A catalytic system for preparing cycloolefin copolymer and its application

Abstract

The present invention relates to a catalytic system for preparing cycloolefin copolymers and its application. The catalytic system includes a main catalyst, a cocatalyst, and a chain transfer agent; the main catalyst is a silane-bridged fluorenylamino dimethyl titanium complex, a silane-bridged fluorenylamino dimethyl zirconium complex, a silane-bridged fluorenylamino dimethyl hafnium complex, or a silane-bridged fluorenylamino dichloride hafnium complex; the cocatalyst is an aluminum compound or a boron compound; the chain transfer agent is one or more of second main / transition metal complexes; during application, the above catalytic system is used, and under its catalytic action, cycloolefins and non-cyclic olefins are copolymerized to obtain cycloolefin copolymers. The catalytic system of the present invention significantly reduces the consumption of expensive silane-bridged metal complexes, and while maintaining high polymerization activity, effectively controls the molecular weight of the polymer; the prepared cycloolefin copolymers have an adjustable molecular weight in a wide range, a narrow molecular weight distribution, and controllable cycloolefin insertion rate and glass transition temperature.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-performance polyolefins, and relates to a catalytic system for preparing cycloolefin copolymers and its applications. Background Art

[0002] Cycloolefin copolymer (COC) is an amorphous thermoplastic polymer material, which has characteristics such as high light transmittance, high refractive index, low birefringence, low water absorption, low specific gravity, excellent thermal stability and low dielectric constant. It is widely used in fields such as optics, medicine, packaging and electrical appliances, and is considered an ideal alternative material to PC, PS, PVC, PMMA and some engineering plastics. It can be used to manufacture optical lenses, films, optical fibers, medical devices, drug packaging, bone materials, bipolar plate materials, etc. Currently, commercial COC products are mainly the Topas series of Polyplastics Co., Ltd. in Japan and the APEL series of Mitsui Chemicals, Inc. in Japan.

[0003] COC is mainly prepared by the addition polymerization reaction of α-olefins and cycloolefins catalyzed by metallocene catalysts. For example, in the literature (Macromolecules, 2011, 44(7): 1986 - 1998.), single metallocene complexes with different substituents were synthesized, realizing the copolymerization of α-olefins and cycloolefins, and the influence of metallocene catalysts with different structures on the copolymerization reaction was explored.

[0004] The polymerization initiation mechanism of metallocene catalytic systems is similar to that of Ziegler-Natta systems, that is, olefin molecules coordinate with transition metals. The coordination polymerization mechanism usually consists of four elementary reactions: chain initiation, chain growth, chain transfer and chain termination. Among them, chain transfer mainly has two types: β-H elimination and chain transfer to alkyl metal. However, metallocene catalysts generally have the disadvantage of "living polymerization", that is, it is difficult for existing metallocene catalytic systems to undergo chain transfer reactions. Each active center can only generate one active chain and continuously grow, ultimately resulting in too high molecular weight of the polymerization product, which is not conducive to processing, and the initiation efficiency of the catalyst system is low.

[0005] To solve the above problems, researchers usually add chain transfer agents such as alkylaluminum, alkylzinc, and alkylmagnesium to the polymerization system. Adding chain transfer agents can significantly increase the chain transfer rate during polymerization, enabling multiple active chains to grow from each active center, significantly reducing the consumption of expensive metallocene catalysts, and controlling the molecular weight of the polymer. The chain transfer process determines the later processing and application conditions of the polymer, so it is a key factor in measuring whether the catalyst can be industrialized. However, it is difficult to reasonably select chain transfer agents during the current preparation of cycloolefin copolymers. The difficulty lies in that the chain transfer reaction can only occur when the end of the growing active chain is a non-cyclic olefin, and conversely, no chain transfer reaction can occur if the end is a cycloolefin. Therefore, the types and dosages of the catalyst and chain transfer agent need to be highly matched and coordinated, otherwise, it will affect the activity of the catalyst, the molecular weight, and molecular weight distribution of the polymer, etc.

[0006] In the prior art, although attempts have been made to regulate the molecular weight of COC by adding chain transfer agents, the addition of chain transfer agents will significantly reduce the polymerization activity, and there are disadvantages such as a narrow range of regulated molecular weights and a wide molecular weight distribution. For example, Patent CN201710928754 discloses a method for preparing COC. An alkylaluminum compound chain transfer agent is added to the metallocene catalytic system to control the molecular weight of COC. However, the sharp increase in the molecular weight distribution width occurs while the polymer molecular weight decreases. Patent CN202110171214 discloses a polymerization method for efficiently regulating the molecular weight of COC by reversible coordination chain transfer. By adding a metal alkyl compound as a chain transfer agent to the metallocene catalytic system, the control of the molecular weight of COC is achieved, but the polymerization activity of the system is significantly reduced and the molecular weight distribution becomes wider.

[0007] Therefore, it is of great significance to study a catalytic system for preparing cycloolefin copolymers and apply it to the preparation of cycloolefin copolymers to solve the problems existing in the prior art. Summary of the Invention

[0008] The object of the present invention is to solve the problems existing in the prior art and provide a catalytic system for preparing cycloolefin copolymers and its application.

[0009] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0010] A catalytic system for preparing cycloolefin copolymers, comprising a main catalyst, a co-catalyst, and a chain transfer agent;

[0011] The main catalyst is a silane-bridged fluorenylamino dimethyl titanium complex, a silane-bridged fluorenylamino dimethyl zirconium complex, a silane-bridged fluorenylamino dimethyl hafnium complex, or a silane-bridged fluorenylamino dichloride hafnium complex;

[0012] The cocatalyst is an aluminum compound cocatalyst or a boron compound cocatalyst, belonging to Group III main group complexes;

[0013] The chain transfer agent is one or more of Group II main / Group IIB metal complexes;

[0014] The molar ratio of the aluminum compound cocatalyst to the main catalyst is 1~1000:1, preferably 200~800:1, more preferably 400:1; the molar ratio of the boron compound cocatalyst to the main catalyst is 1~10:1, preferably 1~5:1, more preferably 2:1; the molar ratio of the chain transfer agent to the main catalyst is 1~500:1, preferably 1~100:1, more preferably 2~20:1.

[0015] The catalytic characteristics of the metallocene catalyst used for COC polymerization are closely related to the type of central metal, the structure of the ligand, the configuration and conformation of the complex. When cycloolefins and non-cyclic olefins are polymerized, due to the large volume of the monomer cycloolefin, steric hindrance will occur, making it difficult for it to coordinate with the metallocene active center with a relatively narrow space and insert into the active chain, resulting in very low polymerization activity or even inability to polymerize of the COC obtained by many metallocene catalysts. The bridged single metallocene catalyst used in the present invention (silyl-bridged fluorenylamino dimethyl titanium complex, silyl-bridged fluorenylamino dimethyl zirconium complex, silyl-bridged fluorenylamino dimethyl hafnium complex or silyl-bridged fluorenylamino dichloride hafnium complex) has the typical characteristics of a half-sandwich structure, with the m ligand covering one side of the metal center and leaving a large coordination space on the other side, which is conducive to the coordination and insertion polymerization of cycloolefin monomers. When preparing COC without adding a chain transfer agent, the polymerization activity is very high, up to 5×10 8 g·mol -1 ·h -1 . At the same time, when the bridged single metallocene catalyst catalyzes the polymerization of cycloolefins and non-cyclic olefins, it is a living polymerization system. When no chain transfer agent is added, the weight-average molecular weight of COC increases with the increase of the feeding amount of cycloolefin monomer and the polymerization time, reaching up to 60×10 4 g / mol (at this time, the molecular weight is too high and not conducive to processing), and the molecular weight distribution is relatively narrow (molecular weight distribution ≤ 3).

