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CN112745431A - Cycloolefin copolymer and preparation method thereof - Google Patents

Cycloolefin copolymer and preparation method thereof Download PDF

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Publication number
CN112745431A
CN112745431A CN202011538511.0A CN202011538511A CN112745431A CN 112745431 A CN112745431 A CN 112745431A CN 202011538511 A CN202011538511 A CN 202011538511A CN 112745431 A CN112745431 A CN 112745431A
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copolymer
structural unit
norbornene
group
cycloolefin copolymer
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CN112745431B (en
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廖恒
赵环宇
刘阳
左洪亮
陈炳琳
黄杰
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Guangdong Teju New Materials Technology Co ltd
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Guangdong Xinhua Yueyusheng Technology Co ltd
Guangdong Xinhuayue Petrochemical Inc Co
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

The invention relates to the field of olefin polymerization, in particular to a cycloolefin copolymer and a preparation method thereof, wherein the cycloolefin copolymer is composed of structural units
Figure DDA0002854240060000011
Structural unit
Figure DDA0002854240060000012
Structural unit

Description

Cycloolefin copolymer and preparation method thereof
Technical Field
The invention relates to the field of olefin polymerization, in particular to a cyclic olefin copolymer and a preparation method thereof.
Background
The cycloolefin copolymer is an amorphous thermoplastic polymer prepared by the addition copolymerization of cycloolefin monomers, has the characteristics of good transparency, good heat resistance, low water absorption, chemical corrosion resistance and the like, has the advantages of high mechanical strength, good dimensional stability, low dielectric constant and the like, and is widely applied to the fields of optical materials, communication equipment, medical materials, packaging materials and the like.
According to the known literature, the cycloolefin copolymer can be prepared by metallocene catalysts (CN95107662, CN94120496) or other non-metallocene transition metal catalysts (CN201610040109), but the polymerization system can generate partially crystalline polyethylene segments due to inevitable ethylene homopolymerization in the polymerization process, which affects the transparency of the polymer. Meanwhile, the heat resistance of the cycloolefin copolymer is desired to be improved.
Disclosure of Invention
In view of the problems involved in the prior art, the first aspect of the present invention provides a cycloolefin copolymer formed from the structural unit (a)
Figure BDA0002854240050000011
Structural unit (b)
Figure BDA0002854240050000012
Structural unit (c)
Figure BDA0002854240050000013
Is composed ofWherein the repeating number x of the structural unit (a) in the molecular chain of the copolymer unit is 0-3, the repeating number y of the structural unit (b) in the molecular chain of the copolymer unit is 1-3, the repeating number z of the structural unit (c) in the molecular chain of the copolymer unit is 1-3, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar groups; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2.
In a preferred embodiment of the present invention, R is any one of hydrogen, methyl, ethyl, isopropyl, n-butyl, hydroxyl, carboxyl, carbomethoxy, amino, dimethylamino, trimethylsilyl, and trimethoxysilyl.
As a preferred technical scheme of the invention, the preparation raw materials of the cycloolefin copolymer comprise ethylene, a norbornene cycloolefin monomer shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst, wherein,
Figure BDA0002854240050000021
a compound of the formula (I),
Figure BDA0002854240050000022
formula (II); m is 0 or 1, R is any one of hydrogen, alkyl and polar group, R1-R5、R8-R12Each independently is any one of hydrogen, alkyl and aryl, R6、R7Independently represents any one of hydrogen, alkyl and aryl or combines the same cyclic substituent, Mt represents nickel or palladium, and X represents halogen and substituted or unsubstituted alkyl.
As a preferable technical means of the present invention, R is1、R5、R8、R12Each independently is any one of methyl, isopropyl, phenyl and benzhydryl, R2-R4、R9-R11Is hydrogen, R6、R7Each independently is any one of hydrogen, methyl, phenyl, acenaphthenyl and dibenzo bucket alkenyl, and X is any one of chlorine, bromine, methyl, benzyl and substituted alkyl.
