CN106243280B - A kind of functionality cycloolefin/styrene copolymer and preparation method thereof - Google Patents
A kind of functionality cycloolefin/styrene copolymer and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract
The present invention relates to a kind of functional cycloolefin/styrene copolymers and preparation method thereof, under the action of major catalyst and co-catalyst, cycloolefin with formula (III) structure is subjected to polymerisation with the phenylethylene co-monomer with formula (IV) structure in atent solvent or halogenated solvent, obtains cycloolefin/styrene copolymer；The major catalyst that the present invention uses is the 10th group 4 transition metal complexes with quinolinamine imidazole ligands, when co-catalyst is polymerization system progress cycloolefin and the styrene monomer copolymerization of alkylaluminoxane or organo-aluminum compound, rate of chain growth is fast, and has very strong copolymerized ability to styrene monomer.Compared to existing cycloolefin/phenylethylene condensate system, the catalyst system and catalyzing notable will be appreciated that can highly active catalytic copolyreaction, obtain the controllable cycloolefin/styrene copolymer of styrene-content.
Description
Technical field
The present invention relates to copolymer fields, and in particular to a kind of preparation side of functionality cycloolefin/styrene copolymer
Method.
Background technology
Cyclic olefine copolymer has excellent heat resistance, chemical resistance, dielectric loss, low water absorbable, birefringence, and
The features such as high grade of transparency, is suitable for the fields such as optics, electronics, biological medicine.Development with modern society and demand, to cyclenes
The performance requirement of hydrocarbon copolymer is also higher and higher, for example higher heat resistance and lower birefringence are applied in advanced optical
Important parameter in Material Field.
The cyclic olefine copolymer of most study is the copolymerization of the monomers such as norbornene and ethylene, propylene, advanced ɑ-alkene at present
Obtained product.However, the insertion due to a small amount of ɑ-alkene in the copolymer, causes the glass transition temperature of copolymer to reduce
Very much, to hardly result in the copolymer of high-fire resistance.In addition, introducing fragrance in the cyclic olefine copolymer with aliphatic ring structure
While ring can effectively control the birefringence of copolymer, the influence to glass transition temperature is little.Therefore, norbornene and
The copolymer of Styrene and its derivatives is paid attention to as the optical material of high-fire resistance by academia and industrial quarters.
The preparation of cyclic olefine copolymer mainly uses the single site catalysts based on early transition metal to carry out cycloolefin
With the addition polymerization of ɑ-alkene.But when these catalyst being applied to the copolymerization of cycloolefin and styrene, since catalyst is to styrene
Copolymerized ability it is poor, cause Copolymerization activity and molecular weight to drastically reduce, and the poor controllability of the content of co-monomer.For example,
Shiono et al. has studied the Copolymerization behavior of the norbornene and styrene of fluorenyl amido dimethyl titanium complex initiation.Gained is total
Styrene insertion rate is up to 5.0mol% in polymers, and polymerization activity and number-average molecular weight are respectively from styrene insertion rate
62kg polymer/(mol titaniums) h when 0.5mol%) kg and 5.6 ten thousand gram/mol, it is reduced to 1.4kg polymer/(mol
Titanium) h) kg and 1.0 ten thousand gram/mol of (J.Polym.Sci., Part A:Polym.Chem.,2011,49,65-71.).
Late transition metal nickel is used also to can get the copolymer ((a) of norbornene and styrene for catalyst
Macromol.Chem.Phys.,1998,199,2221-2227；(b)J.Polym.Sci.,Part A:Polym.Chem.,
2006,44,5237-5246.).But resulting polymers cause should not to form a film or mechanical strength insoluble in organic solvent, molecular weight are low
It is low, therefore cannot be satisfied the performance requirement of optical material.
