CN105985485A - Method for preparing norbornylene copolymer - Google Patents
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Abstract
The invention discloses a method for preparing norbornylene and a derivative thereof with a [beta]-diketone nickel catalyst, wherein the [beta]-diketone nickel non-metallocene catalyst is used as a catalyst for catalyzing copolymerization of the norbornylene and the derivative thereof. The non-metallocene catalyst is easy to synthesize, has good stability and is high in structure adjustable range. Through the [beta]-diketone nickel non-metallocene catalyst for catalyzing copolymerization of the norbornylene and the derivative thereof, solubility and processing performance of the copolymer are improved. The polymerization process is simple, is easy to control and has advantages on industrial application.
Description
Technical field
The present invention relates to a kind of method preparing norbornene copolymer, specifically one and utilize beta-diketon nickel
Non cyclopentadienyl catalyst prepares the method for norborene and norbornene derivative copolymer.
Background technology
Norborene (dicyclo [2,2,1] hept-2-ene") is the one of cycloolefin, and its polymer is a kind of application neck
Territory is the most wide, up-and-coming new material.The polymerization methods of norborene typically have ring-opening metathesis polymerization and
Addition polymerization two kinds.Ring-opening metathesis polymerization is mainly used in the synthesis of plastics and rubber, can synthesize required specific
The high polymer material of function.The homopolymer that addition polymerization obtains has good optical transparence, low-birefringence
Rate, extremely low dielectric constant, excellent thermostability, chemical resistance, fluidity of molten, and dimensional stability
Deng.Meanwhile, also have that cyclic olefin polymerization resin generally has is good every moist and low water absorption.Though
So norbornene polymer has the electrical property of excellence, preferable mechanical strength, the strongest anti-ultraviolet radiation energy
Power, but its dissolubility is poor, and the most crisp under room temperature, therefore processing characteristics is bad.These shortcomings limit norborneol
Alkene polymer is in the application of the aspect such as optical field, microelectronic.Do to improve these shortcomings people
Many research work, mainly have two ways, and one is by norborene and other monomer copolymerization；Two be
Introduce functional group on norbornene monomer, can prepare, by copolymerization, the random copolymer that the transparency is good so that it is
There is excellent optical characteristics and moisture resistance, the most also have the excellent chemical proofing of polyolefin and amorphous concurrently
The transparency of property resin and molding processibility.
In norborene with other monomer copolymerization, the catalyst of employing has metallocene catalyst
(Macromolecules,1998,31:4669；Macromolecules,2003,36:4216；Macromol
Rapid Commun,2001,22:1394；Macromolecules,2008,41:5107).
WO2007026743、JP2000026519、EP749988、WO9640806、JP2004277523、
The patents such as JP2003327618, WO9933882, CN200610008073.0, CN200710056015.X
All disclose the method using metallocene catalyst to prepare cyclic olefine copolymer；JP2008095008 discloses
The method being prepared norborene and norbornene derivative copolymer by the metallocene catalyst of metal scandium；Document
(Macromol Rapid Commun,2004,25:302；Macromol Chem Phys,1998,199:
1951；CN200510069142.4) late transition metal catalyst such as alpha-diimine palladium, pyridine two are reported
Imines cobalt, bigcatkin willow ketone late transition metal complex.US5929181 discloses the neutral nickel catalyst system of using
Standby ethylene and the method for norbornene copolymer；CN200610033017.2 discloses anilino-imine nickel and urges
Agent prepares the method for irregular phenylethylene/norbornene multipolymer；CN 200510016512.8 disclose β-
The method that diimine nickel class catalyst system and catalyzing prepares norborene and ethylene copolymer；CN200510069142.4
A kind of method disclosing forward and backward transition-metal catalyst catalysis cycloolefines/ethylene copolymer ization using bigcatkin willow ketone；
The catalyst that CN02804866.0 discloses containing anion and neutral bidentate ligand prepares ethylene with various
The method of the copolymer of norbornene derivative.Metallocene catalysis system catalysis cyclic olefin polymerization activity is higher,
Copolymerized ability is strong, but owing to metallocene catalyst preparation condition is harsh, relatively costly, anhydrous and oxygen-free is grasped
Being required strict, the problems such as heat stability is the most poor make it apply to be restricted.
