CN105348442B - Cyclic olefine copolymer and preparation method thereof - Google Patents
Cyclic olefine copolymer and preparation method thereof Download PDFInfo
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- CN105348442B CN105348442B CN201510705195.4A CN201510705195A CN105348442B CN 105348442 B CN105348442 B CN 105348442B CN 201510705195 A CN201510705195 A CN 201510705195A CN 105348442 B CN105348442 B CN 105348442B
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08F232/08—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 having condensed rings
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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Abstract
The invention provides the invention provides a kind of cyclic olefine copolymer, with Formulas I structure, in Formulas I, 170≤x≤240,200≤y≤300.The cyclic olefine copolymer that the present invention is provided has good heat endurance and the transparency.Test result indicate that, the present invention provide cyclic olefine copolymer glass transition temperature be 127.3 DEG C~229.6 DEG C, 10% thermal weight loss more than 430 DEG C, the present invention provide cyclic olefine copolymer light transmittance ＞ 90%.
Description
Technical field
The present invention relates to copolymer technical field, more particularly to a kind of cyclic olefine copolymer and preparation method thereof.
Background technology
Cyclic olefine copolymer is a kind of high added value thermoplastic engineering plastic by cycloolefin and alpha-olefine polymerizing, is
The extremely promising optical material of one class, with transparency very high, excellent heat resistance, chemical stability, fluidity of molten and
Dimensional stability etc..Current cyclic olefine copolymer has been widely used in the various optical lens prisms of manufacture, auto bulb, liquid
Crystal display screen optical thin film, contact lenses etc..Cyclic olefine copolymer will replace makrolon, as producing height of future generation
The optimal material of density DVD.Other cycloolefin copolymer resins also have extremely low dielectric constant, can be used for electronics and electrical equipment portion
The manufacture of part, also turns into emerging medicine, packaging material for food every moist because its is good
The heat resistance of cyclic olefine copolymer is the important performance of this material.In the use environment of some higher temperatures
Under, if the heat resistance of cyclic olefine copolymer is poor, cyclic olefine copolymer can be distorted and the change in deformation equidimension
Change, so as to directly affect the optical property and mechanical property of cyclic olefine copolymer.Therefore, the heat resistance of cyclic olefine copolymer is improved
Can greatly expand the use scope of cyclic olefine copolymer.The important indicator of cyclic olefine copolymer heat resistance is weighed for cycloolefin is common
The glass transition temperature of polymers, glass transition temperature is temperature of the copolymer from glassy state to rubber transition, works as environment
Temperature close to or up copolymer glass transition temperature when, copolymer can occur more serious deformation, and mechanical property
It is greatly reduced, this brings totally unfavorable influence to the application of copolymer material.Therefore the glass transition of copolymer is improved
Temperature can effectively improve the heat resistance of copolymer.
The synthetic method of cyclic olefine copolymer has two kinds：A kind of method is that ethene gathers with the chain type of Norbornene derivative
Close, another method is the ring-opening metathesis polymerization (ROMP) of Norbornene derivative and hydrogenates.Currently with ROMP methods gained
Commercialization cyclic olefine copolymer, such as product designation WithCyclic olefine copolymer
With preferable mechanical property, but the glass transition temperature of this cyclic olefine copolymer is relatively low, such asWithGlass transition temperature there was only 140 DEG C,Glass transition temperature be 170 DEG C, therefore this ring
The heat resistance of olefin copolymer is poor.
The content of the invention
In view of this, it is an object of the invention to provide a kind of cyclic olefine copolymer, the cycloolefin copolymer that the present invention is provided
Thing has preferable heat endurance.
The invention provides a kind of cyclic olefine copolymer, with Formulas I structure：
In Formulas I, 170≤x≤240,200≤y≤300.
Preferably, 180≤x≤200,210≤y≤240.
The preparation method of cyclic olefine copolymer, comprises the following steps described in a kind of above-mentioned technical proposal of the present invention：
Compound with Formula II structure and the compound with formula III structure carry out polymerisation, obtain polymerisation
Product；
The polymeric reaction product and hydrogen source are carried out into hydrogenation, cyclic olefine copolymer is obtained；
Preferably, the catalyst of the polymerisation is W-Sn deposits.
Preferably, the compound with Formula II structure and the mol ratio with formula III structural compounds for (3~
0.3)：1.
Preferably, the compound with Formula II structure and the total molal quantity of the compound with formula III structure and urge
The ratio of the molal quantity of agent is (800~1250)：1.
Preferably, the co-catalyst of the polymerisation is aluminum-based catalyst.
Preferably, the catalyst conditioning agent of the polymerisation is alcohols.
Preferably, the molecular weight regulator of the polymerisation is α-linear alkene.
Preferably, the reaction temperature of the polymerisation is 0 DEG C~50 DEG C；Reaction time is 60 minutes~180 minutes.
The invention provides the invention provides a kind of cyclic olefine copolymer, the structure with Formulas I, in Formulas I, 170≤x≤
240,200≤y≤300.The cyclic olefine copolymer that the present invention is provided has good heat endurance and the transparency.Experimental result table
Bright, the glass transition temperature of the cyclic olefine copolymer that the present invention is provided is 127.3 DEG C~229.6 DEG C, and 10% thermal weight loss is equal
More than 430 DEG C, the light transmittance ＞ 90% of the cyclic olefine copolymer that the present invention is provided.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 is obtained；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 2 is obtained；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 3 is obtained and cyclic olefine copolymer；
Fig. 4 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained；
Fig. 5 is thermogravimetric curve of the cyclic olefine copolymer that obtains of 3~embodiment of the embodiment of the present invention 7 in nitrogen；
Fig. 6 is the light transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 4 is obtained and cyclic olefine copolymer；
Fig. 8 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 5 is obtained and cyclic olefine copolymer；
Figure 10 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained；
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 6 is obtained and cyclic olefine copolymer；
Figure 12 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained；
Figure 13 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that the embodiment of the present invention 7 is obtained and cyclic olefine copolymer；
Figure 14 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained；
Figure 15 is the glass transition temperature and cyclenes of the cyclic olefine copolymer that 3~embodiment of the embodiment of the present invention 7 is obtained
Variation relation curve with Formula II structural compounds content in hydrocarbon copolymer.
Specific embodiment
The invention provides a kind of cyclic olefine copolymer, with Formulas I structure：
In Formulas I, 170≤x≤240,200≤y≤300.
In the present invention, it is preferred to, 180≤x≤200；It is furthermore preferred that 185≤x≤195.In the present invention, it is preferred to,
210≤y≤240；It is furthermore preferred that 220≤y≤230.The cyclic olefine copolymer that the present invention is provided has preferable heat resistance simultaneously
And the transparency..
The preparation method of cyclic olefine copolymer, comprises the following steps described in a kind of above-mentioned technical proposal of the present invention：
Compound with Formula II structure and the compound with formula III structure carry out polymerisation, obtain polymerisation
Product；
The polymeric reaction product and hydrogen source are carried out into hydrogenation, cyclic olefine copolymer is obtained；
Compound with Formula II structure and the compound with formula III structure are carried out polymerisation by the present invention first,
Obtain polymeric reaction product.