As a preferred technical scheme of the invention, the norbornene cyclic olefin monomer is any one of norbornene, alkyl substituted norbornene, methyl norbornene, ethyl norbornene, n-propyl norbornene, isopropyl norbornene, n-butyl norbornene, hydroxy norbornene, carboxyl norbornene, carbomethoxynorbornene, amino norbornene, alkylamino norbornene, silyl norbornene, tetracyclododecene, alkyl tetracyclododecene, hydroxy tetracyclododecene, carboxyl tetracyclododecene, estertetracyclododecene, amino tetracyclododecene, alkylamino tetracyclododecene and silyl tetracyclododecene.
As a preferable technical scheme of the invention, the cocatalyst is alkylaluminoxane, the structure is (-AlM-O-) n, n is any positive integer, and M is any one of methyl, ethyl, isobutyl and n-octyl.
As a preferred technical scheme of the invention, the preparation raw material of the cycloolefin copolymer also comprises an inert hydrocarbon solvent.
In a preferred embodiment of the present invention, the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon, preferably n-hexane, cyclohexane, n-heptane, C6-C12One or more of mixed alkane, benzene and toluene.
The second aspect of the present invention provides a method for preparing the cycloolefin copolymer, which comprises: ethylene, norbornene cyclic olefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized under the condition of existence or nonexistence of inert hydrocarbon solvent and the temperature of 0-100 ℃ and the pressure of 0.1-100atm to obtain the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the post-transition metal catalyst with a specific structure with the characteristic of chain walking, avoids the generation of a crystalline ethylene chain segment, improves the transparency of the obtained copolymer, introduces a branched structure into a polymer chain, has higher glass transition temperature than a metallocene ethylene/norbornene copolymer under the same norbornene content, and improves the thermal stability of the polymer. Meanwhile, the catalytic system has good tolerance to water, oxygen and polar groups, can be used for preparing the cyclic olefin copolymer with the polar groups, and has wider application prospect.
Detailed Description
The first aspect of the present invention provides the cycloolefin copolymer, which is composed of the structural unit (a)
Figure BDA0002854240050000031
Structural unit (b)
Figure BDA0002854240050000032
Structural unit (c)
Figure BDA0002854240050000033
Wherein the number of repetition x of the structural unit (a) in the molecular chain of the copolymer unit is 0 to 3, the number of repetition y of the structural unit (b) in the molecular chain of the copolymer unit is 1 to 3, the number of repetition z of the structural unit (c) in the molecular chain of the copolymer unit is 1 to 3, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar groups; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2.
Molecular weight distribution: polymers and low molecular weight compounds are different and do not have a fixed molecular weight but rather a mixed system of homologues of different molecular weights. Thus the polymer molecular weight is an average and has a distribution concept. This heterogeneity of molecular weights is referred to as the polydispersity of the polymer. The polydispersity of a polymer sample is generally characterized by the polydispersity α, which is the ratio of the weight average molecular weight to the number average molecular weight or the ratio of the Z average molecular weight to the weight average molecular weight.
In one embodiment, R is any one of hydrogen, methyl, ethyl, isopropyl, n-butyl, hydroxyl, carboxyl, carbomethoxy, amino, dimethylamino, trimethylsilyl, trimethoxysilyl.
In one embodiment, the starting material for the preparation of the cycloolefin copolymer comprisesEthylene, a norbornene cyclic olefin monomer shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst, wherein,
Figure BDA0002854240050000041
a compound of the formula (I),
Figure BDA0002854240050000042
formula (II); m is 0 or 1, R is any one of hydrogen, alkyl and polar group, R1-R5、R8-R12Each independently is any one of hydrogen, alkyl and aryl, R6、R7Independently represents any one of hydrogen, alkyl and aryl or combines the same cyclic substituent, Mt represents nickel or palladium, and X represents halogen and substituted or unsubstituted alkyl.