Compared with metallocene catalyst, non-metallocene catalyst low price, convieniently synthesized, to oxygen, water
The most sensitive, good stability, structure adjustable extent is big, can be catalyzed norborene and derive with norborene
Thing copolymerization, meanwhile, the processing characteristics of copolymer chain relatively norborene homopolymer can be improved further.
Summary of the invention
Present invention aim at providing a kind of method preparing norbornene copolymer.
The described method preparing norbornene copolymer, its concrete step is: reaction vessel is through nitrogen
Displacement, adds norborene, norbornene derivative monomer, major catalyst solution, solvent, promoter,
Polyreaction starts, and reaction temperature is 0～100 DEG C, and polymerization time is 0.5～4h, is subsequently adding volume basis
Concentration is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, washs, filters, is dried, obtains product.
Described major catalyst is beta-diketon nickel, shown in its structure such as formula (I), and wherein R1、R2It is identical
Or different methyl, phenyl, phenoxy group, 2,6-3,5-dimethylphenyl, 2,6-diisopropyl phenyl, the fluorine-based benzene of 4-
Base, 4-trifluoromethyl or trifluoromethyl.The synthesis of major catalyst beta-diketon nickel is referred to document J Phys
Chem,1958,62:440。
Described major catalyst concentration is 1 × 10-5～1 × 10-3Mol/L, preferably 5 × 10-5～1 × 10-3mol/L。
Described promoter is alkylaluminoxane, preferably MAO (MAO), ethylaluminoxane
(EAO) one or in modified methylaluminoxane (MMAO), promoter rubs with major catalyst
Your ratio is 100～10000:1, preferably 300～8000:1.
Described norbornene derivative be 5-ethylidene-2-norbornene, 5-vinyl-2-norborene,
Ice drops in 5-ethyl-2-norborene, 5-butyl-2-norborene, 5-amyl group-2-norborene, 5-hexyl-2-
One in sheet alkene or dicyclopentadiene.
Described solvent is toluene, dimethylbenzene or o-dichlorohenzene；
Described norborene, the concentration of norbornene derivative monomer are 1 × 10-4～1 × 10-2mol/L。
The invention has the beneficial effects as follows: the present invention is with low price, the β-two the most sensitive to oxygen, water
Ketone nickel non cyclopentadienyl catalyst is as catalyst norborene and norbornene derivative combined polymerization, gained copolymerization
Thing has good dissolubility and relatively low glass transition temperature, and glass transition temperature reduces, processability
Can improve.Compared with metallocene catalyst, non cyclopentadienyl catalyst has convieniently synthesized, good stability, structure
The advantages such as adjustable extent is big, beneficially commercial Application, the preparation condition overcoming metallocene catalyst existence is severe
The problem such as carve, wayward in technique, heat stability is poor.
Detailed description of the invention
Analysis method:
Polymer molecular weight uses gel permeation chromatography (GPC) to measure
Polymer monomers content uses nuclear-magnetism to measure
Glass transition temperature uses differential scanning calorimetry (DSC) to measure
Polymerization activity=polymerizate quality/(amount × response time of catalyst)
Outside unless stated otherwise, " % " refers both to percetage by weight
Below in conjunction with embodiment, the present invention is described further.It should be noted that following embodiment can not
As limiting the scope of the invention, any improvement made on the basis of the present invention is all without prejudice to this
Bright spirit.
Embodiment 1
Replacing through argon in the 100mL reaction vessel of three times, adding 1 × 10-4The norborene of mol/L,
5-ethylidene-2-norbornene (1:1), is subsequently adding 5 × 10-5Mol/L major catalyst beta-diketon nickel (structure
See Formulas I, wherein R1、R2Methyl) solution, toluene, add promoter MAO (promoter
It is 500:1 with the mol ratio of major catalyst), polyreaction starts, and reaction temperature is 20 DEG C, polymerization time
For 1h.Be eventually adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%, make reaction terminating, with water,
Washing with alcohol, filtered polymeric, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.Produce
Containing norborene 52% in thing, polymerization activity 4.6 × 104G/mol h, polymer molecular weight
4.36×104G/mol, glass transition temperature is 289 DEG C, and product can be dissolved in chloroform, dichloro-benzenes equal solvent.