The present invention preferably mixes the compound with Formula II structure, the compound with formula III structure and solvent, carries out
Polymerisation, obtains polymeric reaction product.The present invention preferably under conditions of stirring by the compound with Formula II structure,
Compound and solvent mixing with formula III structure.The method stirred when the present invention is to the mixing does not have special limitation, adopts
With stirring technique scheme well known to those skilled in the art.In the present invention, the time stirred during the mixing is preferably 5
Minute~15 minutes, most preferably more preferably 8 minutes~12 minutes, 10 minutes.
In the present invention, the solvent is preferably toluene.The present invention does not have special limitation, institute to the consumption of the solvent
Stating solvent can provide liquid environment for polymerisation.In order to exclude the air in the solvent, preferred pair institute of the present invention
Stating solvent carries out liquid nitrogen frozen-thawing treatment.In the present invention, the liquid nitrogen frozen-thawing number of processing is preferably 3 times.
The present invention does not have special limitation to the method for the liquid nitrogen frozen-thawing treatment, using liquid well known to those skilled in the art
The technical scheme of chilled nitrogen-thawing treatment.It is cold that the present invention can carry out liquid nitrogen to the organic solvent by the following method
Freeze-thawization treatment：
The organic solvent is fitted into Schlenk bottles, described Schlenk bottles is put into liquid nitrogen and is freezed；
By Schlenk bottles after above-mentioned freezing carry out will be described Schlenk bottles after vacuumize process in solvent thaw.
The present invention has bubble to escape during the solvent is thawed, so as to eliminate the air in the solvent.
The present invention preferably carries out the polymerisation under conditions of drying, anaerobic.In the present invention, the polymerisation
Can be carried out in Braun (Mbraun) glove box, it would however also be possible to employ Xi Laike (Schlenk) technology of standard is in nitrogen
Carried out under protection.The present invention carries out the polymerisation preferably under conditions of stirring, and the present invention is stirred the polymerisation
The method of mixing does not have special limitation, using stirring technique scheme well known to those skilled in the art.
In the present invention, the temperature of the polymerisation is preferably 0 DEG C~50 DEG C, more preferably 10 DEG C~40 DEG C, optimal
Elect 25 DEG C~30 DEG C as.In the present invention, the time of the polymerisation be preferably 60min~180min, more preferably 80min
~150min, most preferably 100min~120min.
In the present invention, the catalyst of the polymerisation is preferably W-Sn deposits, more preferably tungsten hexachloride, pentachloro-
Change tungsten, tungsten tetrachloride, tungsten dichloride or four tungsten oxchlorides；Most preferably tungsten hexachloride.
In the present invention, the W-Sn deposits are preferably the compound with formula IV structure：
Present invention preferably employs polymerisation described in above-mentioned catalyst, above-mentioned catalyst it is active high, cheap,
Polymerization better tolerance；
In the present invention, the catalyst is preferably catalyst solution.In the present invention, it is molten in the catalyst solution
Agent is preferably hydrocarbon compound, halogenated hydrocarbon compound, cyclic hydrocarbon composition or arene compounds；More preferably pentamethylene,
Hexane, hexamethylene, decane, Permethyl 99A, benzene,toluene,xylene, ethylo benzene, dichloromethane, chloroform or tetrahydrofuran；It is optimal
Elect benzene, toluene, dichloromethane, hexamethylene or tetrahydrofuran as.The present invention does not have to the source of solvent in the catalyst solution
Special limitation, using the solvent of mentioned kind well known to those skilled in the art, can be bought by market and obtained.
In the present invention, the molar concentration of the catalyst solution is preferably 1.5 μm of ol/mL~4.5 μm ol/mL, more excellent
Elect 2 μm of ol/mL~4 μm ol/mL, most preferably 2.5 μm ol/mL~3 μm ol/mL as.In order that the catalyst fully dissolves
In the solvent of the catalyst solution, the present invention preferably under conditions of stirring, by the catalyst and catalyst solution
Solvent mixes, and obtains catalyst solution.The present invention does not have special limitation to the method for the stirring, using people in the art
Stirring scheme known to member.In the present invention, the time of the stirring be preferably 10 minutes~30 minutes, more preferably 15
Minute~20 minutes.
The present invention, without special limitation, can be bought by market and obtained to the source of the catalyst, can also use ability
The preparation method of the catalyst of mentioned kind is prepared known to field technique personnel.
In the present invention, the compound with Formula II structure and the mol ratio with formula III structural compounds are preferred
It is (3~0.3)：1, it is more preferably (2~1)：1, most preferably (1.3~2.2)：1.
In the present invention, the compound with Formula II structure and the total molal quantity of the compound with formula III structure
It is preferably (800~1250) with the ratio of the molal quantity of catalyst：1, more preferably (900~1100)：1, most preferably (980
~1050)：1.
The present invention can be by controlling the consumption of the polymerisation raw material to prepare cyclic olefine copolymer glass
Glass transition temperature.The compound with Formula II structure is more in the cyclic olefine copolymer that the present invention is prepared, and cycloolefin is common
The glass transition temperature of polymers is higher.
In the present invention, the co-catalyst of the polymerisation is alkyl aluminum class catalyst, is preferably selected from trimethyl aluminium, chlorination
One kind or several in dimethyl aluminium, dichloromethyl aluminium, diethylaluminum chloride, ethyl aluminum dichloride, triethyl aluminum and triisobutyl aluminium
Plant, more preferably triisobutyl aluminium.The present invention originates without special limitation to the co-catalyst, using art technology
The solvent of mentioned kind known to personnel, can be bought by market and obtained.
In the present invention, the catalyst conditioning agent of the polymerisation is alkyl alcohols, preferably absolute methanol, anhydrous second
One or more in alcohol, anhydrous propyl alcohol and anhydrous butanol, more preferably absolute ethyl alcohol.The present invention is to the catalyst conditioning agent
Source without special limitation, using the solvent of mentioned kind well known to those skilled in the art, can be bought by market
Obtain.
In the present invention, the molecular weight regulator of the polymerisation is α linear alkenes, preferably 1- amylenes, 1- hexenes, 1-
One or more in heptene and 1- octenes, more preferably 1- hexenes.The present invention does not have to the source of the molecular weight regulator
Special limitation, using the solvent of mentioned kind well known to those skilled in the art, can be bought by market and obtained.
In the present invention, the ratio of the molal quantity of the molal quantity of the co-catalyst and catalyst is preferably (0.5~5)：
1, more preferably (1~4)：1, most preferably (2~3)：1.
Preferably, the ratio of the molal quantity of the molal quantity of the catalyst conditioning agent and catalyst is preferably (0.5~5)：
1, more preferably (1~4)：1, most preferably (1.5~3)：1.
Preferably, the ratio of the molal quantity of the molal quantity of the molecular weight regulator and catalyst is (2-10)：1, it is more excellent
Elect as (3-8)：1, most preferably (4-6)：1.
In the present invention, expired by controlling the catalyst, co-catalyst, catalyst conditioning agent, molecular weight regulator
Sufficient aforementioned proportion can trigger the speed with Formula II structural compounds and with the polymerization of formula III structural compounds fast, make above-mentioned
Polymerisation has absolutely polymerisation conversion.