Invention content
The object of the present invention is to provide a kind of preparation method of functional cycloolefin/styrene copolymer, the present invention adopts
Major catalyst be the 10th group 4 transition metal complexes with quinolinamine imidazole ligands, co-catalyst be alkylaluminoxane or
When the polymerization system of organo-aluminum compound carries out cycloolefin with styrene monomer copolymerization, rate of chain growth is fast, and to benzene second
Vinyl monomer has very strong copolymerized ability.Compared to existing cycloolefin/phenylethylene condensate system, which shows
Write will be appreciated that can highly active catalytic copolyreaction, obtain the controllable cycloolefin of styrene-content/phenylethylene copolymerization
Object.
A kind of functional cycloolefin/styrene copolymer of the present invention, the functionality cycloolefin/phenylethylene copolymerization
Object includes the repetitive unit with formula (Ι) and formula (II) structure；
Wherein：
In formula (I) structure, n and m is each independently selected 0,1 or 2；
R1~R4Separate selection hydrogen, halogen, the C for containing or not contain concatenating group1~30Alkyl or polar group, have
The C of substituent group or unsubstituted1~30Alkyl or polar group, or further, R1And R4By monocycle or it is polycyclic in the form of be connected in one
Rise, monocycle or it is polycyclic it is upper can be with double bond, or further, R1And R4Or R3And R4Form alkyl indenes；
The halogen is fluorine, chlorine and bromine atom；
The concatenating group is C1~10Divalent alkyl, carbonyl (- CO-), carbonyloxy group (- COO-), oxygen carbonyl (- OCO-), sulphonyl
Base (- SO2), ehter bond (- O-), thioether bond (- S-), imino group (- NH-), one kind in amido bond (- NHCO-) or siloxanes key
More than；
The substituent group is fluorine, chlorine, bromine, benzenesulfonyl or cyano；
The C1~30Alkyl be alkyl, naphthenic base, alkenyl, cycloalkenyl group, inclined alkylidene or aromatic series base；
The C1~30Polar group be hydroxyl, C1~10Alkoxy, carbonyloxy group, alkoxy carbonyl group, aryloxy carbonyl, cyano, acyl
Amido, imide, three organic group siloxies, sulfonic group or acidic group, the C1~10Alkoxy be methoxyl group or ethoxy
Base, the carbonyloxy group are acetoxyl group, propionyloxy or benzoyloxy, and the alkoxy carbonyl group is methoxycarbonyl group or ethoxy carbonyl
Base, the aryloxy carbonyl are carbobenzoxy, naphthalene oxygen carbonyl, fluorenylmethoxycarbonyl or biphenyl oxygen carbonyl, the three organic groups monosilane oxygen
Base is trimethylsiloxy or silicohetane alkoxy；
In formula (II) structure, R5To R8Identical or different group, respectively arbitrarily selected from hydrogen, straight-chain hydrocarbons, contain branch
Alkyl, halogen, nitro, hydroxyl, one kind in sulfonyl or acyloxy；
FG is polar functional group, specially halogen atom, C1~4Hydroxyalkyl, tert-butyl dimethyl silica ethyl, hydroxyl,
C1~20Alkoxy, C6~20Aryloxy group, C1~20Alkylthio group, C6~20Arylthio, carboxyalkyl, amino, ester group, sulfonyl,
Acyloxy or alkylhalide group；The C1~20Alkoxy be methoxy or ethoxy；The C6~20Aryloxy group be phenoxy group, benzene first
Oxygroup or benzene ethyoxyl；The C1~20Alkylthio group be methyl mercapto, ethylmercapto group or rosickyite base；The C6~20Arylthio be benzene sulphur
Base, benzylthio or benzene ethylmercapto group；The carboxyalkyl is carboxymethyl, carboxyethyl or carboxylic propyl；The ester group is formic acid ester group, second
Perester radical or propionic acid ester group；The alkylhalide group is chloromethyl, chloroethyl, bromomethyl or bromoethyl；
Insertion rate of the repetitive unit with formula (II) structure in the functional cycloolefin/styrene copolymer
More than zero and it is less than or equal to 50mol%；
Number-average molecular weight (the M of the functionality cycloolefin/styrene copolymern) it is 0.5~500,000 grams/mol, point
Son amount profile exponent (Mw/Mn) ranging from 1.8~2.8；
Glass transition temperature (the T of the functionality cycloolefin/styrene copolymerg) it is 250~400 DEG C.