Embodiment 2
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 5 × 10-4The norborene of mol/L,
5-vinyl-2-norborene (2:3), is subsequently adding 8 × 10-5Mol/L major catalyst beta-diketon nickel (structure
See Formulas I, wherein R1It is methyl, R2Phenyl) solution, toluene, add a certain proportion of co-catalysis
Agent EAO (promoter is 300:1 with the mol ratio of major catalyst), polyreaction starts, reaction temperature
Being 70 DEG C, polymerization time is 2h.It is subsequently adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%,
Make reaction terminating, with water, washing with alcohol, filtered polymeric, then in 70 DEG C of vacuum drying ovens, be dried 8
Hour, obtain product.Containing norborene 47% in product, polymerization activity 5.1 × 104G/mol h, polymerization
Thing molecular weight 5.63 × 104G/mol, glass transition temperature is 230 DEG C, and product can be dissolved in chloroform, dichloro
Benzene equal solvent.
Embodiment 3
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-3The norborene of mol/L,
5-ethyl-2-norborene (4:1), is subsequently adding 1 × 10-4Mol/L major catalyst beta-diketon nickel (be shown in by structure
Formulas I, wherein R1It is phenyl, R24-trifluoromethyl) solution, dimethylbenzene, add a definite proportion
The promoter MMAO (promoter is 1000:1 with the mol ratio of major catalyst) of example, polyreaction
Starting, reaction temperature is 20 DEG C, and polymerization time is 1h.Be subsequently adding concentration expressed in percentage by volume be 10% dense
Hydrochloric acid acidic ethanol, makes reaction terminating, with water, washing with alcohol, filtered polymeric, then in 70 DEG C of vacuum
Drying baker is dried 8 hours, obtains product.Containing norborene 87% in product, polymerization activity 2.4 × 105
G/mol h, polymer molecular weight 3.60 × 105G/mol, glass transition temperature is 313 DEG C, and product is permissible
It is dissolved in chloroform, dichloro-benzenes equal solvent.
Embodiment 4
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-2The norborene of mol/L,
5-butyl-2-norborene (1:1), is subsequently adding 1 × 10-3Mol/L major catalyst beta-diketon nickel (be shown in by structure
Formulas I, wherein R1It is phenoxy group, R2The fluorine-based phenyl of 4-) solution, dimethylbenzene, add certain proportion
Promoter MAO (mol ratio of promoter and major catalyst is 8000:1), polyreaction starts,
Reaction temperature is 50 DEG C, and polymerization time is 3h.It is subsequently adding the concentrated hydrochloric acid acid that concentration expressed in percentage by volume is 10%
Change ethanol, make reaction terminating, with water, washing with alcohol, filtered polymeric, then at 70 DEG C of vacuum drying ovens
In be dried 8 hours, obtain product.Containing norborene 56% in product, polymerization activity 8.0 × 105G/mol h,
Polymer molecular weight 6.31 × 104G/mol, glass transition temperature is 242 DEG C, product can be dissolved in chloroform,
Dichloro-benzenes equal solvent.
Embodiment 5
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 6 × 10-3The norborene of mol/L,
5-amyl group-2-norborene (1:4), is subsequently adding 6 × 10-5Mol/L major catalyst beta-diketon nickel (be shown in by structure
Formulas I, wherein R1It is 2,6-3,5-dimethylphenyl, R2Be 2,6-diisopropyl phenyl) solution, o-dichlorohenzene,
(promoter with the mol ratio of major catalyst is to add a certain proportion of promoter MMAO
1000:1), polyreaction starts, and reaction temperature is 40 DEG C, and polymerization time is 3h.It is subsequently adding volume
Percentage concentration is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, gathers with water, washing with alcohol, filtration
Compound, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.Containing norborene in product
29%, polymerization activity 6.7 × 104G/mol h, polymer molecular weight 1.90 × 104G/mol, glass transition temperature
Degree is 195 DEG C, and product can be dissolved in chloroform, dichloro-benzenes equal solvent.