The present invention originates without special limitation to the compound with Formula II structure, using people in the art
The method with Formula II structural compounds is prepared known to member to prepare.In the present invention, it is described with Formula II structure
The preparation method of compound be preferably：
Dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol are reacted, is obtained with Formula II structure
Compound.
The present invention carries out the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyls-right preferably under conditions of vacuum
Cresols reacts.The present invention preferably carries out the dicyclopentadiene, cyclopentadiene and 2,6- under the pressurized conditions of protective gas
Di-t-butyl-paracresol reaction.In the present invention, the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol are anti-
Protective gas is preferably nitrogen in answering.In the present invention, the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-right
The pressure of cresols reaction nitrogen is preferably 15bar~25bar, and more preferably 18bar~22bar, most preferably 20bar. are at this
In invention, the temperature of the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol reaction is preferably 130 DEG C~170
DEG C, more preferably 140 DEG C~160 DEG C, most preferably 150 DEG C.In the present invention, the dicyclopentadiene, cyclopentadiene and 2,
The time of 6- di-t-butyls-paracresol reaction is preferably 10 hours~14 hours, more preferably 11 hours~13 hours.
In the present invention, the mol ratio of the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol is preferably
(800~1200):(2300~2500):1, more preferably (900~1100):(2300~2500):1, most preferably (1000~
1100):(2400~2410):1.The present invention does not have to the source of dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol
There is special limitation, can be bought by market and obtained.
After the completion of the dicyclopentadiene, cyclopentadiene and 2,6- di-t-butyl-paracresol reaction, the present invention is preferably incited somebody to action
The dicyclopentadiene that arrives, cyclopentadiene and 2,6- di-t-butyls-paracresol reactant cooling, vacuum distillation, added to residue alcohol,
Cross and filter insoluble matter, low temperature recrystallization, recrystallized with alcohol low temperature again after separating out solid, obtain the chemical combination with Formula II structure
Thing.The present invention does not have special limitation to the method for the cooling, vacuum distillation, filtering and low temperature recrystallization, using this area
Cooling, vacuum distillation, filtering and low temperature recrystallization technology scheme known to technical staff.In the present invention, the cooling
Temperature be preferably 20 DEG C~30 DEG C, more preferably 24 DEG C~28 DEG C.In the present invention, the temperature of the vacuum distillation is preferably
40 DEG C~80 DEG C, more preferably 50 DEG C~60 DEG C.In the present invention, the temperature of the low temperature recrystallization is preferably -20 DEG C~0
DEG C, more preferably -10 DEG C~-5 DEG C.
The present invention to it is described with formula III structural compounds source without special limitation, using people in the art
The method with formula III structural compounds is prepared known to member to prepare.In the present invention, it is described with formula III knot
The preparation method of the compound of structure is preferably：
Dicyclopentadiene, cyclo-octene and 2,6- di-t-butyl-paracresol are reacted, is obtained with formula III structure
Compound.
The present invention carries out the dicyclopentadiene, cyclo-octene and 2,6- di-t-butyls-to first preferably under conditions of vacuum
Phenol reacts.The present invention carried out preferably under conditions of protective gas the dicyclopentadiene, cyclo-octene and 2,6- di-t-butyls-
Paracresol reacts.In the present invention, protectiveness in the dicyclopentadiene, cyclo-octene and 2,6- di-t-butyl-paracresol reaction
Gas is preferably nitrogen.In the present invention, the temperature of the dicyclopentadiene, cyclo-octene and 2,6- di-t-butyl-paracresol reaction
Degree is preferably 180 DEG C~220 DEG C, most preferably more preferably 190 DEG C~210 DEG C, 200 DEG C.In the present invention, described bicyclic penta
The time of diene, cyclo-octene and 2,6- di-t-butyl-paracresol reaction is preferably 4 hours~8 hours, more preferably 5 hours~7
Hour, most preferably 6 hours.
After the completion of the dicyclopentadiene, cyclo-octene and 2,6- di-t-butyl-paracresol reaction, the present invention will preferably be obtained
Dicyclopentadiene, cyclo-octene and 2,6- di-t-butyl-paracresol product cooling, stand, vacuum distillation, obtain with formula
The compound of III structures.The present invention does not have special limitation to the method for the cooling, standing and vacuum distillation, using ability
The technical scheme of cooling, standing and vacuum distillation known to field technique personnel.In the present invention, the temperature of the cooling is excellent
Elect 20 DEG C~30 DEG C, more preferably 25 DEG C~28 DEG C as.In the present invention, to be preferably 10 hours~16 small the time of the standing
When, more preferably 12 hours~14 hours.In the present invention, the temperature of the vacuum distillation is preferably 110 DEG C~160 DEG C, more
Preferably 120 DEG C~150 DEG C.The present invention 130 DEG C~140 DEG C of cut when preferably collecting the vacuum distillation, the cut is
It is the compound with formula III structure.
In the present invention, the species of the species of the polymerization solvent and source and solvent in above-mentioned catalyst solution and
Source is consistent, will not be repeated here.In the present invention, the solvent of the polymerisation can be catalyzed with described in above-mentioned technical proposal
Solvent in agent solution is identical, it is also possible to different.
The present invention does not have special limitation to the consumption of the polymerization solvent, using well known to those skilled in the art
The consumption of solvent in polymerisation.In the present invention, the volume of the polymerization solvent elects 35~50 milliliters as, more excellent
Elect 40~45 milliliters as.
After the completion of the polymerisation, the polymerisation is terminated present invention preferably employs stirring is stopped, obtaining polymerization anti-
Answer solution；By the polymeric reaction solution and precipitant mix, product is precipitated；By precipitated product filtering, washing, do
It is dry, obtain polymeric reaction product.
After being precipitated product, the precipitated product is preferably filtered, washed, dried by the present invention, obtains polymerisation product
Thing.The present invention does not have special limitation to the method that the precipitated product is filtered, washed and dried, using those skilled in the art
The well known technical scheme being filtered, washed and dried.In the present invention, the reagent of the precipitated product washing is preferably second
Alcohol.In the present invention, the number of times of the precipitated product washing is preferably 2 times~4 times, more preferably 3 times.In the present invention, institute
State the dry method of precipitated product and be preferably vacuum drying.In the present invention, the dry temperature of the precipitated product is preferably 20
DEG C~40 DEG C, most preferably more preferably 25 DEG C~35 DEG C, 30 DEG C.In the present invention, the precipitated product dry time is excellent
Elect as 12 hours~24 hours, more preferably 16 hours~20 hours, most preferably 18 hours.
After obtaining polymeric reaction product, the polymeric reaction product and hydrogen source are carried out hydrogenation by the present invention, obtain ring
Olefin copolymer.The present invention carries out the hydrogenation preferably under conditions of protective gas.In the present invention, the hydrogenation
The protective gas of reaction is preferably nitrogen.The present invention does not have special limitation to the method for the hydrogenation, using ability
Hydrogenation technical scheme known to field technique personnel.
The present invention does not have special limitation to the species of the hydrogen source, and the hydrogen source is preferably hydrogen or hydrazine class compound,
More preferably hydrazine class compound, most preferably unifor.