[0016] The coordination polymerization mechanism of the metallocene catalytic system is the coordination of olefin molecules and transition metals, which is usually composed of four elementary reactions: chain initiation, chain growth, chain transfer, and chain termination. Among them, chain transfer refers to the process in which the active chain transfers from the active center to another molecule, mainly including β-H elimination and chain transfer to alkyl metal. The number of molecular chains of COC obtained by polymerizing the bridged single metallocene catalyst system used in the present invention is less than the amount of catalyst added, indicating that there is no chain transfer reaction caused by β-H elimination in the copolymerization process initiated by the system. After adding the chain transfer agent, the chain transfer reaction (including chain termination) in the system is mainly chain transfer to alkyl metal, and the chain transfer rate kt Far greater than the chain growth rate k p , at this time the chain transfer reaction is usually reversible and rapid, and this process is called coordination chain transfer polymerization (CCTP). In CCTP, the most important is the chain transfer agent, usually some metal alkyls such as alkyl aluminum, alkyl zinc, alkyl magnesium, etc. CCTP solves the disadvantages of metallocene catalysts, that is, most of the existing metallocene catalysts are living polymerization systems, and each active center can only generate one active chain. In CCTP, the active chain growing on the active center transfers to the alkyl metal as the chain transfer agent to form a dormant species, and the active center continues to generate new active chains. A rapid and reversible chain transfer occurs between the growing active chain and the dormant species, reaching a dynamic balance among the active center, the alkyl metal, and the active chain, enabling each active center to generate multiple active chains with uniform chain lengths. Therefore, the obtained COC has a narrow molecular weight distribution. By changing the concentration of the chain transfer agent in the system, the molecular weight of the polymer can be controlled. The higher the ratio of the chain transfer agent to the catalyst, the higher the transfer efficiency, and the more chains each catalyst molecule can grow, reducing the consumption of expensive metallocene catalysts. After adding the chain transfer agent, within a certain range, as the amount of the chain transfer agent added increases, the polymerization activity of the COC obtained from the bridged monocyclopentadienyl metallocene catalyst system remains unchanged or even increases, and the molecular weight continuously decreases. As the addition amount continues to increase, the activity decreases, but still remains above 1×10 7 g·mol -1 ·h -1 or above, and the lowest weight-average molecular weight can reach 1×10 3 g / mol. The cycloolefin copolymer prepared by the present invention has the advantages of adjustable molecular weight in a wide range, narrow molecular weight distribution, controllable cycloolefin insertion rate, and glass transition temperature, etc.

[0017] As a preferred technical solution:

[0018] A catalytic system for preparing cycloolefin copolymer as described above, the main catalyst being methylphenylsilyl-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, diphenylsilyl-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-fluorenyl-tert-butylamino-dimethyltitanium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilyl-fluorenyl-(α-dimethylphenylamino)-dimethyltitanium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-(α-dimethylphenylamino)-dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-(α-dimethylphenylamino)-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-(α-dimethylphenylamino)-dimethyltitanium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-(α-dimethylphenylamino)-dimethyltitanium, dimethylsilyl-fluorenyl-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-fluorenyl-adamantylamino-dimethyltitanium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-fluorenyl-tert-butylamino-dimethylzirconium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-fluorenyl-adamantylamino-dimethylzirconium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-adamantylamino-dimethylzirconium, dimethylsilyl-(3,6 - Di - tert - butylfluorenyl) - adamantanamine - dimethylzirconium, dimethylsilyl - bridged - (3,6 - dimethoxyfluorenyl) - adamantanamine - dimethylzirconium, dimethylsilyl - bridged - (2,6 - bis(1,1,4,4 - tetramethylcyclohexyl)fluorenyl) - adamantanamine - dimethylzirconium, dimethylsilyl - bridged - fluorenyl - tert - butylamine - dimethylhafnium, dimethylsilyl - bridged - fluorenyl - tert - butylamine - dichlorohafnium or dimethylsilyl - bridged - fluorenyl - adamantanamine - dichlorohafnium.,

[0019] A catalytic system for preparing a cycloolefin copolymer as described above, the aluminum compound cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, trialkylaluminum (trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri - n - butylaluminum, triisobutylaluminum, tri - n - hexylaluminum, trioctylaluminum, tridecylaluminum), dialkylaluminum chloride (dimethylaluminum chloride, diethylaluminum chloride, n - propylaluminum monochloride, dibutylaluminum chloride, diisobutylaluminum chloride, di - n - hexylaluminum chloride), monoalkylaluminum dichloride (methylaluminum dichloride, dichloroethylaluminum, isobutylaluminum dichloride, n - hexylaluminum dichloride) and trialkylaluminum dichloride (trimethylaluminum dichloride, triethylaluminum dichloride), preferably methylaluminoxane or modified methylaluminoxane; the boron compound cocatalyst is one or more of N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N - diethylanilinium tetrakis(pentafluorophenyl)borate, N,N - bis(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate and trityl tetrakis(pentafluorophenyl)borate, preferably triphenylcarbenium tetrakis(pentafluorophenyl)borate.,

[0020] A catalytic system for preparing a cycloolefin copolymer as described above, the chain transfer agent is one or more of diphenylzinc, dimethylzinc, diethylzinc, diisopropylzinc, dibutylzinc, diethylmagnesium, diisobutylmagnesium, di - n - butylmagnesium and n - butylethylmagnesium.,

[0021] The present invention also provides a method for preparing a cycloolefin copolymer, using the catalytic system described in any one of the above, and under its catalytic action, cycloolefins and non - cyclic olefins are copolymerized to obtain a cycloolefin copolymer.,

[0022] As a preferred technical solution:

[0023] A method for preparing a cycloolefin copolymer as described above, the cycloolefin is an unsaturated cyclic olefin, and the structural formula is as follows:

[0024] ;

[0025] In the formula, m is 0, 1 or 2, R 2 and R 3 each independently selected from a hydrogen atom, an alkyl group and a cycloalkyl group;

[0026] The cycloolefin is preferably one or more of cyclopentadiene, dicyclopentadiene, norbornene, tetracyclododecene, 1,4,5,8,9,10-trimethylenedodecahydroanthracene, and more preferably norbornene;

[0027] The acyclic olefin is a straight-chain olefin having 2 to 20 carbon atoms, and the structural formula is as follows:

[0028] ;

[0029] In the formula, R 1 is an independent hydrogen or a saturated aliphatic hydrocarbon group having 1 to 19 carbon atoms;

[0030] The acyclic olefin is preferably one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.

[0031] For the preparation method of a cycloolefin copolymer as described above, the reaction adopts a solution polymerization method and the copolymerization reaction is carried out in an organic solvent.

[0032] The organic solvent is one or more of aromatic hydrocarbons (toluene, ethylbenzene, xylene, trimethylbenzene), aliphatic hydrocarbons (n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane), and alicyclic hydrocarbons (cyclohexane, cycloheptane, cyclooctane, cyclohexanone, methylcyclohexane, methylcyclohexanone), preferably one or more of toluene, n-hexane, cyclohexane, and methylcyclohexane, and more preferably toluene.

[0033] For the preparation method of a cycloolefin copolymer as described above, the reaction temperature is 40 to 120 °C, preferably 40 to 60 °C, and more preferably 40 °C; the reaction time is 1 to 30 minutes, preferably 1 to 5 minutes, and more preferably 3 minutes.

[0034] For the preparation method of a cycloolefin copolymer as described above, the molar ratio of the cycloolefin to the acyclic olefin is 1 to 10:1.

[0035] For the preparation method of a cycloolefin copolymer as described in any one of the above, the weight-average molecular weight of the cycloolefin copolymer is 1×10 3 ~60×10 4 g / mol, the molecular weight distribution is 1.5 to 3.0, and the polymerization activity is 1×10 7 ~5×10 8 g mol -1, the polymerization activity refers to the unit mass of the polymer catalyzed and polymerized per unit time using a unit molar amount of the catalyst. The glass transition temperature is 67 - 147 °C, and the cycloolefin insertion rate is 21.0 - 51.1 mol%; the reaction equation is as Figure 6 shown.

[0036] The present invention also provides a cycloolefin copolymer prepared by the preparation method described in any one of the above, and the structural formula is as follows:

[0037] ;

[0038] wherein, 1 ≤ X / Y ≤ 5, 2 ≤ n ≤ 5000;

[0039] R 1 is an independent hydrogen or a saturated aliphatic hydrocarbon group with 1 - 19 carbon atoms;

[0040] R 2 and R 3 each independently selected from a hydrogen atom, an alkyl group and a cycloalkyl group.

[0041] Beneficial effects:

[0042] (1) For a catalytic system for preparing a cycloolefin copolymer of the present invention, the chain transfer agent is a second main / secondary group metal complex. After adding the chain transfer agent, the chain transfer rate in the coordination polymerization process can be significantly increased. The chain transfer from the catalyst to the chain transfer agent allows several polymer chains to grow from each catalyst molecule, significantly reducing the consumption of expensive silane-bridged metal complexes and controlling the molecular weight of the polymer.

[0043] (2) For a preparation method of a cycloolefin copolymer of the present invention, the obtained cycloolefin copolymer has the advantages of adjustable molecular weight in a wide range, narrow molecular weight distribution, controllable cycloolefin insertion rate and glass transition temperature. Description of the drawings

[0044] Figure 1 is the 1 H NMR spectrum (CDCl 3 , 298K) of the main catalyst in Example 2 of the present invention;

[0045] Figure 2 is the 13 C NMR spectrum (C 2 D 2 Cl 4 , 368K) of the cycloolefin copolymer prepared in Example 2 of the present invention;

[0046] Figure 3 is the gel permeation chromatogram of the cycloolefin copolymer prepared in Example 2 of the present invention;

[0047] Figure 4 It is the DSC curve of the cycloolefin copolymer prepared in Example 1 of the present invention;

[0048] Figure 5 It is the DSC curve of the cycloolefin copolymer prepared in Example 2 of the present invention;

[0049] Figure 6 It is the reaction equation for the copolymerization reaction of cycloolefins and non-cyclic olefins to prepare cycloolefin copolymers in the present invention. Specific Embodiments

[0050] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0051] The test methods for the performance indicators in the examples and comparative examples of the present invention are as follows:

[0052] (1) Catalyst catalytic polymerization activity: The calculation formula is as follows:

[0053] ;

[0054] In the calculation formula, the catalyst catalytic polymerization activity (Activity) refers to the unit mass of COC catalytically polymerized using a unit molar amount of catalyst per unit time, with the unit of g·mol -1 ·h -1 . W 聚合物 : The mass of the polymer catalytically polymerized within a certain time (unit: g). [M]: The molar amount of the catalyst in the experiment (unit: mol). t: The polymerization time (unit: h).