The preparation method of a kind of functional cycloolefin/styrol copolymer as described above, in major catalyst and co-catalysis
It is under the action of agent, the cycloolefin with formula (III) structure and the phenylethylene co-monomer with formula (IV) structure is molten in inertia
Polymerisation is carried out in agent or halogenated solvent, obtains cycloolefin/styrene copolymer；
Wherein：
In formula (III) structure, n and m is each independently selected 0,1 or 2；
R1~R4Separate selection hydrogen, halogen, the C for containing or not contain concatenating group1~30Alkyl or polar group, have
The C of substituent group or unsubstituted1~30Alkyl or polar group, or further, R1And R4By monocycle or it is polycyclic in the form of be connected in one
Rise, monocycle or it is polycyclic it is upper can be with double bond, or further, R1And R4Or R3And R4Form alkyl indenes；
The halogen is fluorine, chlorine and bromine atom；
The concatenating group is C1~10Divalent alkyl, carbonyl (- CO-), carbonyloxy group (- COO-), oxygen carbonyl (- OCO-), sulphonyl
Base (- SO2), ehter bond (- O-), thioether bond (- S-), imino group (- NH-), one kind in amido bond (- NHCO-) or siloxanes key
More than；
The substituent group is fluorine, chlorine, bromine, benzenesulfonyl or cyano；
The C1~30Alkyl be alkyl, naphthenic base, alkenyl, cycloalkenyl group, inclined alkylidene or aromatic series base；
The C1~30Polar group be hydroxyl, C1~10Alkoxy, carbonyloxy group, alkoxy carbonyl group, aryloxy carbonyl, cyano, acyl
Amido, imide, three organic group siloxies, sulfonic group or acidic group, the C1~10Alkoxy be methoxyl group or ethoxy
Base, the carbonyloxy group are acetoxyl group, propionyloxy or benzoyloxy, and the alkoxy carbonyl group is methoxycarbonyl group or ethoxy carbonyl
Base, the aryloxy carbonyl are carbobenzoxy, naphthalene oxygen carbonyl, fluorenylmethoxycarbonyl or biphenyl oxygen carbonyl, the three organic groups monosilane oxygen
Base is trimethylsiloxy or silicohetane alkoxy；
The cycloolefin with formula (III) structure is norbornene, 2- norbornene, the chloro- 2- norbornene of 5-, 5- bromo-
2- norbornene, 5- methyl -2- norbornene, 5- ethyl -2- norbornene, 5- butyl -2- norbornene, 5- hexyls -2- drops
Bornylene, 5- decyl -2- norbornene, 5- vinyl -2- norbornene, 5- acrylic -2- norbornene, 5- cyclohexyl -2-
Norbornene, 5- cyclopenta -2- norbornene, 5- cyclohexenyl group -2- norbornene, 5- cyclopentenyl -2- norbornene, 5- benzene
Base -2- norbornene, p- methyl -5- phenyl -2- norbornene, o- methyl -5- phenyl -2- norbornene, m- methyl -5- benzene
Base -2- norbornene, 5- chloromethyl -2- norbornene, the chloro- 5- phenyl -2- norbornene of p-, dicyclopentadiene, methyl bicycle
Pentadiene, dihydro dicyclopentadiene (Fourth Ring [5.2.1.02,6] 11-8- alkene), Fourth Ring [9.2.1.02,10.03,8] 14-3,5,
7,12- tetraenes, Fourth Ring [10.2.1.02,11] 15-4,6,8,13- tetraenes, 5- methyl indenes-2- norbornene, 5- ethyl indenes-2-
Norbornene, 5- propyl indenes -2- norbornene or 5- isopropyl indenes -2- norbornene, Fourth Ring [6.2.1.13,6.02,7] -4- ten
Two carbenes, 9- chlorine Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- bromines Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes,
9- methyl Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- ethyltetracyclos [6.2.1.13,6.02,7] -4- dodecylenes, 9-
Butyl Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- hexyls Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, the 9- last of the ten Heavenly stems
Base Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- vinyl Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- third
Alkenyl Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- cyclohexyl Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9-