Preferably, said R is1、R5、R8、R12Each independently is any one of methyl, isopropyl, phenyl and benzhydryl, R2-R4、R9-R11Is hydrogen, R6、R7Each independently is any one of hydrogen, methyl, phenyl, acenaphthenyl and dibenzo bucket alkenyl, and X is any one of chlorine, bromine, methyl, benzyl and substituted alkyl; the obtained catalyst has good reaction controllability in the catalytic polymerization process, can better avoid the generation of crystalline ethylene chain segments, improves the transparency probability of the obtained copolymer, has better chain walking characteristic under the condition, has a proper branched chain structure on the copolymer chain, and obtains better heat resistance.
In one embodiment, the norbornene-type cycloolefin monomer is any one of norbornene, alkyl-substituted norbornene, methylnorbornene, ethylnorbornene, n-propylnorbornene, isopropylnorbornene, n-butylnorbornene, hydroxynorbornene, carboxynorbornene, carbomethoxynorbornene, aminonorbornene, alkylaminocarbonylene, silylnorbornene, tetracyclododecene, alkyltetracyclododecene, hydroxytetracyclododecene, carboxytetracyclododecene, estertetracyclododecene, aminotetracyclododecene, alkylaminocyclododecene, and silyltetracyclododecene.
Preferably, the norbornene-type cyclic olefin monomer is norbornene or tetracyclododecene.
In the preparation process of the cycloolefin copolymer, the norbornene and the tetracyclododecene have simple structures, easy synthesis and high reaction activity, and the obtained ethylene/norbornene copolymer or ethylene/tetracyclododecene copolymer has regular structures and excellent performance.
In one embodiment, the cocatalyst is an alkylaluminoxane having the structure (-AlM-O-) n, where n is any positive integer.
Preferably, M is any one of methyl, ethyl, isobutyl and n-octyl; more preferably, M is methyl or isobutyl.
In the preparation of the cycloolefin copolymers of the present application, the synergistic effect with the catalyst is better when M is methyl or isobutyl.
In one embodiment, the starting material for the preparation of the cycloolefin copolymer further includes an inert hydrocarbon solvent.
Preferably, the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon; further preferably, the inert hydrocarbon solvent is selected from n-hexane, cyclohexane, n-heptane, C6-C12One or more of mixed alkane, benzene and toluene; more preferably, the inert hydrocarbon solvent is n-heptane and/or toluene.
In one embodiment, the ethylene content is adjusted to provide a pressure of from 0.1 to 100 atm.
The content of the norbornene-type cycloolefin monomer in the present application is not particularly limited, and may be conventionally selected by those skilled in the art as needed.
In one embodiment, the norbornene-type cycloolefin monomer is present in the cycloolefin copolymer in a proportion of 20 to 35 mol%.
The concentrations of the catalyst and the cocatalyst are not particularly limited in the present application and may be routinely selected by those skilled in the art.
In one embodiment, the concentration of the catalyst is from 0.1 to 10. mu. mol/L.
In one embodiment, the concentration of the promoter is from 0.1 to 10 mmol/L.
The second aspect of the present invention provides a method for preparing the cycloolefin copolymer, which comprises: ethylene, norbornene cyclic olefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized under the condition of existence or nonexistence of inert hydrocarbon solvent and the temperature of 0-100 ℃ and the pressure of 0.1-100atm to obtain the catalyst.
In one embodiment, the method of preparing the cyclic olefin copolymer comprises: ethylene, a norbornene cyclic olefin monomer shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst are copolymerized at 0-100 ℃ and 0.1-100atm in the presence or absence of an inert hydrocarbon solvent to obtain a reaction liquid, the reaction liquid is added into a hydrochloric acid/ethanol solution to terminate the reaction, the separated copolymer is filtered, washed by ethanol and dried, and the catalyst is obtained.