[0055] (2) Glass transition temperature: T of the COC product obtained in the experiment gThe measurement was carried out on a TA Q2000 differential scanning calorimeter (DSC) as follows: Weigh about 5 mg of the COC sample, encapsulate it in an aluminum crucible and place it on the instrument test platform. The measurement was carried out under an inert atmosphere environment and a preset temperature program (heating and cooling rate: 10 °C / min; heating range: 40 - 250 °C). First, the sample was held at 40 °C for 2 min, then heated from 40 °C to 250 °C at a heating rate of 10 °C / min to eliminate the thermal history, then cooled from 250 °C to 40 °C at the same cooling rate and held at 40 °C for 5 min again. Finally, it was heated from 40 °C to 250 °C at a heating rate of 10 °C / min again, and the heat flow curve of the second heating was retained. The T was calculated by calibrating the slope midline through a computer program g 。

[0056] (3)Weight-average molecular weight and molecular weight distribution: The measurement and characterization of the polymer molecular weight and its distribution were carried out on an Agilent PL GPC-220 high-temperature gel permeation chromatograph (equipped with a PL# 1110-1120 guard column and a 30 cm PLgel 10 μm MIXED-B 7.5×300 mm column). Weigh about 20 mg of the COC sample into a sample bottle and dissolve it by shaking with 1,2,4-trichlorobenzene (TCB) solvent at 150 °C. After it was completely dissolved, use a filter gun to transfer a part of the solution to a test bottle, and put the test bottle into the auto-sampler for measurement. After setting the test parameters, start the measurement. After the measurement, use CIRRUS software for data analysis. The conditions during the measurement were: temperature: 150 °C; mobile phase: 1,2,4-trichlorobenzene (TCB); flow rate: 1.0 mol / L; calibration standard sample: narrow-distribution polystyrene. If the M w is used as the abscissa, the curve obtained in this way is a curve that almost coincides with the X-axis, and the change in the amount of substance cannot be reflected on the curve. Therefore, usually log M w is used instead of M w for plotting.

[0057] (4)Nuclear magnetic resonance spectrum: The determination of the polymer chain structure was carried out on a Bruker Asend TM 600 MHz nuclear magnetic resonance spectrometer. By 13The ring olefin insertion rate is obtained by formula calculation of the integration results on the 13C NMR spectrum. Weigh about 100 mg of the purified COC sample and put it into a nuclear magnetic tube, using 1,1,2,2-tetrachloroethane-d2 as the solvent. Then seal the sample in the nuclear magnetic test tube and heat it for 6 h. After it is completely dissolved, test it under the protection of liquid nitrogen at 368 K. Taking the copolymerization of ethylene (E) and norbornene (NB) to obtain a cycloolefin copolymer as an example, the insertion rate of the NB monomer is calculated according to the following formula:

[0058] ;

[0059] where I C1 / 4 , I C2 / 3 and I C7 values respectively correspond to the integrated areas of the C1 / 4, C2 / 3 and C7 characteristic peaks of NB, and the I CH2 value corresponds to the sum of the integrated areas of the C5 / C6 of NB and the CH 2 characteristic peak of ethylene;

[0060] .

[0061] The sources of some substances in the examples and comparative examples of the present invention are as follows:

[0062] Methylaluminoxane: Roehn reagent, R129768-100ml.

[0063] Triphenylcarbenium tetrakis(pentafluorophenyl)borate: Roehn reagent, R055487-200mg.

[0064] Modified methylaluminoxane: Alany (Shanghai) Chemical Technology Co., Ltd., 206451-54-9.

[0065] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate: Shanghai Haohong Biopharmaceutical Technology Co., Ltd., 1176862-250mg.

[0066] Diethylaluminum chloride: Shanghai Titan Co., Ltd., 01376488.

[0067] Ethylaluminum dichloride: Shanghai Titan Co., Ltd., 01376488.

[0068] Ethylaluminum dichloride: Shanghai Titan Co., Ltd., 011343043.

[0069] Triphenylmethyltetrakis(pentafluorophenyl)borate: Shanghai Bide Pharmaceutical Technology Co., Ltd., BD232925.

[0070] Diethylzinc: Shanghai Aladdin Biochemical Technology Co., Ltd., D107431-25mL.

[0071] Diphenylzinc: Shanghai Macklin Biochemical Co., Ltd., D776224 - 100mg 5mL.

[0072] Dimethylzinc: Shanghai Aladdin Biochemical Technology Co., Ltd., D140708 - 100mL.

[0073] Di-n-butylmagnesium: Rhawn Reagent, R007478 - 100mL.

[0074] Dibutylzinc: Shanghai Aladdin Biochemical Technology Co., Ltd., D188990 - 100mL.

[0075] Diisopropylzinc: Shanghai Aladdin Biochemical Technology Co., Ltd., D466158 -.

[0076] n-Butylethylmagnesium: Shanghai Aladdin Biochemical Technology Co., Ltd., B140756 - 5mL.

[0077] Toluene: Sinopharm Chemical Reagent Co., Ltd., 10022828.

[0078] Methylcyclohexane: Shanghai Titan Scientific Co., Ltd., 01006977.

[0079] n-Hexane: Sinopharm Chemical Reagent Co., Ltd., 80068618.

[0080] n-Heptane: Rhawn Reagent, R033323 - 500mL.

[0081] n-Pentane: Shanghai Aladdin Biochemical Technology Co., Ltd., P298686 - 2.5L.

[0082] Cycloheptane: Shanghai Titan Scientific Co., Ltd., 013556616.

[0083] Cyclohexane: Sinopharm Chemical Reagent Co., Ltd., 80039728.

[0084] n-Pentane: MACKLIN / Macklin, P816220 - 500mL.

[0085] Xylene: Sinopharm Chemical Reagent Co., Ltd., 10023428.

[0086] Norbornene: Shanghai Merck, M17722 - 100G.

[0087] Tetracyclododecene: Shanghai Titan Scientific Co., Ltd., 013629869.

[0088] Cyclopentadiene: MACKLIN / Macklin, C875529 - 100g.

[0089] Dicyclopentadiene: Shanghai Titan Co., Ltd., 01115014.

[0090] Ethylene: Shanghai Qihui, YG0020.

[0091] 1-Butene: Shanghai Titan Co., Ltd., 016240820.

[0092] 1-Heptene: Shanghai Merrill, M20715-100 mL.

[0093] Propylene: Shanghai Qihui, YG0019.

[0094] 1-Hexene: Shanghai Titan Co., Ltd., 01092680

[0095] 1-Pentene: Shanghai Bailingwei Chemical Technology Co., Ltd., P0316.

[0096] 1-Octene: Shanghai J&K Chemical Technology Co., Ltd., 914719.

[0097] 1-Dodecene: Sane Chemical Technology (Shanghai) Co., Ltd., W3300890250.

[0098] Nitrogen: Shanghai Qihui, YG0003.

[0099] Argon: Shanghai Qihui, YG0008.

[0100] Helium: Shanghai Qihui, YG0001.

[0101] Methanol: Shanghai Titan Co., Ltd., 01273159.

[0102] Ethanol: Ron's reagent, R051411-500mL.

[0103] Isopropyl alcohol: Shanghai Merrill, M23307-500mL.

[0104] Acetone: Sinopharm Chemical Reagent Co., Ltd., 10000428.

[0105] Cyclohexanone: Shanghai Titan Co., Ltd., 01007022.

[0106] Example 1

[0107] A catalytic system for preparing cycloolefin copolymers, comprising a main catalyst, a co-catalyst and a chain transfer agent;

[0108] The main catalyst is dimethylsilyl bridge group-(2,7-di-tert-butylfluorenyl)-tert-butylamino-dimethyltitanium;

[0109] The co-catalyst is methylaluminoxane;

[0110] The chain transfer agent is diethylzinc;

[0111] The molar ratio of the cocatalyst to the main catalyst is 400:1; the molar ratio of the chain transfer agent to the main catalyst is 20:1.