Cyclopenta Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- cyclohexenyl groups Fourth Ring [6.2.1.13,6.02,7] 12 carbon of -4-
Alkene, 9- cyclopentenyls Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- phenyl Fourth Ring [6.2.1.13,6.02,7] -4- 12
Carbene, 9- chloromethyls Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes, 9- methyl indenes Fourth Ring [6.2.1.13,6.02,7] -4- ten
Two carbenes or 9- ethyl indenes Fourth Ring [6.2.1.13,6.02,7] -4- dodecylenes；
In formula (IV) structure, R5To R8Identical or different group, respectively arbitrarily selected from hydrogen, straight-chain hydrocarbons, contain branch
Alkyl, halogen, nitro, hydroxyl, one kind in sulfonyl or acyloxy；
FG is polar functional group, specially halogen atom, C1~4Hydroxyalkyl, tert-butyl dimethyl silica ethyl, hydroxyl,
C1~20Alkoxy, C6~20Aryloxy group, C1~20Alkylthio group, C6~20Arylthio, carboxyalkyl, amino, ester group, sulfonyl,
Acyloxy or alkylhalide group；The C1~20Alkoxy be methoxy or ethoxy；The C6~20Aryloxy group be phenoxy group, benzene first
Oxygroup or benzene ethyoxyl；The C1~20Alkylthio group be methyl mercapto, ethylmercapto group or rosickyite base；The C6~20Arylthio be benzene sulphur
Base, benzylthio or benzene ethylmercapto group；The carboxyalkyl is carboxymethyl, carboxyethyl or carboxylic propyl；The ester group is formic acid ester group, second
Perester radical or propionic acid ester group；The alkylhalide group is chloromethyl, chloroethyl, bromomethyl or bromoethyl；
It is described have formula (IV) structure styrene class monomer be styrene, 4- chlorostyrenes, 2- methyl -4- chlorostyrenes,
2- ethyl -4- chlorostyrenes, 2,6- dimethyl -4- chlorostyrenes, 2,3,5,6- tetramethyl -4- chlorostyrenes, 4- methoxybenzenes
Ethylene, 2- ethyl -4- methoxy styrenes, 2,6- diethyl -4- methoxy styrenes, 2,3,5,6- tetraethyl -4- methoxyl groups
Styrene, 4- methylthio phenyls ethylene, 2- nitro -4- methylthio phenyls ethylene, 2,6- dinitro -4- methylthio phenyls ethylene, 2,3,5,
6- tetranitro -4- methylthio phenyls ethylene, 4- phenoxy groups styrene, the chloro- 4- phenoxy groups styrene of 2-, bis- chloro- 4- phenoxy groups of 2,6-
Styrene, tetra- chloro- 4- phenoxy groups styrene of 2,3,5,6-, 4-Vinyl phenol, the bromo- 4-Vinyl phenols of 2-, bis- bromo- 4- of 2,6-
Hydroxy styrenes, tetra- bromo- 4-Vinyl phenols of 2,3,5,6- or 4- methoxy styrenes；
The major catalyst is the late transition metal complex that the quinolinamine imidazoles with formula (V) structure is ligand；
Wherein：
R9To R18It is identical or different group, respectively arbitrarily selected from hydrogen, halogen, C1~4Alkyl, naphthenic base, carry halogen
Element or C1~4One kind in the aryl of carbon substitution；
X1With X2Each identical or different group, respectively arbitrarily selected from halogen, C1~4One kind in alkyl；
M is transition metal, is iron, cobalt, nickel or palladium；
The co-catalyst is alkylaluminoxane or organo-aluminum compound；The alkylaluminoxane is methylaluminoxane, changes
One or more of property methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide；The organo-aluminum compound is diethyl
Base aluminium or ethylaluminium dichloride.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, the specific steps are：
1) under nitrogen atmosphere, be added atent solvent or halogenated solvent, the cycloolefin with formula (III) structure and
Catalyst and co-catalyst is added in formula (IV) structure styrene class monomer after stirring, carry out polymerisation；
2) obtained reactive polymeric product hydrochloric acid/ethanol solution terminated, be filtered, washed and dried, obtained
Cycloolefin/styrol copolymer.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, the atent solvent be aromatic hydrocarbons,
Alkanes or cyclic hydrocar-bons solvent；Aromatic hydrocarbon solvent be toluene, dimethylbenzene or ethylbenzene, alkane solvents be n-hexane, normal heptane or