Preferably, the preparation method of the cycloolefin copolymer includes: ethylene, a norbornene cyclic olefin monomer shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst are copolymerized for 30min at 20-80 ℃ and 1-30atm in the presence or absence of an inert hydrocarbon solvent to obtain a reaction solution, the reaction solution is added into a 10 vol% hydrochloric acid/ethanol solution to terminate the reaction, the separated copolymer is filtered, washed by ethanol and dried in vacuum at 80 ℃ for 24h to obtain the catalyst.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
The content of cycloolefine monomer in the copolymer is measured by a nuclear magnetic resonance apparatus, and deuterated chloroform is used as a solvent. The molecular weight and molecular weight distribution of the copolymer were measured by high temperature gel chromatography (HTGPC) using 1,2, 4-trichlorobenzene as a solvent. The glass transition temperature of the copolymer was measured by a Differential Scanning Calorimeter (DSC).
Example 1
Example 1 of the present invention provides the cycloolefin copolymer, which is prepared by the following method:
under nitrogen atmosphere, adding 38mL of pre-prepared 0.30mol/L norbornene toluene solution and 1mL of 10 wt% methylaluminoxane toluene solution (cocatalyst) into a 100mL glass bottle, adjusting ethylene pressure to 1atm, and stirring and balancing at 20 ℃ for 30 min; adding 1mL of toluene solution of 1 mu mol/mL of catalyst 1 to start reaction, keeping the ethylene pressure at 1atm, and carrying out polymerization reaction for 30 min; the reaction mixture was added to a 10 vol% hydrochloric acid/ethanol solution to terminate the reaction, and the precipitated copolymer was filtered, washed with ethanol, and vacuum-dried at 80 ℃ for 24 hours to obtain 0.55g of a copolymer.
The catalyst 1 has the structure
Figure BDA0002854240050000061
R in catalyst 11-R12Physical properties of Mt, and copolymer are illustrated in table 1 below.
Example 2
Example 2 of the present invention provides the cycloolefin copolymer, which was prepared in the same manner as in example 1 except that the catalyst 1 was replaced with the catalyst 2 to obtain a copolymer weight of 0.52 g.
The catalyst 2 has the structure
Figure BDA0002854240050000062
R in catalyst 21-R12Physical properties of Mt, and copolymer are illustrated in table 1 below.
Example 3
Example 3 of the present invention provides the cycloolefin copolymer described above, which is prepared in the same manner as in example 1 except that the catalyst 3 is used in place of the catalyst 1 to give a copolymer having a weight of 0.72 g.
The catalyst 3 has the structure
Figure BDA0002854240050000071
R in catalyst 31-R12Physical properties of Mt, and copolymer are illustrated in table 1 below.
Example 4
Example 4 of the present invention provides the cycloolefin copolymer described above, which is prepared in a manner similar to that of example 1, except that the catalyst 4 is used in place of the catalyst 1, giving a copolymer weight of 0.46 g.
The catalyst 4 has the structure
Figure BDA0002854240050000072
R in catalyst 41-R12Physical properties of Mt, and copolymer are illustrated in table 1 below.
Example 5
Example 5 of the present invention provides the cycloolefin copolymer described above, which is prepared in the same manner as in example 1 except that catalyst 5 is used in place of catalyst 1 to give a copolymer having a weight of 0.58 g.
The catalyst 5 has the structure
Figure BDA0002854240050000073
R in catalyst 51-R12Physical properties of Mt, and copolymer are illustrated in table 1 below.
TABLE 1
Figure BDA0002854240050000074
Figure BDA0002854240050000081
Example 6
Example 6 of the present invention provides a cycloolefin copolymer as described in the detailed description of the process for preparing the cycloolefin copolymer in example 1, except that methylnorbornene was used in place of norbornene and the weight of the copolymer was 0.42 g.
The physical properties of the copolymer are illustrated in Table 2 below.