[0112] A method for preparing a cycloolefin copolymer comprises the following specific steps:

[0113] (1) Preparation of raw materials:

[0114] Organic solvent: toluene;

[0115] Cycloolefin: norbornene;

[0116] Non-cyclic olefin: propylene;

[0117] The above-mentioned catalytic system for preparing the cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0118] Propylene gas at a pressure of 5 atm;

[0119] Methanol;

[0120] Acidified precipitant: the acid is hydrochloric acid, the precipitant is methanol, Shanghai Titan Co., Ltd.;

[0121] (2) Under nitrogen protection, successively add the organic solvent, cycloolefin, chain transfer agent, cocatalyst into the reaction vessel, introduce the non-cyclic olefin, then add the main catalyst, and then carry out copolymerization reaction at 40 °C for 3 min. After the reaction is completed, add methanol to terminate the polymerization;

[0122] Among them, the molar ratio of the organic solvent to the cycloolefin is 16:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 5:1; the molar ratio of the cycloolefin to the chain transfer agent is 67:1;

[0123] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with methanol 3 times and vacuum drying to obtain the cycloolefin copolymer;

[0124] Among them, the vacuum degree of vacuum drying is 0.01 atm, the temperature is 60 °C, and the time is 12 hours.

[0125] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 1.6×10 3 g / mol, the molecular weight distribution is 1.7, and the polymerization activity is 4.7×10 8 g mol -1 , the cycloolefin insertion rate is 50.80 mol%; as Figure 4 shown, the glass transition temperature is 145 °C.

[0126] Comparative Example 1

[0127] A catalytic system for preparing cycloolefin copolymer is basically the same as that in Example 1, except that: no chain transfer agent is added.

[0128] A method for preparing cycloolefin copolymer is catalyzed by the above catalytic system.

[0129] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 58×10 4 g / mol, the molecular weight distribution is 1.5, and the polymerization activity is 4.8×10 8 g mol -1 h -1 .

[0130] Comparing Comparative Example 1 with Example 1, it can be found that the weight-average molecular weight of the cycloolefin copolymer obtained in Comparative Example 1 is significantly higher than that in Example 1. This is because the catalyst catalyzes the polymerization of cycloolefin and non-cyclic olefin as "living polymerization", and it is difficult to occur chain transfer reaction in the system. Each active center can only generate one active chain and continuously grow, so the molecular weight of the finally obtained cycloolefin copolymer is very high.

[0131] Comparative Example 2

[0132] A catalytic system for preparing cycloolefin copolymer is basically the same as that in Example 1, except that: the cocatalyst is sodium tetrakis(pentafluorophenyl)borate.

[0133] A method for preparing cycloolefin copolymer is catalyzed by the above catalytic system.

[0134] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 2.1×10 3 g / mol, the molecular weight distribution is 1.8, and the polymerization activity is 6.0×10 6 g mol -1 h -1 .

[0135] Comparing Comparative Example 2 with Example 1, it can be found that the polymerization activity of the cycloolefin copolymer obtained in Comparative Example 2 is significantly lower than that in Example 1. This is because although sodium tetrakis(pentafluorophenyl)borate can initiate the formation of active centers of metallocene complexes, the stability of the active centers is poor, causing some active centers to be directly inactivated, so the polymerization activity is greatly reduced.

[0136] Comparative Example 3

[0137] A catalytic system for preparing cycloolefin copolymer is basically the same as that in Example 1, except that: the chain transfer agent is phenylsilane.

[0138] A method for preparing cycloolefin copolymer is catalyzed by the above catalytic system.

[0139] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 69.1×10 4 g / mol, the molecular weight distribution is 2.1, and the polymerization activity is 4.2×10 8 g mol -1 h -1 .

[0140] Comparing Comparative Example 3 with Example 1, it can be found that the weight-average molecular weight of the cycloolefin copolymer obtained in Comparative Example 3 is significantly higher than that in Example 1. This is because the reaction between the growing active chain and the dormant species is an irreversible chain transfer reaction. The growing active chain on the active center transfers to the chain transfer agent and terminates directly, and the active center continues to generate new active chains.

[0141] Comparative Example 4

[0142] A catalytic system for preparing a cycloolefin copolymer is basically the same as that in Example 1, except that: the molar ratio of the aluminum complex cocatalyst to the main catalyst is 1050:1.

[0143] A method for preparing a cycloolefin copolymer is catalyzed by the above catalytic system.

[0144] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 1.9×10 3 g / mol, the molecular weight distribution is 1.6, and the polymerization activity is 1.4×10 6 g mol -1 h -1 .

[0145] Comparing Comparative Example 4 with Example 1, it can be found that the polymerization activity of the cycloolefin copolymer obtained in Comparative Example 4 is significantly lower than that in Example 1. This is because there are unreacted raw materials in the process of synthesizing the aluminum compound cocatalyst. As the amount of the aluminum compound cocatalyst added increases, the raw materials are more likely to form a double-coordinated product with the main catalyst, making the metallocene complex after alkylation unable to generate vacancies, reducing the active species formed by the metallocene complex, and thus reducing the polymerization activity.

[0146] Comparative Example 5

[0147] A catalytic system for preparing a cycloolefin copolymer is basically the same as that in Example 1, except that: the ratio of the chain transfer agent to the main catalyst is 510:1.

[0148] A method for preparing a cycloolefin copolymer is catalyzed by the above catalytic system.

[0149] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 2.8×10 3 g / mol, the molecular weight distribution is 1.8, and the polymerization activity is 8.9×106 g mol -1 h -1 。

[0150] Comparing Comparative Example 5 with Example 1, it can be found that the polymerization activity of the cycloolefin copolymer obtained in Comparative Example 5 is significantly lower than that in Example 1. This is because as the addition amount of the chain transfer agent increases, the concentration of the chain transfer agent in the system increases, and the probability of chain transfer increases accordingly. The active chain growing on the active center is transferred to the chain transfer agent before sufficient chain growth, resulting in a decrease in polymerization activity.

[0151] Example 2

[0152] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst, and a chain transfer agent;

[0153] As Figure 1 shown, the main catalyst is dimethylsilyl-bridged-fluorenyl-tert-butylamino-dimethyltitanium;

[0154] The cocatalyst is triphenylcarbenium tetrakis(pentafluorophenyl)borate;

[0155] The chain transfer agent is diethylzinc;

[0156] The molar ratio of the cocatalyst to the main catalyst is 2:1; the molar ratio of the chain transfer agent to the main catalyst is 10:1.

[0157] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0158] (1) Preparation of raw materials:

[0159] Organic solvent: toluene;

[0160] Cycloolefin: norbornene;

[0161] Non-cyclic olefin: ethylene;

[0162] The above-mentioned catalytic system for preparing a cycloolefin copolymer: main catalyst, cocatalyst, and chain transfer agent;

[0163] Ethylene gas at a pressure of 5 atm;

[0164] Methanol;

[0165] Acidified precipitant: the acid is hydrochloric acid, and the precipitant is ethanol;

[0166] (2) Under nitrogen protection, add the organic solvent, cycloolefin, chain transfer agent, and cocatalyst to the reaction vessel in sequence, introduce the non-cyclic olefin, then add the main catalyst, and carry out copolymerization reaction at 40 °C for 3 min. After the reaction is completed, add methanol to terminate the polymerization;

[0167] Among them, the molar ratio of the organic solvent to the cycloolefin is 16:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 5:1; the molar ratio of the cycloolefin to the chain transfer agent is 135:1;

[0168] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing an acidified precipitant, and then perform filtration, ethanol washing three times, and vacuum drying in sequence to obtain a cycloolefin copolymer;

[0169] Among them, the vacuum degree of the vacuum drying is 0.05 atm, the temperature is 65 °C, and the time is 9 hours.

[0170] As Figure 3 shown, the weight-average molecular weight of the finally obtained cycloolefin copolymer is 1.0×10 3 g / mol, the molecular weight distribution is 1.5, and the polymerization activity is 5.0×10 8 g mol -1 , as Figure 2 shown, the cycloolefin insertion rate is 51.10 mol%; as Figure 5 shown, the glass transition temperature is 147 °C.

[0171] Comparative Example 6

[0172] A catalytic system for preparing a cycloolefin copolymer is basically the same as that in Example 2, except that: the molar ratio of the cocatalyst to the main catalyst is 11:1.

[0173] A method for preparing a cycloolefin copolymer is catalyzed by the above catalytic system.

[0174] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 71.3×10 4 g / mol, the molecular weight distribution is 1.5, and the polymerization activity is 4.7×10 8 g mol -1 h -1 .

[0175] Comparing Comparative Example 6 with Example 2, it can be found that the weight-average molecular weight of the cycloolefin copolymer obtained in Comparative Example 6 is significantly higher than that in Example 2. This is because the addition amount of the cocatalyst increases, the concentration of the boron compound in the system is higher, it is easier to form an active center with the metallocene complex, occupies the vacancy on the metallocene complex for a long time, and slows down the speed of the active chain transferring to the chain transfer agent.