Normal octane, cyclic hydrocar-bons solvent are hexamethylene, cycloheptane or cyclooctane；
The halogenated solvent is dichloroethanes or chlorobenzene.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, the atent solvent or halogenated molten
The molar ratio of agent and the cycloolefin with formula (III) structure is 2~50；The cycloolefin and formula with formula (III) structure
(IV) molar ratio of structure styrene class monomer is 0.1~10.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, the major catalyst with there is formula
(III) molar ratio of the cycloolefin of structure is 0.00025~0.0025；The molar ratio of the major catalyst and co-catalyst is
1:50~5000.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, the temperature of the polymerisation is 0
~90 DEG C, the time is 1~180min.
A kind of preparation method of functional cycloolefin/styrol copolymer as described above, salt in the hydrochloric acid/ethanol solution
The volume ratio of acid and ethyl alcohol is 1:20~60；The time of the stirring is 10~30min.
The present invention preferably carries out the polymerisation under conditions of drying, anaerobic, and the polymerisation can be in gloves
It is carried out in case, the Schlenk technologies of standard can also be used to carry out under nitrogen protection.
The preparation method of cycloolefin/styrene copolymer of the present invention, in this preparation process, the present invention is using catalysis
Agent is the 10th group 4 transition metal complexes with quinolinamine imidazole ligands, and co-catalyst is alkylaluminoxane or organo-aluminium chemical combination
When the polymerization system of object carries out cycloolefin with styrene monomer copolymerization, rate of chain growth is fast, and has to styrene monomer
There is very strong copolymerized ability.Compared to existing cycloolefin/styrene polymerization system, the notable superior of the catalyst system and catalyzing is in
In can highly active catalytic copolyreaction, obtain the controllable high molecular weight cyclic olefine copolymer of styrene-content.The result shows that this
The number-average molecular weight of the cycloolefin/styrene copolymer obtained in invention is 0.5~500,000 grams/mol, and molecular weight distribution refers to
Number is 1.8~2.8, and phenylethylene co-monomer is adjustable between 0~50mol% of insertion rate in cyclic olefine copolymer, and keeps
High glass-transition temperature.
Advantageous effect：
Cycloolefin/styrene copolymer of the present invention is obtained by the copolymerization of cycloolefin and phenylethylene co-monomer
The controllable high molecular weight cycloolefin/styrene copolymer with excellent heat resistance and optical characteristics of styrene insertion rate.
Catalyst system of the present invention has very strong copolymerized ability to styrene, to effectively obtain cyclenes
Hydrocarbon/styrol copolymer.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1-8
A kind of preparation method of functionality cycloolefin/styrol copolymer, the specific steps are：
1) under nitrogen atmosphere, toluene, norbornene and formula (IV) structure styrene class monomer is added, wherein toluene and 2-
The molar ratio of norbornene is 8, and major catalyst (wherein, R is added after stirring 15min9To R18It is hydrogen, X1With X2It is successively
Bromine, M Ni) and methylaluminoxane (MMAO), the molar ratio of major catalyst and methylaluminoxane (MMAO) is 1:1000, gathered
Reaction is closed, the temperature of polymerisation is 30 DEG C, time 60min；
2) by obtained reactive polymeric product hydrochloric acid/ethanol solution, (volume ratio of hydrochloric acid and ethyl alcohol is 1:30) terminate,
It is filtered, washed and dried, obtains cycloolefin/styrol copolymer.
