of the present application should be considered as falling within the scope of protection of the present application.

Claims

1. A method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor, characterized in that: The integrated microreactor has a catalyst pre-activation section and a polymerization section arranged sequentially along the material flow direction inside its cavity. The inlet of the integrated microreactor is connected to the catalyst pre-activation section, and the outlet of the catalyst pre-activation section is connected to the polymerization section. The starting materials for the reaction include ethylene, cyclic olefin monomer solution, main catalyst solution and co-catalyst solution; the main catalyst solution and co-catalyst solution are mixed in the catalyst pre-activation section, and then enter the polymerization section together with the ethylene and cyclic olefin monomer solution to react, and the cyclic olefin copolymer is discharged from the outlet of the integrated microreactor; The temperature of the catalyst pre-activation section is 0-150℃, the temperature of the polymerization section is 60-200℃, the reaction pressure of the catalyst pre-activation section and the polymerization section is 1-200 bar, and the total residence time of the material in the catalyst pre-activation section and the polymerization section is ≤300s; The main catalyst is a catalyst containing metal atoms; The cocatalyst is any one of the following: alkylaluminoxane, or a combination of alkylaluminum and boron-containing compounds; The molar ratio of ethylene to cyclic olefin monomers is 0.2 to 8:1; The molar ratio of cyclic olefin monomers to the main catalyst is 4 × 10⁻⁶. 4 ~5×10 5 :1; When an alkylaluminoxane is selected as the co-catalyst, the molar ratio of Al in the alkylaluminoxane to the metal atoms in the main catalyst is 300 to 1000:

1. When the co-catalyst is a combination of alkylaluminum and boron-containing compounds, the molar ratio of aluminum atoms in the alkylaluminum to metal atoms in the main catalyst to boron atoms in the boron-containing compound is 300-500:1:5-10. The cyclic olefin monomer is at least one of the compounds shown in the following structural formulas: In equations (1) to (29), R1 to R 108 Each group is independently selected from H, aliphatic hydrocarbon groups, or aromatic hydrocarbon groups; the aliphatic hydrocarbon groups include C1 to C2 groups. 20 hydrocarbon group; The aromatic hydrocarbon group includes C6 to C6. 10 Aryl groups.

2. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 1, characterized in that: Relative to 1g of main catalyst, the yield of cyclic olefin copolymer is not less than 10kg, the number average molecular weight is 20000~200000g / mol, and the glass transition temperature Tg is -10~220℃.

3. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 2, characterized in that: The main catalyst is: Methylene-bis(cyclopentadienyl)zirconia, diphenylmethylene-bis(cyclopentadienyl)zirconia, isopropene-bis(cyclopentadienyl)zirconia, biscyclopentadienylzirconia, biscyclopentadienylmethylzirconia, biscyclopentadienyldiphenylzirconia, biscyclopentadienyldibenzylzirconia, biscyclopentadienylbistrimethylsilylzirconia, bis(methylcyclopentadienyl)zirconia, bis(1,2-dimethylcyclopentadienyl)zirconia, bis(1,3-dimethylcyclopentadienyl)zirconia, bis(1,2,4-trimethylcyclopentadienyl)zirconia, bis(pentamethylcyclopentadienyl)zirconia, bis(ethylcyclopentadienyl)zirconia, bis... (propylcyclopentadienyl)zirconia dichloride, bis(butylcyclopentadienyl)zirconia dichloride, bisfluorenylzirconia dichloride, bisindenylzirconia dichloride, diphenylmethylene(9-fluorenyl)(cyclopentadienyl)zirconia dichloride, diphenylmethylene(9-indenyl)(cyclopentadienyl)zirconia dichloride, dimethylsilyl-bis(cyclopentadienyl)zirconia dichloride, dimethylsilyl-(9-fluorenyl)zirconia dichloride, dimethylsilyl-(9-indenyl)zirconia dichloride, isopropylidene-(9-fluorenyl)zirconia dichloride, isopropylidene-(9-indenyl)zirconia dichloride, ethylene-bis(1-indenyl)zirconia dichloride, ethylene-bis(1-fluorenyl)zirconia dichloride, ethylene-bis-1 -(4,5,6,7-tetrahydroindenyl)zirconia dichloride, isopropyl-(cyclopentadienyl)zirconia dichloride, isopropyl-(3-methylcyclopentadienyl)zirconia dichloride, methyl ethylidene-bis(1-fluorenyl)zirconia dichloride, methylphenyl divalent carbonyl(9-fluorenyl)(cyclopentadienyl)zirconia dichloride, diphenylmethylsilyl(9-fluorenyl)(cyclopentadienyl)zirconia dichloride, isopropyl(9-fluorenyl)(1-(3-methylcyclopentadienyl))zirconia dichloride, dimethylsilyl(9-fluorenyl)(1-(3-methylcyclopentadienyl))zirconia dichloride, isopropyl(9-fluorenyl)(1-indenyl)zirconia dichloride, dimethylsilyl(9-fluorenyl)(1- At least one of the following: indene(zirconium dichloride), (tert-butylamide)dimethyl-9-fluorenylsilane titanium dichloride, cyclopentadienyl(di-tert-butylamino) titanium dichloride, indene(2,6-diisopropylphenolyl) titanium dichloride, dichloro[(1,2,3,4,5-η)-1-(1,1-dimethylethyl)-2,4-cyclopentadien-1-yl](2,2,4,4-tetramethyl-3-pentanediamine) titanium, (isopropylamide)dimethyl-9-fluorenylsilane dimethyl titanium, (tert-butylamide)dimethyl-9-fluorenylsilane dimethyl titanium, and dichloro[H(5):H(1)-N-dimethyl(tetramethylcyclopentadienyl)silyl(tert-butyl)amide] titanium.

4. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 3, characterized in that: The alkylaluminoxane is at least one of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane (EAO), and isobutylaluminoxane (i-BAO); The alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, trisec-butylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, diethylmethylaluminum, dimethylaluminum, dichlorodimethylaluminum, dichlorodiethylaluminum, dichlorodiethylaluminum, dichlorodi-n-propylaluminum, dichlorodiisobutylaluminum, dichlorodiisobutylaluminum, dichlorodi-n-butylaluminum, dichlorodipentylaluminum, dichlorodi-n-hexylaluminum, dichlorodiisohexylaluminum, dichlorodiisohexylaluminum, and dimethylmethoxide aluminum. The boron-containing compound is selected from tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-tetrafluorophenyl)borane, tris(2,3,4,-tetrafluorophenyl)borane, phenylbis(pentafluorophenyl)borane, tetra(pentafluorophenyl)borate, tetra(2,3,5,6-pentafluorophenyl)borate, tetra(2,3,4,5-tetrafluorophenyl)borate, tetra(3,4,5-tetrafluorophenyl)borate, triphenylmethyltetra(pentafluorophenyl)borate, tetra(2,3,4-tetrafluorophenyl)borate, phenylbis(pentafluorophenyl)borate, triethylammonium tetra(pentafluorophenyl)boronic acid. Salts, tripropylammonium tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, N,N-dimethylammonium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylammonium tetra(pentafluorophenyl)borate, N,N-2,4,6-pentamethylammonium tetra(pentafluorophenyl)borate, diisopropylammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetra(pentafluorophenyl)borate, triphenylphosphine tetra(pentafluorophenyl)borate, tri(methylphenyl)phosphine tetra(pentafluorophenyl)borate, tri(pentafluorophenyl)borane and triphenylmethyl tetra(pentafluorophenyl)borate, triphenylmethyl tetra(pentafluorophenyl)borate.

5. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 4, characterized in that: The temperature of the catalyst pre-activation section is 30–130℃, and the temperature of the polymerization section is 70–180℃; The reaction pressure of the catalyst pre-activation section and polymerization section is 2–120 bar, and the total residence time is 5–300 s.

6. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 5, characterized in that: The solvents used in the cycloolefin monomer solution, the main catalyst solution, and the co-catalyst solution are all inert organic solvents; The inert organic solvent is at least one of the following: straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydrocarbons, substituted cyclic aliphatic hydrocarbons, unsubstituted cyclic aliphatic hydrocarbons, substituted aromatic hydrocarbons, and unsubstituted aromatic hydrocarbons.

7. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 6, characterized in that: The inert solvent is hexane, heptane, cyclohexane, cyclooctane, toluene, or xylene.

8. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to claim 7, characterized in that: In the cyclic olefin monomer solution, the mass fraction of the cyclic olefin monomer is 5 wt% to 90 wt%.

9. The method for preparing cyclic olefin copolymers using a continuous flow integrated microreactor according to any one of claims 1 to 8, characterized in that: A catalyst inlet is provided in the catalyst pre-activation section, and the main catalyst solution and the co-catalyst solution enter the catalyst pre-activation section from the catalyst inlet. A feed inlet is set at the connection between the catalyst pre-activation section and the polymerization section, and ethylene and cyclic olefin monomer solutions enter the polymerization section from the feed inlet.

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