[0176] Comparative Example 7

[0177] A catalytic system for preparing a cycloolefin copolymer is basically the same as that in Example 2, except that: no chain transfer agent is added.

[0178] A method for preparing a cycloolefin copolymer, which is catalyzed by the above-mentioned catalytic system.

[0179] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 60×10 4 g / mol, the molecular weight distribution is 1.6, and the polymerization activity is 4.9×10 8 g mol -1 h -1 .

[0180] Comparing Comparative Example 7 with Example 2, it can be found that the weight-average molecular weight of the cycloolefin copolymer obtained in Comparative Example 7 is significantly greater than that in Example 2. This is because when the catalyst catalyzes the polymerization of cycloolefins and non-cyclic olefins, it is "living polymerization", and it is difficult for chain transfer reactions to occur in the system. Each active center can only generate one active chain and continuously grow. Therefore, the molecular weight of the finally obtained cycloolefin copolymer is very high.

[0181] Example 3

[0182] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0183] The main catalyst is dimethylsilyl-bis(3,6-di-tert-butylfluorenyl)-(α-dimethylanilino)dimethyltitanium;

[0184] The cocatalyst is modified methylaluminoxane;

[0185] The chain transfer agent is dimethylzinc;

[0186] The molar ratio of the cocatalyst to the main catalyst is 200:1; the molar ratio of the chain transfer agent to the main catalyst is 40:1.

[0187] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0188] (1) Preparation of raw materials:

[0189] Organic solvent: cyclohexane;

[0190] Cycloolefin: tetracyclododecene;

[0191] Non-cyclic olefin: propylene;

[0192] The above-mentioned catalytic system for preparing a cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0193] Propylene gas with a pressure of 3 atm;

[0194] Methanol;

[0195] Acidified precipitant: the acid is hydrochloric acid and the precipitant is methanol;

[0196] (2) Under the protection of helium, organic solvent, cycloolefin, chain transfer agent, and cocatalyst were successively added to the reaction vessel. Non-cyclic olefin was introduced, and then the main catalyst was added. Then, copolymerization reaction was carried out at 50 °C for 1 min. After the reaction was completed, methanol was added to terminate the polymerization;

[0197] Among them, the molar ratio of the organic solvent to the cycloolefin was 13:1; the molar ratio of the cycloolefin to the non-cyclic olefin was 7:1; the molar ratio of the cycloolefin to the chain transfer agent was 74:1;

[0198] (3) The reaction solution obtained from the polymerization reaction in step (2) was poured into a container containing an acidified precipitant, and then filtration, ethanol washing three times, and vacuum drying were carried out in sequence to obtain a cycloolefin copolymer;

[0199] Among them, the vacuum degree of vacuum drying was 0.02 atm, the temperature was 65 °C, and the time was 8 hours.

[0200] The weight-average molecular weight of the finally obtained cycloolefin copolymer was 5.4×10 3 g / mol, the molecular weight distribution was 1.8, the polymerization activity was 1.2×10 8 g mol -1 , the glass transition temperature was 121 °C, and the cycloolefin insertion rate was 42.10 mol%.

[0201] Example 4

[0202] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst, and a chain transfer agent;

[0203] The main catalyst was dimethylsilylene-bis(2,7-di-tert-butylfluorenyl)-adamantylamine-dimethyltitanium;

[0204] The cocatalyst was triphenylcarbenium tetrakis(pentafluorophenyl)borate;

[0205] The chain transfer agent was dibutylzinc;

[0206] The molar ratio of the cocatalyst to the main catalyst was 1:1; the molar ratio of the chain transfer agent to the main catalyst was 80:1.

[0207] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0208] (1) Preparation of raw materials:

[0209] Organic solvent: n-hexane;

[0210] Cycloolefin: norbornene;

[0211] Non-cyclic olefin: ethylene;

[0212] The catalytic system for preparing the cycloolefin copolymer described above: the main catalyst, the cocatalyst, and the chain transfer agent;

[0213] Ethylene gas at a pressure of 3 atm;

[0214] Methanol;

[0215] The acidified precipitant: the acid is hydrochloric acid and the precipitant is ethanol;

[0216] (2) Under argon protection, successively add an organic solvent, a cycloolefin, a chain transfer agent, and a cocatalyst to the reaction vessel, introduce an acyclic olefin, then add the main catalyst, and then carry out a copolymerization reaction at 50 °C for 5 min. After the reaction is completed, add methanol to terminate the polymerization;

[0217] Among them, the molar ratio of the organic solvent to the cycloolefin is 21:1; the molar ratio of the cycloolefin to the acyclic olefin is 10:1; the molar ratio of the cycloolefin to the chain transfer agent is 104:1;

[0218] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with isopropanol 4 times, and vacuum drying to obtain the cycloolefin copolymer;

[0219] Among them, the vacuum degree of the vacuum drying is 0.04 atm, the temperature is 70 °C, and the time is 7 hours.

[0220] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 7.1×10 3 g / mol, the molecular weight distribution is 2.0, the polymerization activity is 2.1×10 8 g mol -1 , the glass transition temperature is 128 °C, and the cycloolefin insertion rate is 43.40 mol%.

[0221] Example 5

[0222] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst, and a chain transfer agent;

[0223] The main catalyst is dimethylsilylene-bis(3,6-dimethoxyfluorenyl)-adamantylamine-dimethyltitanium;

[0224] The cocatalyst is modified methylaluminoxane;

[0225] The chain transfer agent is diphenylzinc;

[0226] The molar ratio of the cocatalyst to the main catalyst is 800:1; the molar ratio of the chain transfer agent to the main catalyst is 100:1.

[0227] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0228] (1) Preparation of raw materials:

[0229] Organic solvent: methylcyclohexane;

[0230] Cycloolefin: tetracyclododecene;

[0231] Non-cyclic olefin: ethylene;

[0232] The above-mentioned catalytic system for preparing cycloolefin copolymer: main catalyst, co-catalyst and chain transfer agent;

[0233] Ethylene gas with a pressure of 3 atm;

[0234] Methanol;

[0235] Acidified precipitant: the acid is hydrochloric acid and the precipitant is isopropanol;

[0236] (2) Under the protection of argon, successively add the organic solvent, cycloolefin, chain transfer agent, co-catalyst into the reaction vessel, introduce the non-cyclic olefin, then add the main catalyst, and then carry out the copolymerization reaction at 60 °C for 5 min. After the reaction is completed, add methanol to terminate the polymerization;

[0237] Among them, the molar ratio of the organic solvent to the cycloolefin is 100:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 1:1; the molar ratio of the cycloolefin to the chain transfer agent is 2.7:1;

[0238] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with isopropanol 5 times and vacuum drying to obtain the cycloolefin copolymer;

[0239] Among them, the vacuum degree of the vacuum drying is 0.1 atm, the temperature is 70 °C, and the time is 6 hours.

[0240] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 7.7×10 3 g / mol, the molecular weight distribution is 2.1, and the polymerization activity is 1.8×10 8 g mol -1 , the glass transition temperature is 113 °C, and the cycloolefin insertion rate is 40.40 mol%.

[0241] Example 6

[0242] A catalytic system for preparing cycloolefin copolymer, comprising a main catalyst, a co-catalyst and a chain transfer agent;

[0243] The main catalyst is dimethylsilyl-bis(3,6-dimethoxyfluorenyl)-(α-dimethylnaphthylamido)-dimethyltitanium;

[0244] The cocatalyst is N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate;

[0245] The chain transfer agent is dimethylzinc;

[0246] The molar ratio of the cocatalyst to the main catalyst is 4:1; the molar ratio of the chain transfer agent to the main catalyst is 1:1.

[0247] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0248] (1) Preparation of raw materials:

[0249] Organic solvent: n-hexane;

[0250] Cycloolefin: tetracyclododecene;

[0251] Non-cyclic olefin: propylene;

[0252] The above catalytic system for preparing the cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0253] Propylene gas at a pressure of 3 atm;

[0254] Methanol;

[0255] Acidified precipitant: the acid is hydrochloric acid and the precipitant is acetone;

[0256] (2) Under nitrogen protection, add the organic solvent, cycloolefin, chain transfer agent, cocatalyst to the reaction vessel in sequence, introduce the non-cyclic olefin, then add the main catalyst, and then carry out copolymerization reaction at 60 °C for 1 min. After the reaction is completed, add methanol to terminate the polymerization;

[0257] Among them, the molar ratio of the organic solvent to the cycloolefin is 1:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 10:1; the molar ratio of the cycloolefin to the chain transfer agent is 54:1;

[0258] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then carry out filtration, acetone washing once and vacuum drying in sequence to obtain the cycloolefin copolymer;

[0259] Among them, the vacuum degree of vacuum drying is 0.02 atm, the temperature is 62 °C, and the time is 11 hours.