When formula (IV) structure styrene class monomer is styrene or 4- chlorostyrenes, and norbornene and formula (IV) structure benzene
When the molar ratio of vinyl monomer is 0.1~10, the insertion rate of functional cycloolefin/styrene copolymer, vitrifying turn
Temperature (Tg) performance parameter see the table below：
Embodiment 9-13
A kind of preparation method of functionality cycloolefin/styrol copolymer, the specific steps are：
1) under nitrogen atmosphere, toluene, norbornene and styrene is added, wherein the molar ratio of toluene and norbornene
It is 8, the molar ratio of norbornene and styrene is 1.5, and major catalyst (wherein, R is added after stirring 25min9To R18It is
Hydrogen, X1With X2It is bromine, M Ni) and methylaluminoxane (MMAO), the molar ratio of major catalyst and norbornene is
0.000417, the molar ratio of major catalyst and methylaluminoxane (MMAO) is 1:1000, carry out polymerisation 60min；
2) by obtained reactive polymeric product hydrochloric acid/ethanol solution, (volume ratio of hydrochloric acid and ethyl alcohol is 1:40) terminate,
It is filtered, washed and dried, obtains cycloolefin/styrol copolymer.
When the temperature of polymerisation is 0-90 DEG C, number-average molecular weight (Mn), molecular weight distributing index (Mw/Mn) performance
Parameter see the table below：(remarks：Molecular weight has reached macromolecule level, can be used as material)
| Embodiment | Polymerization temperature | Mn | Mw/Mn |
| 9 | 30℃ | 24000 | 2.1 |
| 10 | 50℃ | 12000 | 2.3 |
| 11 | 60℃ | 13000 | 2.1 |
| 12 | 70℃ | 9000 | 2.2 |
| 13 | 90℃ | 7000 | 2.1 |
Embodiment 14
A kind of preparation method of functionality cycloolefin/styrol copolymer, the specific steps are：
1) under nitrogen atmosphere, toluene, norbornene and styrene is added, wherein the molar ratio of toluene and norbornene
It is 8, the molar ratio of norbornene and styrene is 1.5, and major catalyst (wherein, R is added after stirring 25min9To R18It is
Hydrogen, X1With X2It is bromine, M Ni) and methylaluminoxane (MMAO), the molar ratio of major catalyst and norbornene is
0.000417, the molar ratio of major catalyst and methylaluminoxane (MMAO) is 1:1000, carry out polymerisation, polymeric reaction temperature
It is 90 DEG C, polymerization reaction time 3h；
2) by obtained reactive polymeric product hydrochloric acid/ethanol solution, (volume ratio of hydrochloric acid and ethyl alcohol is 1:40) terminate,
It is filtered, washed and dried, obtains cycloolefin/styrol copolymer.
Test shows that the insertion rate of functional cycloolefin/styrene copolymer obtained is 8%, number-average molecular weight (Mn)
It is 7000, molecular weight distributing index (Mw/Mn) it is 2.1, glass transition temperature (Tg) it is 317 DEG C.
Embodiment 15
A kind of preparation method of functionality cycloolefin/styrol copolymer, the specific steps are：
1) under nitrogen atmosphere, toluene, norbornene and styrene is added, wherein the molar ratio of toluene and norbornene
It is 8, the molar ratio of norbornene and styrene is 1.5, and major catalyst (wherein, R is added after stirring 25min9To R18It is
Hydrogen, X1With X2It is bromine, M Ni) and methylaluminoxane (MMAO), the molar ratio of major catalyst and norbornene is
0.000417, the molar ratio of major catalyst and methylaluminoxane (MMAO) is 1:1500, carry out polymerisation, polymeric reaction temperature
It is 90 DEG C, polymerization reaction time 3h；
2) by obtained reactive polymeric product hydrochloric acid/ethanol solution, (volume ratio of hydrochloric acid and ethyl alcohol is 1:40) terminate,
It is filtered, washed and dried, obtains cycloolefin/styrol copolymer.