Embodiment 6
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 2 × 10-4The norborene of mol/L,
5-hexyl-2-norborene (3:7), is subsequently adding 1 × 10-4Mol/L major catalyst beta-diketon nickel (be shown in by structure
Formulas I, wherein R1、R24-trifluoromethyl) solution, toluene, add a certain proportion of helping and urge
Agent MAO (promoter is 2000:1 with the mol ratio of major catalyst), polyreaction starts, reaction
Temperature is 30 DEG C, and polymerization time is 1h.It is subsequently adding the concentrated hydrochloric acid acidifying second that concentration expressed in percentage by volume is 10%
Alcohol, makes reaction terminating, with water, washing with alcohol, filtered polymeric more dry in 70 DEG C of vacuum drying ovens
Dry 8 hours, obtain product.Containing norborene 34% in product, polymerization activity 7.4 × 105G/mol h,
Polymer molecular weight 1.13 × 104G/mol, glass transition temperature is 218 DEG C, product can be dissolved in chloroform,
Dichloro-benzenes equal solvent.
Embodiment 7
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-3The norborene of mol/L,
5-ethylidene-2-norbornene (3:2), is subsequently adding 8 × 10-4Mol/L major catalyst beta-diketon nickel (structure
See Formulas I, wherein R1、R2It is the fluorine-based phenyl of 4-).Solution, toluene, add a certain proportion of helping and urge
Agent MMAO (promoter is 800:1 with the mol ratio of major catalyst), polyreaction starts, reaction
Temperature is 60 DEG C, and polymerization time is 2h.It is subsequently adding the concentrated hydrochloric acid acidifying second that concentration expressed in percentage by volume is 10%
Alcohol, makes reaction terminating, with water, washing with alcohol, filtered polymeric more dry in 70 DEG C of vacuum drying ovens
Dry 8 hours, obtain product.Containing norborene 68% in product, polymerization activity 5.5 × 105G/mol h,
Polymer molecular weight 4.01 × 104G/mol, glass transition temperature is 312 DEG C, product can be dissolved in chloroform,
Dichloro-benzenes equal solvent.
Embodiment 8
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-2The norborene of mol/L,
Dicyclopentadiene (9:1), is subsequently adding 5 × 10-5Mol/L major catalyst beta-diketon nickel (structure is shown in Formulas I,
Wherein R1It is phenyl, R2Trifluoromethyl) solution, dimethylbenzene, add a certain proportion of promoter
EAO (promoter is 2000:1 with the mol ratio of major catalyst), polyreaction starts, reaction temperature
Being 80 DEG C, polymerization time is 3h.It is subsequently adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%,
Make reaction terminating, with water, washing with alcohol, filtered polymeric, then in 70 DEG C of vacuum drying ovens, be dried 8
Hour, obtain product.Containing norborene 93% in product, polymerization activity 7.6 × 105G/mol h, polymerization
Thing molecular weight 1.80 × 105G/mol, glass transition temperature is 270 DEG C, and product can be dissolved in chloroform, dichloro
Benzene equal solvent.
Embodiment 9
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 2 × 10-4The norborene of mol/L,
5-hexyl-2-norborene (7:3), is subsequently adding 1 × 10-4Mol/L major catalyst beta-diketon nickel (be shown in by structure
Formulas I, wherein R1、R2Phenyl) solution, toluene, add a certain proportion of promoter MAO and (help
Catalyst is 1000:1 with the mol ratio of major catalyst), polyreaction starts, and reaction temperature is 60 DEG C,
Polymerization time is 1h.It is subsequently adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%, makes reaction eventually
Only, with water, washing with alcohol, filtered polymeric, then it is dried 8 hours in 70 DEG C of vacuum drying ovens,
To product.Containing norborene 78% in product, polymerization activity 8.4 × 105G/mol h, polymer molecular weight
7.3×104G/mol, glass transition temperature is 298 DEG C, and product can be dissolved in chloroform, dichloro-benzenes equal solvent.
Comparative example 1
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-2The norborene of mol/L,
It is subsequently adding 1 × 10-3(structure is shown in Formulas I to mol/L major catalyst beta-diketon nickel, wherein R1、R2It is methyl)
Solution, toluene, add a certain proportion of promoter MAO (promoter and major catalyst mole
Ratio is 800:1), polyreaction starts, and reaction temperature is 60 DEG C, and polymerization time is 1h.It is subsequently adding
Concentration expressed in percentage by volume is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, by water, washing with alcohol, mistake
Filter polymer, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.Polymerization activity 9.6 × 105
G/mol h, polymer molecular weight 2.80 × 105G/mol, glass transition temperature is 358 DEG C, norborene
Homopolymer at normal temperatures insoluble in the Conventional solvents such as chloroform.