[0260] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 8.2×10 3 g / mol, the molecular weight distribution is 1.9, the polymerization activity is 9.6×10 7 g mol -1 , the glass transition temperature is 123 °C, and the cycloolefin insertion rate is 42.70 mol%.

[0261] Example 7

[0262] A catalytic system for preparing cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0263] The main catalyst is diphenylsilyl-bis(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)dimethyltitanium;

[0264] The cocatalyst is modified methylaluminoxane;

[0265] The chain transfer agent is di-n-butylmagnesium;

[0266] The molar ratio of the cocatalyst to the main catalyst is 1000:1; the molar ratio of the chain transfer agent to the main catalyst is 500:1.

[0267] A method for preparing cycloolefin copolymer, the specific steps are as follows:

[0268] (1) Preparation of raw materials:

[0269] Organic solvent: n-heptane;

[0270] Cycloolefin: norbornene;

[0271] Non-cyclic olefin: 1-hexene;

[0272] The above-mentioned catalytic system for preparing cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0273] The pressure is 1 atm;

[0274] Methanol;

[0275] Acidified precipitant: the acid is hydrochloric acid and the precipitant is methanol;

[0276] (2) Under nitrogen protection, add organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, cocatalyst to the reaction vessel in sequence, then add the main catalyst, and carry out copolymerization reaction at 120 °C for 30 min. After the reaction is completed, add methanol to terminate the polymerization;

[0277] Among them, the molar ratio of the organic solvent to the cycloolefin is 11:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 7:1; the molar ratio of the cycloolefin to the chain transfer agent is 108:1;

[0278] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then carry out filtration, washing with cyclohexanone twice and vacuum drying in sequence to obtain the cycloolefin copolymer;

[0279] Among them, the vacuum degree of the vacuum drying is 0.04 atm, the temperature is 64 °C, and the time is 10 hours.

[0280] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 2.5×10 4 g / mol, the molecular weight distribution is 3.0, and the polymerization activity is 2.6×10 7 g mol -1 , the glass transition temperature is 84 °C, and the cycloolefin insertion rate is 33.80 mol%.

[0281] Example 8

[0282] A catalytic system for preparing cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0283] The main catalyst is dimethylsilyl-bridged-fluorenyl-tert-butylamino-dimethylzirconium;

[0284] The cocatalyst is triphenylmethyltetrakis(pentafluorophenyl)borate;

[0285] The chain transfer agent is dibutylzinc;

[0286] The molar ratio of the cocatalyst to the main catalyst is 10:1; the molar ratio of the chain transfer agent to the main catalyst is 200:1.

[0287] A method for preparing cycloolefin copolymer, the specific steps are as follows:

[0288] (1) Preparation of raw materials:

[0289] Organic solvent: cyclohexane;

[0290] Cycloolefin: norbornene;

[0291] Non-cyclic olefin: 1-octene;

[0292] The above-mentioned catalytic system for preparing cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0293] The pressure is 1 atm;

[0294] Methanol;

[0295] Acidified precipitant: the acid is hydrochloric acid and the precipitant is ethanol;

[0296] (2) Under argon protection, add organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, cocatalyst to the reaction vessel in sequence, then add the main catalyst, and carry out copolymerization reaction at 80 °C for 15 min. After the reaction is completed, add methanol to terminate the polymerization;

[0297] Among them, the molar ratio of the organic solvent to the cycloolefin is 23:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 4:1; the molar ratio of the cycloolefin to the chain transfer agent is 95:1;

[0298] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing an acidified precipitant, and then perform filtration, ethanol washing three times, and vacuum drying in sequence to obtain a cycloolefin copolymer;

[0299] Among them, the vacuum degree of the vacuum drying is 0.06 atm, the temperature is 66 °C, and the time is 8 hours.

[0300] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 6×10 4 g / mol, the molecular weight distribution is 2.6, and the polymerization activity is 3.8×10 7 g mol -1 , the glass transition temperature is 78 °C, and the cycloolefin insertion rate is 31.30 mol%.

[0301] Example 9

[0302] A catalytic system for preparing a cycloolefin copolymer, including a main catalyst, a cocatalyst, and a chain transfer agent;

[0303] The main catalyst is dimethylsilylene-bis(2,7-di-tert-butylfluorenyl)-adamantylamine dimethylzirconium;

[0304] The cocatalyst is dichloroethylaluminum;

[0305] The chain transfer agent is diisopropylzinc;

[0306] The molar ratio of the cocatalyst to the main catalyst is 1:1; the molar ratio of the chain transfer agent to the main catalyst is 300:1.

[0307] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0308] (1) Preparation of raw materials:

[0309] Organic solvent: n-pentane;

[0310] Cycloolefin: cyclopentadiene;

[0311] Non-cyclic olefin: 1-pentene;

[0312] The above-mentioned catalytic system for preparing a cycloolefin copolymer: main catalyst, cocatalyst, and chain transfer agent;

[0313] The pressure is 1 atm;

[0314] Methanol;

[0315] Acidified precipitant: The acid is hydrochloric acid, and the precipitant is isopropanol;

[0316] (2) Under helium protection, organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, and co-catalyst were successively added to the reaction vessel, then the main catalyst was added, and then copolymerization reaction was carried out at 90 °C for 30 min. After the reaction was completed, methanol was added to terminate the polymerization;

[0317] Among them, the molar ratio of the organic solvent to the cycloolefin was 46:1; the molar ratio of the cycloolefin to the non-cyclic olefin was 2:1; the molar ratio of the cycloolefin to the chain transfer agent was 5.4:1;

[0318] (3) The reaction solution obtained from the polymerization reaction in step (2) was poured into a container containing an acidified precipitant, and then filtered, washed with isopropanol 4 times, and vacuum dried in sequence to obtain a cycloolefin copolymer;

[0319] Among them, the vacuum degree of the vacuum drying was 0.08 atm, the temperature was 68 °C, and the time was 7 hours.

[0320] The weight-average molecular weight of the finally obtained cycloolefin copolymer was 4.7×10 4 g / mol, the molecular weight distribution was 2.5, the polymerization activity was 1.0×10 7 g mol -1 , the glass transition temperature was 67 °C, and the cycloolefin insertion rate was 21.00 mol%.

[0321] Example 10

[0322] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a co-catalyst, and a chain transfer agent;

[0323] The main catalyst was dimethylsilylene-bis(fluorenyl)-tert-butylamido-dimethylhafnium;

[0324] The co-catalyst was triphenylmethyltetrakis(pentafluorophenyl)borate;

[0325] The chain transfer agent was n-butylethylmagnesium;

[0326] The molar ratio of the co-catalyst to the main catalyst was 1:1; the molar ratio of the chain transfer agent to the main catalyst was 400:1.

[0327] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0328] (1) Preparation of raw materials:

[0329] Organic solvent: xylene;

[0330] Cycloolefin: dicyclopentadiene;

[0331] Non-cyclic olefin: 1-dodecene;

[0332] The catalytic system for preparing the cycloolefin copolymer described above: the main catalyst, the cocatalyst, and the chain transfer agent;

[0333] The pressure is 1 atm;

[0334] Methanol;

[0335] The acidified precipitant: the acid is hydrochloric acid and the precipitant is acetone;

[0336] (2) Under nitrogen protection, successively add the organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, and cocatalyst into the reaction vessel, then add the main catalyst, and then carry out the copolymerization reaction at 100 °C for 20 min. After the reaction is completed, add methanol to terminate the polymerization;

[0337] Among them, the molar ratio of the organic solvent to the cycloolefin is 1:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 10:1; the molar ratio of the cycloolefin to the chain transfer agent is 27:1;

[0338] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with acetone 5 times, and vacuum drying to obtain the cycloolefin copolymer;

[0339] Among them, the vacuum degree of the vacuum drying is 0.09 atm, the temperature is 70 °C, and the time is 6 hours.

[0340] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 8.6×10 4 g / mol, the molecular weight distribution is 3.0, and the polymerization activity is 4.2×10 7 g mol -1 , the glass transition temperature is 74 °C, and the cycloolefin insertion rate is 30.20 mol%.

[0341] Example 11

[0342] A catalytic system for preparing a cycloolefin copolymer, including a main catalyst, a cocatalyst, and a chain transfer agent;

[0343] The main catalyst is dimethylsilyl-bis(2,7-di-tert-butylfluorenyl)-tert-butylamido-zirconium dimethyl;

[0344] The cocatalyst is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate;

[0345] The chain transfer agent is di-n-butylmagnesium;

[0346] The molar ratio of the cocatalyst to the main catalyst is 900:1; the molar ratio of the chain transfer agent to the main catalyst is 500:1.