Test shows that the insertion rate of functional cycloolefin/styrene copolymer obtained is 9%, number-average molecular weight (Mn)
It is 5000, molecular weight distributing index (Mw/Mn) it is 2.4, glass transition temperature (Tg) it is 315 DEG C.
Claims (8)
1. a kind of functionality cycloolefin/styrene copolymer, it is characterized in that：The functionality cycloolefin/phenylethylene copolymerization
Object includes the repetitive unit with formula (Ι) and formula (II) structure；
Wherein：
In formula (I) structure, n and m is each independently selected 0,1 or 2；
R1~R4Separate selection hydrogen, halogen, the C for containing or not contain concatenating group1~30Alkyl, the company of containing or not contain
Tie the C of base1~30Polar group, the C of substituted base or unsubstituted1~30Alkyl, the C of substituted base or unsubstituted1~30
Polar group, R1And R4By monocycle or it is polycyclic in the form of connect together, monocycle or it is polycyclic on can carry double bond；
The halogen is fluorine, chlorine and bromine；
The concatenating group is C1~10Divalent alkyl, carbonyl, carbonyloxy group, oxygen carbonyl, sulfonyl, ehter bond, thioether bond, imino group, acyl
One or more of amine key or siloxanes key；
The substituent group is fluorine, chlorine, bromine, benzenesulfonyl or cyano；
The C1~30Alkyl be alkyl, naphthenic base, alkenyl, cycloalkenyl group or aromatic series base；
The C1~30Polar group be C1~10Alkoxy, carbonyloxy group, alkoxy carbonyl group, aryloxy carbonyl, cyano, amide groups, acyl it is sub-
Amido, three organic group siloxies, sulfonic group or acidic group, the C1~10Alkoxy be methoxy or ethoxy, the carbonyl
Oxygroup is acetoxyl group, propionyloxy or benzoyloxy, and the alkoxy carbonyl group is methoxycarbonyl group or carbethoxyl group, the virtue oxygen
Carbonyl is carbobenzoxy, naphthalene oxygen carbonyl, fluorenylmethoxycarbonyl or biphenyl oxygen carbonyl, and the three organic groups siloxy is trimethyl first
Siloxy or silicohetane alkoxy；
In formula (II) structure, R5To R8For hydrogen, FG is chlorine atom；
The repetitive unit with formula (II) structure is more than in the insertion rate of the functional cycloolefin/styrene copolymer
Zero and be less than or equal to 50mol%；
The number-average molecular weight of the functionality cycloolefin/styrene copolymer is 0.5~500,000 grams/mol, molecular weight distribution
Ranging from the 1.8~2.8 of index；
The glass transition temperature of the functionality cycloolefin/styrene copolymer is 250~400 DEG C.