Comparative example 2
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-4The norborene of mol/L,
It is subsequently adding 5 × 10-5(structure is shown in Formulas I to mol/L major catalyst beta-diketon nickel, wherein R1、R2It is methyl)
Solution, toluene, add a certain proportion of promoter MAO (promoter and major catalyst mole
Ratio is 500:1), polyreaction starts, and reaction temperature is 20 DEG C, and polymerization time is 1h.It is subsequently adding
Concentration expressed in percentage by volume is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, by water, washing with alcohol, mistake
Filter polymer, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.Polymerization activity 5.3 × 105
G/mol h, polymer molecular weight 3.26 × 104G/mol, glass transition temperature is 379 DEG C, norborene
Homopolymer at normal temperatures insoluble in the Conventional solvents such as chloroform.
Comparative example 3
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 2 × 10-4The norborene of mol/L,
It is subsequently adding 1 × 10-4(structure is shown in Formulas I to mol/L major catalyst beta-diketon nickel, wherein R1、R2It it is 4-trifluoro
Aminomethyl phenyl) solution, toluene, add a certain proportion of promoter MAO (promoter with sponsor
The mol ratio of agent is 2000:1), polyreaction starts, and reaction temperature is 30 DEG C, and polymerization time is 1h.
It is subsequently adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%, makes reaction terminating, with water, ethanol
Washing, filtered polymeric, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.Polymerization is lived
Property 6.3 × 105G/mol h, polymer molecular weight 1.02 × 104G/mol, glass transition temperature is 396 DEG C,
The homopolymer of norborene is at normal temperatures insoluble in Conventional solvents such as chloroforms.
Comparative example 4
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-2The norborene of mol/L,
It is subsequently adding 1 × 10-3Mol/L major catalyst metallocene catalyst Et (Ind)2ZrCl2, toluene, add one
The promoter MAO (promoter is 800:1 with the mol ratio of major catalyst) of certainty ratio, polymerization is anti-
Should start, reaction temperature is 60 DEG C, and polymerization time is 1h.Being subsequently adding concentration expressed in percentage by volume is 10%
Concentrated hydrochloric acid acidic ethanol, makes reaction terminating, with water, washing with alcohol, filtered polymeric trueer at 70 DEG C
Empty drying baker is dried 8 hours, obtains product.Polymerization activity 4.3 × 105G/mol h, polymer molecular weight
2.30×105G/mol, glass transition temperature is 405 DEG C, and the homopolymer of norborene does not dissolves at normal temperatures
The Conventional solvents such as chloroform.
Comparative example 5
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 1 × 10-4The norborene of mol/L,
It is subsequently adding 5 × 10-5Mol/L major catalyst metallocene catalyst (t-BuNSiMe2Flu)TiMe2, toluene,
Add a certain proportion of promoter MAO (promoter is 500:1 with the mol ratio of major catalyst),
Polyreaction starts, and reaction temperature is 20 DEG C, and polymerization time is 1h.Being subsequently adding concentration expressed in percentage by volume is
The concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, with water, washing with alcohol, filtered polymeric, then
70 DEG C of vacuum drying ovens are dried 8 hours, obtain product.Polymerization activity 4.2 × 105G/mol h, polymer
Molecular weight 2.8 × 104G/mol, glass transition temperature is 412 DEG C, and the homopolymer of norborene is at normal temperatures
Insoluble in Conventional solvents such as chloroforms.
Comparative example 6
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 2 × 10-4The norborene of mol/L,
It is subsequently adding 1 × 10-4Mol/L major catalyst metallocene catalyst (t-BuNSiMe2Flu)TiMe2, toluene,
Add a certain proportion of promoter MAO (promoter is 2000:1 with the mol ratio of major catalyst),
Polyreaction starts, and reaction temperature is 30 DEG C, and polymerization time is 1h.Being subsequently adding concentration expressed in percentage by volume is
The concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, with water, washing with alcohol, filtered polymeric, then
70 DEG C of vacuum drying ovens are dried 8 hours, obtain product.Polymerization activity 4.5 × 105G/mol h, polymer
Molecular weight 0.98 × 104G/mol, glass transition temperature is 430 DEG C, and the homopolymer of norborene is at normal temperatures
Insoluble in Conventional solvents such as chloroforms.