[0347] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0348] (1) Preparation of raw materials:

[0349] Organic solvent: methylcyclohexane;

[0350] Cycloolefin: cyclopentadiene;

[0351] Non-cyclic olefin: 1-hexene;

[0352] The catalytic system for preparing the cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0353] The pressure is 1 atm;

[0354] Methanol;

[0355] Acidified precipitant: the acid is hydrochloric acid and the precipitant is acetone;

[0356] (2) Under the protection of helium, successively add the organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, cocatalyst into the reaction vessel, then add the main catalyst, and then carry out the copolymerization reaction at 70 °C for 10 min. After the reaction is completed, add methanol to terminate the polymerization;

[0357] Among them, the molar ratio of the organic solvent to the cycloolefin is 46:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 7:1; the molar ratio of the cycloolefin to the chain transfer agent is 46:1;

[0358] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with isopropanol twice and vacuum drying to obtain the cycloolefin copolymer;

[0359] Among them, the vacuum degree of the vacuum drying is 0.01 atm, the temperature is 70 °C, and the time is 7 hours.

[0360] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 1.7×10 4 g / mol, the molecular weight distribution is 2.4, and the polymerization activity is 5.3×10 7 g mol -1 , the glass transition temperature is 77 °C, and the cycloolefin insertion rate is 31.20 mol%.

[0361] Example 12

[0362] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0363] The main catalyst is dimethylsilyl-bridged-fluorenyl-tert-butylamido-hafnium dichloride;

[0364] The cocatalyst is dichloroethylaluminum;

[0365] The chain transfer agent is diphenylzinc;

[0366] The molar ratio of the cocatalyst to the main catalyst is 8:1; the molar ratio of the chain transfer agent to the main catalyst is 200:1.

[0367] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0368] (1) Preparation of raw materials:

[0369] Organic solvent: n-heptane;

[0370] Cycloolefin: dicyclopentadiene;

[0371] Non-cyclic olefin: 1-octene;

[0372] The above-mentioned catalytic system for preparing the cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0373] The pressure is 1 atm;

[0374] Methanol;

[0375] Acidified precipitant: the acid is hydrochloric acid and the precipitant is isopropanol;

[0376] (2) Under nitrogen protection, add organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, cocatalyst to the reaction vessel in sequence, then add the main catalyst, and then carry out copolymerization reaction at 110 °C for 10 min. After the reaction is completed, add methanol to terminate the polymerization;

[0377] Among them, the molar ratio of the organic solvent to the cycloolefin is 58:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 6:1; the molar ratio of the cycloolefin to the chain transfer agent is 68:1;

[0378] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then carry out filtration, isopropanol washing once and vacuum drying in sequence to obtain the cycloolefin copolymer;

[0379] Among them, the vacuum degree of the vacuum drying is 0.1 atm, the temperature is 60 °C, and the time is 6 hours.

[0380] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 2.3×10 4 g / mol, the molecular weight distribution is 2.2, and the polymerization activity is 1.6×10 7 g mol -1 -1, the glass transition temperature is 81 °C, and the cycloolefin insertion rate is 33.40 mol%.

[0381] Example 13

[0382] A catalytic system for preparing cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0383] The main catalyst is dimethylsilylene-bis(3,6-di-tert-butylfluorenyl)-tert-butylamido-dimethyltitanium;

[0384] The cocatalyst is diethylaluminum chloride;

[0385] The chain transfer agent is dibutylzinc;

[0386] The molar ratio of the cocatalyst to the main catalyst is 200:1; the molar ratio of the chain transfer agent to the main catalyst is 60:1.

[0387] A method for preparing cycloolefin copolymer, the specific steps are as follows:

[0388] (1) Preparation of raw materials:

[0389] Organic solvent: cycloheptane;

[0390] Cycloolefin: tetracyclododecene;

[0391] Non-cyclic olefin: 1-heptene;

[0392] The above-mentioned catalytic system for preparing cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0393] The pressure is 1 atm;

[0394] Methanol;

[0395] Acidified precipitant: the acid is hydrochloric acid and the precipitant is methanol;

[0396] (2) Under the protection of helium, successively add organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, cocatalyst into the reaction vessel, then add the main catalyst, and carry out copolymerization reaction at 50 °C for 5 min. After the reaction is completed, add methanol to terminate the polymerization;

[0397] Among them, the molar ratio of the organic solvent to the cycloolefin is 13:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 8:1; the molar ratio of the cycloolefin to the chain transfer agent is 67:1;

[0398] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with methanol 3 times and vacuum drying to obtain cycloolefin copolymer;

[0399] Among them, the vacuum degree of vacuum drying is 0.02 atm, the temperature is 60 °C, and the time is 8 hours.

[0400] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 8.5×10 3 g / mol, the molecular weight distribution is 2.0, and the polymerization activity is 9.5×10 8 g mol -1 , the glass transition temperature is 102 °C, and the cycloolefin insertion rate is 38.40 mol%.

[0401] Example 14

[0402] A catalytic system for preparing cycloolefin copolymer, comprising a main catalyst, a cocatalyst and a chain transfer agent;

[0403] The main catalyst is dimethylsilylene-bis(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-tert-butylamido-dimethyltitanium;

[0404] The cocatalyst is triphenylcarbenium tetrakis(pentafluorophenyl)borate;

[0405] The chain transfer agent is di-n-butylmagnesium;

[0406] The molar ratio of the cocatalyst to the main catalyst is 5:1; the molar ratio of the chain transfer agent to the main catalyst is 300:1.

[0407] A method for preparing cycloolefin copolymer, the specific steps are as follows:

[0408] (1) Preparation of raw materials:

[0409] Organic solvent: n-pentane;

[0410] Cycloolefin: cyclopentadiene;

[0411] Non-cyclic olefin: ethylene;

[0412] The above-mentioned catalytic system for preparing cycloolefin copolymer: main catalyst, cocatalyst and chain transfer agent;

[0413] Ethylene gas with a pressure of 3 atm;

[0414] Methanol;

[0415] Acidified precipitant: the acid is hydrochloric acid and the precipitant is ethanol;

[0416] (2) Under nitrogen protection, add the organic solvent, cycloolefin, chain transfer agent, cocatalyst to the reaction vessel in sequence, introduce the non-cyclic olefin, then add the main catalyst, and carry out copolymerization reaction at 60 °C for 4 min. After the reaction is completed, add methanol to terminate the polymerization;

[0417] Among them, the molar ratio of the organic solvent to the cycloolefin is 16:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 10:1; the molar ratio of the cycloolefin to the chain transfer agent is 74:1;

[0418] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing an acidified precipitant, and then perform filtration, ethanol washing twice, and vacuum drying in sequence to obtain a cycloolefin copolymer;

[0419] Among them, the vacuum degree of the vacuum drying is 0.03 atm, the temperature is 65 °C, and the time is 8 hours.

[0420] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 9.4×10 3 g / mol, the molecular weight distribution is 1.9, and the polymerization activity is 8.9×10 8 g mol -1 , the glass transition temperature is 110 °C, and the cycloolefin insertion rate is 40.00 mol%.

[0421] Example 15

[0422] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst, and a chain transfer agent;

[0423] The main catalyst is dimethylsilyl-bridged-fluorenyl-(α-dimethylnaphthylamine)-dimethyltitanium;

[0424] The cocatalyst is diethylaluminum chloride;

[0425] The chain transfer agent is dimethylzinc;

[0426] The molar ratio of the cocatalyst to the main catalyst is 800:1; the molar ratio of the chain transfer agent to the main catalyst is 100:1.

[0427] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0428] (1) Preparation of raw materials:

[0429] Organic solvent: cycloheptane;

[0430] Cycloolefin: tetracyclododecene;

[0431] Non-cyclic olefin: propylene;

[0432] The above-mentioned catalytic system for preparing a cycloolefin copolymer: main catalyst, cocatalyst, and chain transfer agent;

[0433] Propylene gas with a pressure of 2 atm;

[0434] Methanol;

[0435] Acidified precipitant: the acid is hydrochloric acid, and the precipitant is isopropanol;

[0436] (2) Under helium protection, organic solvent, cycloolefin, chain transfer agent, and cocatalyst were successively added to the reaction vessel. Non-cyclic olefin was introduced, and then the main catalyst was added. Then, copolymerization reaction was carried out at 80 °C for 10 min. After the reaction was completed, methanol was added to terminate the polymerization;

[0437] Among them, the molar ratio of the organic solvent to the cycloolefin was 23:1; the molar ratio of the cycloolefin to the non-cyclic olefin was 4:1; the molar ratio of the cycloolefin to the chain transfer agent was 54:1;

[0438] (3) The reaction solution obtained from the polymerization reaction in step (2) was poured into a container containing an acidified precipitant, and then filtered, washed with isopropanol 5 times, and vacuum dried to obtain a cycloolefin copolymer;

[0439] Among them, the vacuum degree of the vacuum drying was 0.01 atm, the temperature was 70 °C, and the time was 10 hours.