In the present invention, when the hydrogen source is hydrazine class compound, the present invention preferably carries out hydrogenating instead by the following method
Cyclic olefine copolymer should be prepared：
The polymeric reaction product and hydrazine class compound are carried out into hydrogenation in a solvent, cyclic olefine copolymer is obtained.
In the present invention, the ratio of the molal quantity of the molal quantity and hydrazine class compound of double bond is excellent in the polymeric reaction product
Elect 1 as:(3~6), more preferably 1:(4~5).In the present invention, the hydrogenation solvent is preferably toluene.The present invention is right
The consumption of the hydrogenation solvent does not have special limitation, and the solvent for using can provide liquid environment for above-mentioned hydrogenation
.In the present invention, the reaction temperature when polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 110
DEG C~150 DEG C, most preferably more preferably 120 DEG C~140 DEG C, 130 DEG C.In the present invention, the polymeric reaction product and hydrazine
Reaction time when class compound carries out hydrogenation is preferably 12 hours~20 hours, more preferably 13 hours~16 hours.
In order to prevent above-mentioned polymeric reaction product and hydrazine class compound from carrying out crosslinking reaction, institute in hydriding process
State polymeric reaction product and reaction raw materials when hydrazine class compound carries out hydrogenation preferably also include free radical scavenger.This hair
It is bright there is no special limitation to the species of the free radical scavenger and source, using free radical well known to those skilled in the art
Agent for capturing, can be bought by market and obtained.In the present invention, the free radical scavenger is preferably 2,6- di-t-butyls -4-
Methylphenol.The present invention does not have special limitation to the consumption of the free radical scavenger, is known using those skilled in the art
Free radical scavenger consumption.In the present invention, the consumption of the free radical scavenger is preferably relative to above-mentioned skill
The consumption of the molal quantity 0.05eqv~3eqv of catalyst described in art scheme.
In the present invention, when the hydrogen source is hydrogen, the present invention preferably carries out hydrogenation preparation by the following method
Obtain cyclic olefine copolymer：
The polymeric reaction product and hydrogen are carried out into hydrogenation in a solvent, cyclic olefine copolymer is obtained.
In the present invention, the ratio of the molal quantity of the molal quantity and hydrogen of double bond is preferably 1 in the polymeric reaction product:
(3~6), more preferably 1:(4~5).In the present invention, the hydrogenation solvent is preferably toluene.The present invention is to the hydrogen
The consumption for changing reaction dissolvent does not have special limitation, and the solvent for using can provide liquid environment for above-mentioned hydrogenation.
In the present invention, the reaction temperature when polymeric reaction product and hydrogen carry out hydrogenation is preferably 130 DEG C~170 DEG C,
More preferably 140 DEG C~160 DEG C, most preferably 150 DEG C.In the present invention, the polymeric reaction product and hydrogen are hydrogenated
Reaction time during reaction is preferably 20 hours~28 hours, more preferably 22 hours~24 hours.
In order to prevent above-mentioned polymeric reaction product and hydrogen from carrying out crosslinking reaction, the polymerization in hydriding process
Reaction raw materials when product and hydrogen carry out hydrogenation preferably also include free radical scavenger.The present invention is to the freedom
The species of base agent for capturing and source do not have special limitation, using free radical scavenger well known to those skilled in the art,
Can be bought by market and obtained.In the present invention, the free radical scavenger is preferably 2,6- di-tert-butyl-4-methy phenols.This
Invention does not have special limitation to the consumption of the free radical scavenger, using radical-scavenging well known to those skilled in the art
The consumption of agent.In the present invention, the consumption of the free radical scavenger is preferably and is urged relative to described in above-mentioned technical proposal
The consumption of the molal quantity 0.05eqv~3eqv of agent.
After the completion of the hydrogenation, the hydrogenation reaction product that the present invention will preferably be obtained mixes with ethanol, by what is obtained
Mix products are filtered, wash, dried, and obtain cyclic olefine copolymer.In the present invention, the purity of the ethanol be preferably 97%~
99%.The present invention does not have special limitation to the method that the mix products are filtered, washed and dried, using people in the art
The technical scheme being filtered, washed and dried known to member.In the present invention, the drying means of the mix products is preferably
Vacuum drying.In the present invention, the drying time of the mix products be preferably 12 hours~24 hours, more preferably 16 hours
~20 hours.In the present invention, the drying temperature of the mix products is preferably 40 DEG C~70 DEG C, more preferably 50 DEG C~65
DEG C, most preferably 60 DEG C.
After preparing cyclic olefine copolymer, present invention preferably employs in the following manner to the cyclic olefine copolymer for preparing
It is measured：
Proton nmr spectra is detected：The present invention carries out proton nmr spectra detection to the cyclic olefine copolymer for obtaining, described
The detection method of proton nmr spectra detection is to be surveyed at 125 DEG C using Varian Unity-400 types nuclear magnetic resonance chemical analysers
Fixed, tetramethylsilane (TMS) is internal standard, and deuterated o-dichlorohenzene is solvent, while being detected through carbon-13 nmr spectra, testing result is
The cyclic olefine copolymer that the present invention is provided has the structure of Formulas I.
Glass transition temperature：The glass of the cyclic olefine copolymer that the present invention is obtained using differential thermal analysis and thermogravimetry test
Glass transition temperature, detection method is to carry out differential thermal analysis survey using Perkin-ElmerPyris1DSC differential scanning calorimeters
Fixed, the speed of heating, cooling is 10 DEG C/min, carries out rescan.Surveyed using the type instruments of Perkin-Elmer Pyris 1
Determine thermal weight loss.The glass transition temperature of the cyclic olefine copolymer that testing result is provided for the present invention is 127 DEG C~229 DEG C, tool
There is preferable heat endurance.
The transparency：The present invention is obtained using Shimadzu UV-3600 ultraviolet-visible lights-near infrared spectrometer test
Cyclic olefine copolymer the transparency, test wavelength be 400nm~800nm.Test result is that the cycloolefin that the present invention is obtained is total to
The light transmittance ＞ 90% of polymers.
Molecular weight distribution and number-average molecular weight：The cyclic olefine copolymer that the present invention is obtained using gel permeation chromatography test
Molecular weight distribution and number-average molecular weight, detection method are to be measured using the type high-temperature gel permeation chromatography instrument of PL-GPC 220；
Detected using RI-Laser detectors；Detection solvent is trichloro-benzenes, and detection temperature is 150 DEG C；Flow rate of mobile phase is 1.0mL/
Min, it is standard specimen to use PL EasiCal PS-1.The molecular weight distribution of the cyclic olefine copolymer that test result is provided for the present invention
It is 2.2~3.8, number-average molecular weight is 3.5 × 104G/mol~5.6 × 104g/mol。
Conversion ratio：The present invention tests the polymerization conversion of polymerisation described in above-mentioned technical proposal using the method for Weighed product
Rate, test result is that the polymerisation conversion of above-mentioned polymerisation is 100%.
The invention provides a kind of cyclic olefine copolymer, the structure with Formulas I, in Formulas I, 170≤x≤240,200≤y≤
300.The cyclic olefine copolymer that the present invention is provided has preferable heat resistance.Additionally, the cyclic olefine copolymer that the present invention is provided is also
With the preferable transparency.