Comparative example 7
Replacing through nitrogen in the 100mL reaction vessel of three times, adding 6 × 10-4The norborene of mol/L,
Dicyclopentadiene (1:1), is subsequently adding 6 × 10-4Mol/L major catalyst metallocene catalyst
(t-BuNSiMe2Flu)TiMe2, toluene, add a certain proportion of promoter MAO (promoter
It is 400:1 with the mol ratio of major catalyst), polyreaction starts, and reaction temperature is 40 DEG C, polymerization time
For 0.5h.It is subsequently adding the concentrated hydrochloric acid acidic ethanol that concentration expressed in percentage by volume is 10%, makes reaction terminating, use
Water, washing with alcohol, filtered polymeric, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product.
Polymerization activity 5.1 × 105G/mol h, polymer molecular weight 1.3 × 105G/mol, glass transition temperature is
379 DEG C, product can be dissolved in chloroform, dichloro-benzenes equal solvent.
Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and essence thereof
In the case of, those of ordinary skill in the art can make various corresponding change and change according to the present invention
Shape, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (9)
1. the method preparing norbornene copolymer, it is characterised in that carry out according to following steps:
Reaction vessel through nitrogen replace after, add norborene, norbornene derivative monomer, major catalyst solution,
Solvent, promoter, maintaining reaction temperature is 0～100 DEG C, and polymerization time is 0.5～4h, is subsequently adding
Concentrated hydrochloric acid acidic ethanol terminates reaction, washs, filters, is dried, obtains described copolymer；
Wherein, described major catalyst is beta-diketon nickel, shown in its formula such as formula (I), and wherein R1、R2
Be identical or different methyl, phenyl, phenoxy group, 2,6-3,5-dimethylphenyl, 2,6-diisopropyl phenyl,
The fluorine-based phenyl of 4-, 4-trifluoromethyl or trifluoromethyl.
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating promoter is alkylaluminoxane, and promoter is 100～10000:1 with the mol ratio of major catalyst.
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating promoter is MAO, ethylaluminoxane or modified methylaluminoxane, promoter and main catalytic
The mol ratio of agent is 300～8000:1.
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating major catalyst concentration is 1 × 10-5～1 × 10-3mol/L。
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating major catalyst concentration is 5 × 10-5～1 × 10-3mol/L。
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating solvent is toluene, dimethylbenzene or o-dichlorohenzene.
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that institute
Stating norbornene derivative monomer is 5-ethylidene-2-norbornene, 5-vinyl-2-norborene, 5-second
Base-2-norborene, 5-butyl-2-norborene, 5-amyl group-2-norborene, 5-hexyl-2-norborene
Or the one in dicyclopentadiene.
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that described
Norborene, the concentration of norbornene derivative monomer are 1 × 10-4～1 × 10-2mol/L。
The method preparing norbornene copolymer the most according to claim 1, it is characterised in that described
Reaction temperature be 20～80 DEG C, polymerization time is 1～3h.
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| CN112940183A (en) * | 2021-03-01 | 2021-06-11 | 扬州工业职业技术学院 | High-activity iron catalyst and application thereof in preparation of norbornene and ethylidene norbornene copolymer |
| CN114380931A (en) * | 2021-12-27 | 2022-04-22 | 宁波职业技术学院 | Polyvinyl norbornene and preparation method thereof |
| CN114685716A (en) * | 2020-12-31 | 2022-07-01 | 江苏博睿光电股份有限公司 | Crosslinkable cycloolefin copolymer and preparation method and application thereof |
| 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 |
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| CN114685716A (en) * | 2020-12-31 | 2022-07-01 | 江苏博睿光电股份有限公司 | Crosslinkable cycloolefin copolymer and preparation method and application thereof |
| CN114685716B (en) * | 2020-12-31 | 2024-02-02 | 江苏博睿光电股份有限公司 | Crosslinkable cycloolefin copolymer and preparation method and application thereof |
| CN112940183A (en) * | 2021-03-01 | 2021-06-11 | 扬州工业职业技术学院 | High-activity iron catalyst and application thereof in preparation of norbornene and ethylidene norbornene copolymer |
| CN114380931A (en) * | 2021-12-27 | 2022-04-22 | 宁波职业技术学院 | Polyvinyl norbornene and preparation method thereof |
| 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 |
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