Examples7
Example 7 of the present invention provides a cycloolefin copolymer as described in the detailed description of the preparation process of example 1, except that carbomethoxynorbornene is used in place of norbornene, and the weight of the copolymer obtained is 0.56 g.
The physical properties of the copolymer are illustrated in Table 2 below.
Example 8
Example 8 of the present invention provides the cycloolefin copolymer prepared in the same manner as in example 1, except that dimethylaminobornene was used in place of norbornene and that the weight of the copolymer was 0.49 g.
The physical properties of the copolymer are illustrated in Table 2 below.
Example 9
Example 9 of the present invention provides a cycloolefin copolymer as described in the detailed description of the process for preparing the cycloolefin copolymer in example 1, except that trimethoxysilylnorbornene is used in place of norbornene, and the weight of the copolymer obtained is 0.55 g.
The physical properties of the copolymer are illustrated in Table 2 below.
Example 10
Example 10 of the present invention provides the cycloolefin copolymer according to the specific embodiment of the production method other than that in example 1, in which tetracyclododecene was used in place of norbornene and the weight of the copolymer was 0.50 g.
The physical properties of the copolymer are illustrated in Table 2 below.
TABLE 2
Examples Content of cycloolefin monomer mol% Glass transition temperature of
6 28 79
7 23 65
8 21 60
9 26 76
10 20 57
Example 11
Example 11 of the present invention provides the cycloolefin copolymer, which is prepared by the following method:
under nitrogen atmosphere, adding 200mL of 2.00mol/L norbornene toluene solution prepared in advance and 5mL of 10 wt% methylaluminoxane toluene solution into a 500mL glass bottle, adjusting the ethylene pressure to 30atm, and stirring and balancing at 80 ℃ for 30 min; then 5mL of toluene solution of 1 mu mol/mL of catalyst 1 is added to start the reaction, the ethylene pressure is kept at 30atm, and the polymerization reaction is carried out for 30 min; the reaction mixture was added to a 10 vol% hydrochloric acid/ethanol solution to terminate the reaction, and the precipitated copolymer was filtered, washed with ethanol, and vacuum-dried at 80 ℃ for 24 hours to give 56.2g of a copolymer. The copolymer had a glass transition temperature of 73 ℃, a molecular weight of 25.2kDa and a molecular weight distribution of 1.8.
Example 12
Example 12 of the present invention provides a cycloolefin copolymer according to the specific embodiment which is the same as in example 11, except that the norbornene toluene solution having a concentration of 3.00mol/L was used in place of the norbornene toluene solution having a concentration of 2.00mol/L to give 42.3g of a copolymer, the glass transition temperature was 95 ℃, the molecular weight was 31.8kDa, and the molecular weight distribution was 1.9.
Example 13
Example 13 of the present invention provides a cycloolefin copolymer that is similar to example 11 in specific embodiment except that the norbornene toluene solution having a concentration of 5.00mol/L is used instead of the norbornene toluene solution having a concentration of 2.00mol/L to give 38.6g of a copolymer, the glass transition temperature is 133 ℃, the molecular weight is 37.4kDa, and the molecular weight distribution is 1.7.
Example 14
Example 14 of the present invention provides a cycloolefin copolymer that is similar to example 11 in specific embodiment except that the norbornene toluene solution having a concentration of 6.00mol/L is used instead of the norbornene toluene solution having a concentration of 2.00mol/L to give 32.7g of a copolymer, the glass transition temperature is 165 ℃, the molecular weight is 45.6kDa, and the molecular weight distribution is 1.8.
Example 15
Example 15 of the present invention provides a cycloolefin copolymer according to the same manner as in example 11, except that isobutylaluminoxane was used in place of methylaluminoxane to give 50.5g of a copolymer having a glass transition temperature of 75 ℃, a molecular weight of 19.2kDa and a molecular weight distribution of 2.0.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. A cycloolefin copolymer characterized by comprising a structural unit (a)
Figure FDA0002854240040000011
Structural unit (b)
Figure FDA0002854240040000012
Structural unit (c)
Figure FDA0002854240040000013
Wherein the number of repetition x of the structural unit (a) in the molecular chain of the copolymer unit is 0 to 3, the number of repetition y of the structural unit (b) in the molecular chain of the copolymer unit is 1 to 3, the number of repetition z of the structural unit (c) in the molecular chain of the copolymer unit is 1 to 3, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar groups; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2.