In order to further appreciate that the present invention, the cyclic olefine copolymer to present invention offer and its preparation with reference to embodiment
Method is described in detail, but it is to be understood that these descriptions are intended merely to further illustrate the features and advantages of the present invention, and
They can not be interpreted as limiting the scope of the present invention.
Reaction raw materials used in following examples of the present invention are commercial goods.
Embodiment 1
To sequentially adding 320 grams of dicyclopentadienes, 160 grams of cyclopentadiene, 1 gram of 2,6- bis- in 1 liter of stainless steel autoclave
T-butyl-p-cresol, repeats to vacuumize the operation of rear inflated with nitrogen for 3 times to the autoclave；The autoclave nitrogen is added
It is pressed onto 20 handkerchiefs and is heated to 150 DEG C, the reaction for making the material in the autoclave be carried out under conditions of stirring 12 hours.
After the reaction terminates, the product that will be obtained is cooled to 25 DEG C, and vacuum distillation obtains lower boiling unreacted
380 grams of thing.To 1 liter of ethanol is added in residue, cross filtrate after filtering insoluble matter and freeze 3 hours.Solid 84 is filtered to obtain after recrystallization
Gram, obtain 67 grams of solid with 800 milliliters of ethyl alcohol recrystallizations again.The method that the embodiment of the present invention 1 is provided prepares the product of product
Rate is 67%.
Product obtained above is carried out into proton nmr spectra detection, testing result such as Fig. 1, Fig. 1 are the embodiment of the present invention 1
The hydrogen nuclear magnetic resonance spectrogram of the product for obtaining, as shown in Figure 1, the product that the embodiment of the present invention 1 is obtained is with Formula II structure
Compound.
Embodiment 2
To sequentially adding 115 grams of dicyclopentadienes, 310 grams of cyclo-octene, 1 gram of 2,6- bis- in 1 liter of stainless steel autoclave
T-butyl-p-cresol, repeats to vacuumize the operation of rear inflated with nitrogen for 3 times to the autoclave；The autoclave is heated to
200 DEG C, the reaction for making the material in the autoclave be carried out under conditions of stirring 6 hours.
After reaction terminates, the product that will be obtained is cooled to 25 DEG C, and decompression steaming is carried out at 65 DEG C after standing 12 hours
Evaporate, collect unreacted dicyclopentadiene and cyclopentadiene；The product obtained after vacuum distillation is subtracted again at 135 DEG C
Pressure distillation, collects cut during vacuum distillation, obtains 114 grams of products.The method that the embodiment of the present invention 2 is provided prepares product
Yield is 70%.
Product obtained above is carried out into proton nmr spectra detection, testing result such as Fig. 2, Fig. 2 are the embodiment of the present invention 2
The hydrogen nuclear magnetic resonance spectrogram of the product for obtaining, as shown in Figure 2, the product that the embodiment of the present invention 2 is obtained is with formula III structure
Compound.
Embodiment 3
At 25 DEG C to dry polymerisation bottle in add that what 6 mMs of embodiments of (1.2g) 1 prepared have
The compound of Formula II structure, plus 40 milliliters of lower fully dissolvings of toluene stirring.To be separately added into solution 0.06 mM 1- oneself
Alkene, 18 micromolar absolute ethyl alcohols and 18 micromolar triisobutyl aluminiums are simultaneously sufficiently stirred for.To addition in 100 milliliters of branch mouthful bottle
28.06 milligrams of tungsten hexachloride, then to adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, it is substantially dissolved in tungsten hexachloride
In toluene, tungsten hexachloride catalyst solution is obtained；Under conditions of stirring, the tungsten hexachloride catalyst solution is taken into 2.5 millis
Rise the polymerisation for being added in above-mentioned polymerisation bottle and carrying out 120min；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.It is computed, this hair
The yield of the polymeric reaction product that the polymerization that bright embodiment 3 is provided is obtained is 100%, and purity is more than 99.9%.
In dry polymerisation bottle, sequentially add the above-mentioned polymeric reaction product of 1.2g, the unifor of 1g,
2,6- di-tert-butyl-4-methy phenols (BHT) and the toluene of 40mL relative to the molal quantity 1eqv of above-mentioned tungsten hexachloride,
Being refluxed at 130 DEG C 16 hours carries out hydrogenation, obtains hydrogenation reaction product；The hydrogenation reaction product is added drop-wise to
During the purity of 300mL is 98% ethanol, toluene again with 40mL is molten at 130 DEG C after the mix products filtering that will be obtained is drained
Solution 30 minutes, the solution after dissolving is added in the ethanol that the purity of 300mL is 98% again, and the mix products that will be obtained are put
Enter vacuum drying oven to be dried 12 hours at 60 DEG C, obtain 1.17g cyclic olefine copolymers.The hydrogenation that the embodiment of the present invention 3 is provided is anti-
The yield that the method answered obtains cyclic olefine copolymer is 98%, and purity is more than 99.9%.
According to the method described in above-mentioned technical proposal, nuclear-magnetism is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained
Resonance hydrogen spectrum detection, testing result such as Fig. 3, Fig. 3 are the polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 3 is obtained
Hydrogen nuclear magnetic resonance spectrogram, curve 1 is the proton nmr spectra of polymeric reaction product that the embodiment of the present invention 3 is obtained in Fig. 3, bent
Line 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained, as seen from Figure 3, the embodiment of the present invention
3 polymeric reaction products for obtaining are wholly absent by double bond peak after hydrogenation, and hydrogenation effect is preferable.
Gel infiltration is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained according to above-mentioned technical proposal methods described
Chromatogram is tested, and test result is that the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained is 2.7, the equal molecule of number
Measure is 3.5 × 104g/mol。
Differential thermal point is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained according to the method described in above-mentioned technical proposal
Analysis method is tested, and test result such as Fig. 4, Fig. 4 are that the differential scanning calorimetry of the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained is bent
Line, as shown in Figure 4, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained does not have melt temperature, is amorphous state, and the present invention is implemented
The glass transition temperature of the cyclic olefine copolymer that example 3 is obtained is 229.6 DEG C.According to above-mentioned technical proposal methods described to this hair
The cyclic olefine copolymer that bright embodiment 3 is obtained carries out thermogravimetry test, and test result such as Fig. 5, Fig. 5 are the embodiment of the present invention 3
Thermogravimetric curve of the cyclic olefine copolymer that~embodiment 7 is obtained in nitrogen, curve 1 is what the embodiment of the present invention 3 was obtained in Fig. 5
Thermogravimetric curve of the cyclic olefine copolymer in nitrogen；As shown in Figure 5, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained is 446
DEG C when resolution ratio be 10%, with heat endurance higher.
The transparency of the cyclic olefine copolymer obtained according to the above-mentioned technical proposal methods described test embodiment of the present invention 3,
Test result such as Fig. 6, Fig. 6 are the light transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3, embodiment 5 and embodiment 7 are obtained,
Curve 1 is the light transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained in Fig. 6, it will be appreciated from fig. 6 that the embodiment of the present invention 3
The light transmittance ＞ 90% of the cyclic olefine copolymer for arriving.