[0440] The weight-average molecular weight of the finally obtained cycloolefin copolymer was 2.1×10 4 g / mol, the molecular weight distribution was 2.6, the polymerization activity was 3.2×10 7 g mol -1 , the glass transition temperature was 85 °C, and the cycloolefin insertion rate was 33.90 mol%.

[0441] Example 16

[0442] A catalytic system for preparing a cycloolefin copolymer, comprising a main catalyst, a cocatalyst, and a chain transfer agent;

[0443] The main catalyst was dimethylsilylene-bis(3,6-di-tert-butylfluorenyl)-tert-butylamido-zirconium dimethyl;

[0444] The cocatalyst was triphenylmethyltetrakis(pentafluorophenyl)borate;

[0445] The chain transfer agent was n-butylethylmagnesium;

[0446] The molar ratio of the cocatalyst to the main catalyst was 1:1; the molar ratio of the chain transfer agent to the main catalyst was 200:1.

[0447] A method for preparing a cycloolefin copolymer, the specific steps are as follows:

[0448] (1) Preparation of raw materials:

[0449] Organic solvent: n-pentane;

[0450] Cycloolefin: cyclopentadiene;

[0451] Non-cyclic olefin: 1-hexene;

[0452] The catalytic system for preparing the cycloolefin copolymer described above: the main catalyst, the cocatalyst, and the chain transfer agent;

[0453] The pressure is 1 atm;

[0454] Methanol;

[0455] The acidified precipitant: the acid is hydrochloric acid and the precipitant is ethanol;

[0456] (2) Under nitrogen protection, successively add the organic solvent, cycloolefin, non-cyclic olefin, chain transfer agent, and cocatalyst into the reaction vessel, then add the main catalyst, and carry out the copolymerization reaction at 100 °C for 30 min. After the reaction is completed, add methanol to terminate the polymerization;

[0457] Among them, the molar ratio of the organic solvent to the cycloolefin is 11:1; the molar ratio of the cycloolefin to the non-cyclic olefin is 2:1; the molar ratio of the cycloolefin to the chain transfer agent is 5.4:1;

[0458] (3) Pour the reaction solution obtained from the polymerization reaction in step (2) into a container containing the acidified precipitant, and then successively carry out filtration, washing with acetone once, and vacuum drying to obtain the cycloolefin copolymer;

[0459] Among them, the vacuum degree of the vacuum drying is 0.06 atm, the temperature is 60 °C, and the time is 9 hours.

[0460] The weight-average molecular weight of the finally obtained cycloolefin copolymer is 4.2×10 4 g / mol, the molecular weight distribution is 2.4, the polymerization activity is 5.6×10 7 g mol -1 , the glass transition temperature is 90 °C, and the cycloolefin insertion rate is 34.40 mol%.

Claims

1. A catalytic system for preparing cycloolefin copolymers, characterized in that: Including main catalyst, co-catalyst and chain transfer agent; The main catalyst is a silane-bridged fluorenylamino dimethyl titanium complex, a silane-bridged fluorenylamino dimethyl zirconium complex, a silane-bridged fluorenylamino dimethyl hafnium complex or a silane-bridged fluorenylamino dichloro hafnium complex; The co-catalyst is an aluminum compound co-catalyst or a boron compound co-catalyst; The boron compound co-catalyst is one or more of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate and trityltetrakis(pentafluorophenyl)borate; The chain transfer agent is one or more of diphenyl zinc, dimethyl zinc, diethyl zinc, diisopropyl zinc, dibutyl zinc, diethyl magnesium, diisobutyl magnesium, di-n-butyl magnesium and n-butylethyl magnesium; The molar ratio of the aluminum compound co-catalyst to the main catalyst is 1-1000:1; the molar ratio of the boron compound co-catalyst to the main catalyst is 1-10:1; and the molar ratio of the chain transfer agent to the main catalyst is 1-500:

1.

2. A catalytic system for preparing cycloolefin copolymers according to claim 1, characterized in that: The main catalyst is methylphenylsilicon bridge group-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, diphenylsilicon bridge group-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilicon bridge group-fluorenyl-tert-butylamino-dimethyltitanium, dimethylsilicon bridge group-(2,7-di-tert-butylfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilicon bridge group-(3,6-di-tert-butylfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilicon bridge group-(3,6-dimethoxyfluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilicon bridge group-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-tert-butylamino-dimethyltitanium, dimethylsilicon Bridge group-fluorenyl-(α-dimethylanilino)-dimethyltitanium, dimethylsilicon bridge group-(2,7-di-tert-butylfluorenyl)-(α-dimethylanilino)-dimethyltitanium, dimethylsilicon bridge group-(3,6-di-tert-butylfluorenyl)-(α-dimethylanilino)-dimethyltitanium, dimethylsilicon bridge group-(3,6-dimethoxyfluorenyl)-(α-dimethylanilino)-dimethyltitanium, dimethylsilicon bridge group-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-(α-dimethylanilino)-dimethyltitanium, dimethylsilicon bridge group-fluorenyl-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilicon bridge group-(2,7-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino) -dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium, dimethylsilyl-(fluorenyl-adamantylamino)-dimethyltitanium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-adamantylamino-dimethyltitanium, dimethylsilyl-(2,6-di(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-(α-dimethylnaphthylamino)-dimethyltitanium (1,1,4,4-tetramethylcyclohexyl)fluorenyl)-adamantaneamine-dimethyltitanium, dimethylsilyl-fluorenyl-tert-butylamino-dimethylzirconium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(3,6-di-tert-butylfluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(3,6-dimethoxy Dimethylsilyl-(2,6-bis(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-tert-butylamino-dimethylzirconium, dimethylsilyl-(fluorenyl)-adamantylamino-dimethylzirconium, dimethylsilyl-(2,7-di-tert-butylfluorenyl)-adamantylamino-dimethylzirconium, dimethylsilyl-(3,6-di-tert-butylfluorenyl) -adamantanamido-dimethylzirconium, dimethylsilyl-(3,6-dimethoxyfluorenyl)-adamantanamido-dimethylzirconium, dimethylsilyl-(2,6-di(1,1,4,4-tetramethylcyclohexyl)fluorenyl)-adamantanamido-dimethylzirconium, dimethylsilyl-fluorenyl-tert-butylamino-dimethylhafnium, dimethylsilyl-fluorenyl-tert-butylamino-dimethylhafnium, dimethylsilyl-fluorenyl-tert-butylamino-dichlorohafnium or dimethylsilyl-fluorenyl-adamantanamido-dichlorohafnium.

3. A catalytic system for preparing cycloolefin copolymers according to claim 1, characterized in that: The aluminum compound co-catalyst is one or more of methylaluminoxane, modified methylaluminoxane, trialkylaluminum, dialkylaluminum chloride, monoalkylaluminum dichloride and trialkylaluminum trichloride.

4. A method for preparing a cycloolefin copolymer, characterized in that: The catalytic system as claimed in any one of claims 1 to 3 is used to copolymerize cycloolefins and non-cyclic olefins under the catalytic action to obtain cycloolefin copolymers.

5. The method for preparing a cycloolefin copolymer according to claim 4, characterized in that: Cycloolefins are unsaturated cyclic olefins with the following structural formula: In the formula, m is 0, 1 or 2, and R2 and R3 are each independently selected from a hydrogen atom, an alkyl group and a cycloalkyl group; Acyclic olefins are C2 to C20 straight chain olefins with the following structural formula: In the formula, R1 is independently hydrogen or a saturated aliphatic hydrocarbon group having 1 to 19 carbon atoms.

6. The method for preparing a cycloolefin copolymer according to claim 4, characterized in that: The reaction adopts solution polymerization method, and the copolymerization reaction is carried out in an organic solvent; The organic solvent is one or more of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons.

7. The method for preparing a cycloolefin copolymer according to claim 6, characterized in that: The reaction temperature is 40-120°C; The reaction time is 1 to 30 minutes.

8. The method for preparing a cycloolefin copolymer according to claim 4, characterized in that: The molar ratio of the cyclic olefin to the non-cyclic olefin is 1 to 10:

1.

9. The method for preparing a cycloolefin copolymer according to any one of claims 4 to 8, characterized in that: The weight average molecular weight of the cycloolefin copolymer is 1×10 3 ~60×10 4 g / mol, molecular weight distribution is 1.5-3.0, polymerization activity is 1×10 7 ~5×10 8 g mol -1 h -1 , the glass transition temperature is 67 to 147°C, and the cycloolefin insertion rate is 21.0 to 51.1 mol%.

10. The method for preparing a cycloolefin copolymer according to claim 9, characterized in that: The structural formula of cycloolefin copolymer is as follows: Among them, 1≤X / Y≤5, 2≤n≤5000; R1 is independently hydrogen or a saturated aliphatic hydrocarbon group having 1 to 19 carbon atoms; R2 and R3 are each independently selected from a hydrogen atom, an alkyl group and a cycloalkyl group.

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