2. The cycloolefin copolymer according to claim 1, wherein R is any one of hydrogen, methyl group, ethyl group, isopropyl group, n-butyl group, hydroxyl group, carboxyl group, carbomethoxy group, amino group, dimethylamino group, trimethylsilyl group and trimethoxysilyl group.
3. The cycloolefin copolymer according to claim 1, wherein the raw materials for the preparation of the cycloolefin copolymer include ethylene, a norbornene-type cycloolefin monomer represented by the formula (I), a catalyst represented by the formula (II), and a co-catalyst, wherein,
Figure FDA0002854240040000014
m is 0 or 1, R is any one of hydrogen, alkyl and polar group, R1-R5、R8-R12Each independently is any one of hydrogen, alkyl and aryl, R6、R7Independently represents any one of hydrogen, alkyl and aryl or combines the same cyclic substituent, Mt represents nickel or palladium, and X represents halogen and substituted or unsubstituted alkyl.
4. The cycloolefin copolymer according to claim 3, characterized in that R is1、R5、R8、R12Each independently is any one of methyl, isopropyl, phenyl and benzhydryl, R2-R4、R9-R11Is hydrogen, R6、R7Each independently is any one of hydrogen, methyl, phenyl, acenaphthenyl and dibenzo bucket alkenyl, and X is any one of chlorine, bromine, methyl, benzyl and substituted alkyl.
5. The cycloolefin copolymer according to claim 4, wherein the norbornene-type cycloolefin monomer is any one of norbornene, alkyl-substituted norbornene, methylnorbornene, ethylnorbornene, n-propylnorbornene, isopropylnorbornene, n-butylnorbornene, hydroxynorbornene, carboxynorbornene, carbomethoxynorbornene, aminonorbornene, alkylamininonorbornene, silylnorbornene, tetracyclododecene, alkyltetracyclododecene, hydroxytetracyclododecene, carboxytetracyclododecene, estertetracyclododecene, aminotetracyclododecene, alkylaminocyclododecene, and silyltetracyclododecene.
6. The cycloolefin copolymer according to any one of claims 3 to 5, characterized in that the cocatalyst is an alkylaluminoxane having the structure (-AlM-O-) n, n being any positive integer, M being any one of methyl, ethyl, isobutyl and n-octyl.
7. The cyclic olefin copolymer according to claim 6, wherein the raw materials for the preparation of the cyclic olefin copolymer further comprise an inert hydrocarbon solvent.
8. The cycloolefin copolymer according to claim 7, characterized in that the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon.
9. The cycloolefin copolymer according to claim 8, characterized in that the inert solvent is selected from the group consisting of n-hexane, cyclohexane, n-heptane, C6-C12One or more of mixed alkane, benzene and toluene.
10. A method for preparing a cycloolefin copolymer according to any one of claims 1 to 9, characterized in that it comprises: ethylene, norbornene cyclic olefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized under the condition of existence or nonexistence of inert hydrocarbon solvent and the temperature of 0-100 ℃ and the pressure of 0.1-100atm to obtain the catalyst.
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CN115947892A (en) * 2022-11-30 2023-04-11 宁夏清研高分子新材料有限公司 high-Tg high-temperature-resistant COC material and preparation method thereof
CN116217772A (en) * 2023-01-10 2023-06-06 中国科学院长春应用化学研究所 A kind of cyclic olefin copolymer and preparation method thereof
CN116262796A (en) * 2023-03-14 2023-06-16 中山大学 A kind of hyperbranched cyclic olefin copolymer and preparation method thereof

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