Embodiment 4
At 25 DEG C to dry polymerisation bottle in add the tool for preparing of 4.5 mMs of embodiments of (0.9g) 1
The compound with formula III structure that the compound and 1.5 mMs of embodiments of (0.3g) 2 for having Formula II structure are prepared,
Plus 40 milliliters of lower fully dissolvings of toluene stirring.To the 1- hexenes that 0.06 mM is separately added into solution, 12 is micromolar anhydrous
Ethanol and 15 micromolar triisobutyl aluminiums are simultaneously sufficiently stirred for.To the chlordene that 28.06 milligrams are added in 100 milliliters of branch mouthful bottle
Tungsten, then to adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, the tungsten hexachloride is substantially dissolved in toluene, obtain six
The catalyst solution of tungsten chloride；Under conditions of stirring, the catalyst solution of the tungsten hexachloride is taken 2.5 milliliters and is added to
State the polymerisation that 120min is carried out in polymerisation bottle；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.The present invention is implemented
The yield of the polymeric reaction product that the polymerization that example 4 is provided is obtained is 100%, and purity is more than 99.9%.
In dry polymerisation bottle, sequentially add the above-mentioned polymeric reaction product of 1.2g, the unifor of 1g,
2,6- di-tert-butyl-4-methy phenols (BHT) and the toluene of 40mL relative to the molal quantity 1eqv of above-mentioned tungsten hexachloride,
Being refluxed at 130 DEG C 16 hours carries out hydrogenation, obtains hydrogenation reaction product；The hydrogenation reaction product is added drop-wise to
During the purity of 300mL is 98% ethanol, toluene again with 40mL is molten at 130 DEG C after the mix products filtering that will be obtained is drained
Solution 30 minutes, the solution after dissolving is added in the ethanol that the purity of 300mL is 98% again, and the mix products that will be obtained are put
Enter vacuum drying oven to be dried 12 hours at 60 DEG C, obtain 1.13g cyclic olefine copolymers.The hydrogenation that the embodiment of the present invention 4 is provided is anti-
The yield that the method answered obtains cyclic olefine copolymer is 94.6%, and purity is more than 99.9%.
According to the method described in above-mentioned technical proposal, nuclear-magnetism is carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained
Resonance hydrogen spectrum detection, testing result such as Fig. 7, Fig. 7 are the polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 4 is obtained
Hydrogen nuclear magnetic resonance spectrogram, curve 1 is the proton nmr spectra of polymeric reaction product that the embodiment of the present invention 4 is obtained in Fig. 7, bent
Line 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained, as seen from Figure 7, the embodiment of the present invention
4 polymeric reaction products for obtaining are wholly absent by double bond peak after hydrogenation, and hydrogenation effect is preferable.
Gel infiltration is carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained according to above-mentioned technical proposal methods described
Chromatogram is tested, and test result is that the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained is 3.8, the equal molecule of number
Measure is 4.9 × 104g/mol。
Differential thermal point is carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained according to the method described in above-mentioned technical proposal
Analysis method is tested, and test result such as Fig. 8, Fig. 8 are that the differential scanning calorimetry of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained is bent
Line, as shown in Figure 8, the glass transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained is 190.8 DEG C.According to upper
State technical scheme methods described carries out thermogravimetry test, test result to the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained
Such as Fig. 5, curve 2 is thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 4 in nitrogen in Fig. 5；Can by Fig. 5
Know, resolution ratio of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained at 435 DEG C is 10%, with preferable heat endurance.
The transparency of the cyclic olefine copolymer obtained according to the above-mentioned technical proposal methods described test embodiment of the present invention 4,
Test result is the light transmittance ＞ 90% of the cyclic olefine copolymer that the embodiment of the present invention 4 is obtained.
Turn according to polymerization of the above-mentioned technical proposal methods described test embodiment of the present invention 4 when above-mentioned polymerisation is carried out
Rate, test result is that the polymerisation conversion when embodiment of the present invention 4 carries out above-mentioned polymerisation is 100%.
Embodiment 5
At 25 DEG C to dry polymerisation bottle in add that what 3 mMs of embodiments of (0.6g) 1 prepared have
The compound with formula III structure that the compound of Formula II structure and 3 mMs of embodiments of (0.6g) 2 are prepared, plus 40
The lower fully dissolving of milliliter toluene stirring.To the 1- hexenes that 0.06 mM is separately added into solution, 12 micromolar absolute ethyl alcohols
With 15 micromolar triisobutyl aluminiums and be sufficiently stirred for.To the tungsten hexachloride that 28.06 milligrams are added in 100 milliliters of branch mouthful bottle, then
To adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, the tungsten hexachloride is substantially dissolved in toluene, obtain chlordene
Tungsten catalyst solution；Under conditions of stirring, the catalyst solution of the tungsten hexachloride is taken 2.5 milliliters and is added to above-mentioned polymerization
The polymerisation of 120min is carried out in reaction bulb；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.The present invention is implemented
The yield of the polymeric reaction product that the polymerization that example 5 is provided is obtained is 100%, and purity is more than 99.9%.
In dry polymerisation bottle, sequentially add the above-mentioned polymeric reaction product of 1.2g, the unifor of 1g,
2,6- di-tert-butyl-4-methy phenols (BHT) and the toluene of 40mL relative to the molal quantity 1eqv of above-mentioned tungsten hexachloride,
Being refluxed at 130 DEG C 16 hours carries out hydrogenation, obtains hydrogenation reaction product；The hydrogenation reaction product is added drop-wise to
During the purity of 300mL is 98% ethanol, toluene again with 40mL is molten at 130 DEG C after the mix products filtering that will be obtained is drained
Solution 30 minutes, the solution after dissolving is added in the ethanol that the purity of 300mL is 98% again, and the mix products that will be obtained are put
Enter vacuum drying oven to be dried 12 hours at 60 DEG C, obtain 1.15g cyclic olefine copolymers.The hydrogenation that the embodiment of the present invention 5 is provided is anti-
The yield that the method answered obtains cyclic olefine copolymer is 96%, and purity is more than 99.9%.
According to the method described in above-mentioned technical proposal, nuclear-magnetism is carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained
Resonance hydrogen spectrum detection, testing result such as Fig. 9, Fig. 9 are the polymeric reaction product and cyclic olefine copolymer that the embodiment of the present invention 5 is obtained
Hydrogen nuclear magnetic resonance spectrogram, curve 1 is the proton nmr spectra of polymeric reaction product that the embodiment of the present invention 5 is obtained in Fig. 9, bent
Line 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained, as seen from Figure 9, the embodiment of the present invention
5 polymeric reaction products for obtaining are wholly absent by double bond peak after hydrogenation, and hydrogenation effect is preferable.
Gel infiltration is carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained according to above-mentioned technical proposal methods described
Chromatogram is tested, and test result is that the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained is 2.9, the equal molecule of number
Measure is 4.2 × 104g/mol。
Differential thermal point is carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained according to the method described in above-mentioned technical proposal
Analysis method is tested, and test result such as Figure 10, Figure 10 are that the differential scanning calorimetry of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained is bent
Line, as shown in Figure 10, the glass transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained is 175.3 DEG C.According to upper
State technical scheme methods described carries out thermogravimetry test, test result to the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained
Such as Fig. 5, curve 3 is thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 5 in nitrogen in Fig. 5；Can by Fig. 5
Know, resolution ratio of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained at 444 DEG C is 10%, with preferable heat endurance.