2. a kind of preparation method of functional cycloolefin/styrol copolymer as described in claim 1, it is characterized in that：In master
Under the action of catalyst and co-catalyst, by the cycloolefin with formula (III) structure and the phenylethylene with formula (IV) structure
Co-monomer carries out polymerisation in atent solvent or halogenated solvent, obtains cycloolefin/styrene copolymer；
Wherein：
In formula (III) structure, n and m is each independently selected 0,1 or 2；
R1~R4Separate selection hydrogen, halogen, the C for containing or not contain concatenating group1~30Alkyl, the company of containing or not contain
Tie the C of base1~30Polar group, the C of substituted base or unsubstituted1~30Alkyl, the C of substituted base or unsubstituted1~30
Polar group, R1And R4By monocycle or it is polycyclic in the form of connect together, monocycle or it is polycyclic on can carry double bond；
The halogen is fluorine, chlorine and bromine；
The concatenating group is C1~10Divalent alkyl, carbonyl, carbonyloxy group, oxygen carbonyl, sulfonyl, ehter bond, thioether bond, imino group, acyl
One or more of amine key or siloxanes key；
The substituent group is fluorine, chlorine, bromine, benzenesulfonyl or cyano；
The C1~30Alkyl be alkyl, naphthenic base, alkenyl, cycloalkenyl group or aromatic series base；
The C1~30Polar group be C1~10Alkoxy, carbonyloxy group, alkoxy carbonyl group, aryloxy carbonyl, cyano, amide groups, acyl it is sub-
Amido, three organic group siloxies, sulfonic group or acidic group, the C1~10Alkoxy be methoxy or ethoxy, the carbonyl
Oxygroup is acetoxyl group, propionyloxy or benzoyloxy, and the alkoxy carbonyl group is methoxycarbonyl group or carbethoxyl group, the virtue oxygen
Carbonyl is carbobenzoxy, naphthalene oxygen carbonyl, fluorenylmethoxycarbonyl or biphenyl oxygen carbonyl, and the three organic groups siloxy is trimethyl first
Siloxy or silicohetane alkoxy；
In formula (IV) structure, R5To R8For hydrogen, FG is chlorine atom；
The major catalyst is the late transition metal complex that the quinolinamine imidazoles with formula (V) structure is ligand；
Wherein：
R9To R18It is identical or different group, respectively arbitrarily selected from hydrogen, halogen, C1~4Alkyl, naphthenic base, with halogen or
C1~4One kind in the aryl of carbon substitution；
X1With X2Each identical or different group, respectively arbitrarily selected from halogen, C1~4One kind in alkyl；
M is transition metal, is iron, cobalt, nickel or palladium；
The co-catalyst is alkylaluminoxane or organo-aluminum compound；The alkylaluminoxane is methylaluminoxane, modified first
One or more of base aikyiaiurnirsoxan beta, ethylaluminoxane or isobutyl aluminium alkoxide；The organo-aluminum compound is diethylaluminum chloride
Or ethylaluminium dichloride.
3. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 2, which is characterized in that
The specific steps are：
1) under nitrogen atmosphere, atent solvent or halogenated solvent, cycloolefin and formula (IV) structure benzene with formula (III) structure is added
Catalyst and co-catalyst is added in vinyl monomer after stirring, carry out polymerisation；
2) obtained reactive polymeric product hydrochloric acid/ethanol solution terminated, be filtered, washed and dried, obtain cycloolefin/benzene second
Alkene copolymer.
4. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 2 or 3, feature exist
In the atent solvent is aromatic hydrocarbons, alkanes or cyclic hydrocar-bons solvent；Aromatic hydrocarbon solvent is toluene, dimethylbenzene or ethylbenzene, alkane
Class solvent is n-hexane, normal heptane or normal octane, and cyclic hydrocar-bons solvent is hexamethylene, cycloheptane or cyclooctane；The halogenated solvent
For dichloroethanes or chlorobenzene.
5. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 2 or 3, feature exist
In the atent solvent or the molar ratio of halogenated solvent and the cycloolefin with formula (III) structure are 2~50；It is described that there is formula
(III) molar ratio of the cycloolefin of structure and formula (IV) structure styrene class monomer is 0.1~10.
6. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 2 or 3, feature exist
In the molar ratio of the major catalyst and the cycloolefin with formula (III) structure is 0.00025~0.0025；The main catalytic
The molar ratio of agent and co-catalyst is 1:50~5000.
7. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 2 or 3, feature exist
In the temperature of the polymerisation is 0~90 DEG C, and the time is 1~180min.
8. a kind of preparation method of functional cycloolefin/styrol copolymer according to claim 3, which is characterized in that
The volume ratio of hydrochloric acid and ethyl alcohol is 1 in the hydrochloric acid/ethanol solution:20~60；The time of the stirring is 10~30min.
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