The transparency of the cyclic olefine copolymer obtained according to the above-mentioned technical proposal methods described test embodiment of the present invention 5,
Test result is the light transmittance ＞ 90% of the cyclic olefine copolymer that the embodiment of the present invention 5 is obtained.
Turn according to polymerization of the above-mentioned technical proposal methods described test embodiment of the present invention 5 when above-mentioned polymerisation is carried out
Rate, test result is that the polymerisation conversion when embodiment of the present invention 5 carries out above-mentioned polymerisation is 100%.
Embodiment 6
At 25 DEG C to dry polymerisation bottle in add the tool for preparing of 1.5 mMs of embodiments of (0.3g) 1
The compound with formula III structure that the compound and 4.5 mMs of embodiments of (0.9g) 2 for having Formula II structure are prepared,
Plus 40 milliliters of lower fully dissolvings of toluene stirring.To the 1- hexenes that 0.06 mM is separately added into solution, 12 is micromolar anhydrous
Ethanol and 12 micromolar triisobutyl aluminiums are simultaneously sufficiently stirred for.To the chlordene that 28.06 milligrams are added in 100 milliliters of branch mouthful bottle
Tungsten, then to adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, the tungsten hexachloride is substantially dissolved in toluene, obtain six
Tungsten chloride catalyst solution；Under conditions of stirring, the tungsten hexachloride catalyst solution is taken 2.5 milliliters and is added to above-mentioned gathering
The polymerisation of 120min is carried out in conjunction reaction bulb；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.The present invention is implemented
The yield of the polymeric reaction product that the polymerization that example 6 is provided is obtained is 100%, and purity is more than 99.9%.
In dry polymerisation bottle, sequentially add the above-mentioned polymeric reaction product of 1.2g, the unifor of 1g,
2,6- di-tert-butyl-4-methy phenols (BHT) and the toluene of 40mL relative to the molal quantity 1eqv of above-mentioned tungsten hexachloride,
Being refluxed at 130 DEG C 16 hours carries out hydrogenation, obtains hydrogenation reaction product；The hydrogenation reaction product is added drop-wise to
During the purity of 300mL is 98% ethanol, toluene again with 40mL is molten at 130 DEG C after the mix products filtering that will be obtained is drained
Solution 30 minutes, the solution after dissolving is added in the ethanol that the purity of 300mL is 98% again, and the mix products that will be obtained are put
Enter vacuum drying oven to be dried 12 hours at 60 DEG C, obtain 1.14g cyclic olefine copolymers.The hydrogenation that the embodiment of the present invention 6 is provided is anti-
The yield that the method answered obtains cyclic olefine copolymer is 95.2%, and purity is more than 99.9%.
According to the method described in above-mentioned technical proposal, nuclear-magnetism is carried out to the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained
Resonance hydrogen spectrum detection, testing result such as Figure 11, Figure 11 are the polymeric reaction product and cycloolefin copolymer that the embodiment of the present invention 6 is obtained
The hydrogen nuclear magnetic resonance spectrogram of thing, curve 1 is the hydrogen nuclear magnetic resonance of the polymeric reaction product that the embodiment of the present invention 6 is obtained in Figure 11
Spectrum, curve 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained, as seen from Figure 11, the present invention
The polymeric reaction product that embodiment 6 is obtained is wholly absent by double bond peak after hydrogenation, and hydrogenation effect is preferable.
Gel infiltration is carried out to the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained according to above-mentioned technical proposal methods described
Chromatogram is tested, and test result is that the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained is 2.7, the equal molecule of number
Measure is 3.8 × 104g/mol。
Differential thermal point is carried out to the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained according to the method described in above-mentioned technical proposal
Analysis method is tested, and test result such as Figure 12, Figure 12 are that the differential scanning calorimetry of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained is bent
Line, as shown in Figure 12, the glass transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained is 155.6 DEG C.According to upper
State technical scheme methods described carries out thermogravimetry test, test result to the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained
Such as Fig. 5, curve 4 is thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 6 in nitrogen in Fig. 5；Can by Fig. 5
Know, resolution ratio of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained at 447 DEG C is 10%, with preferable heat endurance.
The transparency of the cyclic olefine copolymer obtained according to the above-mentioned technical proposal methods described test embodiment of the present invention 6,
Test result is the light transmittance ＞ 90% of the cyclic olefine copolymer that the embodiment of the present invention 6 is obtained.
Turn according to polymerization of the above-mentioned technical proposal methods described test embodiment of the present invention 6 when above-mentioned polymerisation is carried out
Rate, test result is that the polymerisation conversion when embodiment of the present invention 6 carries out above-mentioned polymerisation is 100%.
Embodiment 7
At 25 DEG C to dry polymerisation bottle in add that what 6 mMs of embodiments of (1.2g) 2 prepared have
The compound of formula III structure, plus 40 milliliters of lower fully dissolvings of toluene stirring.To be separately added into solution 0.06 mM 1- oneself
Alkene, 9 micromolar absolute ethyl alcohols and 12 micromolar triisobutyl aluminiums are simultaneously sufficiently stirred for.To addition in 100 milliliters of branch mouthful bottle
28.06 milligrams of tungsten hexachloride, then to adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, make the tungsten hexachloride fully molten
Solution obtains tungsten hexachloride solution in toluene；Under conditions of stirring, the tungsten hexachloride catalyst solution is taken 2.5 milliliters
Being added in above-mentioned polymerisation bottle carries out the polymerisation of 120min；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.The present invention is implemented
The yield of the polymeric reaction product that the polymerization that example 7 is provided is obtained is 100%, and purity is more than 99.9%.
In dry polymerisation bottle, sequentially add the above-mentioned polymeric reaction product of 1.2g, the unifor of 1g,
2,6- di-tert-butyl-4-methy phenols (BHT) and the toluene of 40mL relative to the molal quantity 1eqv of above-mentioned tungsten hexachloride,
Being refluxed at 130 DEG C 16 hours carries out hydrogenation, obtains hydrogenation reaction product；The hydrogenation reaction product is added drop-wise to
During the purity of 300mL is 98% ethanol, toluene again with 40mL is molten at 130 DEG C after the mix products filtering that will be obtained is drained
Solution 30 minutes, the solution after dissolving is added in the ethanol that the purity of 300mL is 98% again, and the mix products that will be obtained are put
Enter vacuum drying oven to be dried 12 hours at 60 DEG C, obtain 1.12g cyclic olefine copolymers.The hydrogenation that the embodiment of the present invention 7 is provided is anti-
The yield that the method answered obtains cyclic olefine copolymer is 93.3%, and purity is more than 99.9%.
According to the method described in above-mentioned technical proposal, nuclear-magnetism is carried out to the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained
Resonance hydrogen spectrum detection, testing result such as Figure 13, Figure 13 are the polymeric reaction product and cycloolefin copolymer that the embodiment of the present invention 7 is obtained
The hydrogen nuclear magnetic resonance spectrogram of thing, curve 1 is the hydrogen nuclear magnetic resonance of the polymeric reaction product that the embodiment of the present invention 7 is obtained in Figure 13
Spectrum, curve 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained, as seen from Figure 13, the present invention
The polymeric reaction product that embodiment 7 is obtained is wholly absent by double bond peak after hydrogenation, and hydrogenation effect is preferable.
Gel infiltration is carried out to the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained according to above-mentioned technical proposal methods described
Chromatogram is tested, and test result is that the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained is 2.2, the equal molecule of number
Measure is 5.6 × 104g/mol。
Differential thermal point is carried out to the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained according to the method described in above-mentioned technical proposal
Analysis method is tested, and test result such as Figure 14, Figure 14 are that the differential scanning calorimetry of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained is bent
Line, as shown in Figure 14, the glass transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained is 127.3 DEG C.According to upper
State technical scheme methods described carries out thermogravimetry test, test result to the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained
Such as Fig. 5, curve 5 is thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 7 in nitrogen in Fig. 5；Can by Fig. 5
Know, resolution ratio of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained at 442 DEG C is 10%, with preferably thermally-stabilised
Property..
The transparency of the cyclic olefine copolymer obtained according to the above-mentioned technical proposal methods described test embodiment of the present invention 7,
Test result is the light transmittance ＞ 90% of the cyclic olefine copolymer that the embodiment of the present invention 7 is obtained.
Turn according to polymerization of the above-mentioned technical proposal methods described test embodiment of the present invention 7 when above-mentioned polymerisation is carried out
Rate, test result is that the polymerisation conversion when embodiment of the present invention 7 carries out above-mentioned polymerisation is 100%.
Figure 15 is the glass transition temperature and cyclenes of the cyclic olefine copolymer that 3~embodiment of the embodiment of the present invention 7 is obtained
Variation relation curve with Formula II structural compounds content in hydrocarbon copolymer, as shown in Figure 15, the cycloolefin that the present invention is obtained
The compound with Formula II structure is more in copolymer, and the glass transition temperature of cyclic olefine copolymer is higher.
Embodiment 8
At 25 DEG C to dry polymerisation bottle in add that what 6 mMs of embodiments of (1.2g) 1 prepared have
The compound of Formula II structure, plus 40 milliliters of lower fully dissolvings of toluene stirring.To be separately added into solution 0.06 mM 1- oneself
Alkene, 18 micromolar absolute ethyl alcohols and 18 micromolar triisobutyl aluminiums are simultaneously sufficiently stirred for.To addition in 100 milliliters of branch mouthful bottle
28.06 milligrams of tungsten hexachloride, then to adding 25 milliliters of toluene to stir 15 minutes in branch mouthful bottle, it is substantially dissolved in tungsten hexachloride
In toluene, tungsten hexachloride catalyst solution is obtained；Under conditions of stirring, the tungsten hexachloride catalyst solution is taken into 2.5 millis
Rise the polymerisation for being added in above-mentioned polymerisation bottle and carrying out 120min；
After the completion of the polymerisation, under conditions of stirring to above-mentioned polymerisation bottle in add certain toluene to molten
Liquid dilutes, after the polymeric reaction solution that will obtain pour into absolute ethyl alcohol, be precipitated product；After the precipitated product is filtered
Washed with ethanol 3 times, dried 12 hours in 40 DEG C of vacuum drying oven, obtain the polymeric reaction product of 1.2g.It is computed, this hair
The yield of the polymeric reaction product that the polymerization that bright embodiment 8 is provided is obtained is 100%, and purity is more than 99.9%.
By predrying 5 hours under conditions of vacuum, to being added in the autoclave, 1g is above-mentioned to be prepared in autoclave
Polymeric reaction product, the hexamethylene of 300mL, the Pd/Al of 0.5g2O3Catalyst, carries out the autoclave for 3 times and substitutes gas
The hydrogen of 3MPa is filled with the backward autoclave of operation, the hydrogenation of 24h is carried out at 150 DEG C, the hydrogenation that will be obtained
Solution filters to reclaim Pd/Al therein2O3Catalyst, obtains hydrogenation reaction product；The hydrogenation reaction product is poured into ethanol
Middle precipitation, is put into vacuum drying oven and is dried 12 hours at 60 DEG C after the precipitated product filtering that will be obtained, and obtains the cycloolefin of 0.90g
Copolymer.
The structure and performance of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 8 described in embodiment 3,
Test result is that the cyclic olefine copolymer that obtains of the embodiment of the present invention 8 has structure shown in Formulas I, and x is for 190, y in Formulas I
230.The glass transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 8 is obtained is 229.1 DEG C, the embodiment of the present invention 8
The molecular weight distribution of the cyclic olefine copolymer for arriving is 2.6, and number-average molecular weight is 3.3 × 104g/mol.The embodiment of the present invention 8 is obtained
Cyclic olefine copolymer light transmittance ＞ 90%.The polymerisation conversion of polymerisation is 100%, purity in the embodiment of the present invention 8
More than 99.9%.The cyclic olefine copolymer that the embodiment of the present invention 8 is obtained has glass transition temperature and the transparency higher.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.To these embodiments
Various modifications are for those skilled in the art it will be apparent that generic principles defined herein can be not
Realized in other embodiments in the case of departing from the spirit or scope of the present invention.Therefore, the present invention is not intended to be limited to this
These embodiments of text, and it is to fit to the most wide scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. a kind of cyclic olefine copolymer, with Formulas I structure：
In Formulas I, 170≤x≤240,200≤y≤300.
2. cyclic olefine copolymer according to claim 1, it is characterised in that 180≤x≤200,210≤y≤240.
3. a kind of preparation method of cyclic olefine copolymer described in claim 1, comprises the following steps：
Compound with Formula II structure and the compound with formula III structure carry out polymerisation, obtain polymeric reaction product；
The polymeric reaction product and hydrogen source are carried out into hydrogenation, cyclic olefine copolymer is obtained；
4. preparation method according to claim 3, it is characterised in that the catalyst of the polymerisation is the catalysis of tungsten system
Agent.
5. preparation method according to claim 3, it is characterised in that the compound with Formula II structure and with formula
The mol ratio of III structural compounds is (3~0.3)：1.
6. preparation method according to claim 4, it is characterised in that the compound with Formula II structure and with formula
The ratio of the molal quantity of the total molal quantity of the compound of III structures and catalyst is (800~1250)：1.
7. preparation method according to claim 3, it is characterised in that the co-catalyst of the polymerisation is the catalysis of aluminium system
Agent.
8. preparation method according to claim 3, it is characterised in that the catalyst conditioning agent of the polymerisation is alcohol
Class.
9. preparation method according to claim 3, it is characterised in that the molecular weight regulator of the polymerisation is α-straight
Olefine.
10. preparation method according to claim 3, it is characterised in that the reaction temperature of the polymerisation is 0 DEG C~50
℃；Reaction time is 60 minutes~180 minutes.
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| CN107226888B (en) * | 2017-07-20 | 2019-10-25 | 中国科学院长春应用化学研究所 | A kind of cyclic olefine copolymer and preparation method thereof |
| CN112480374A (en) * | 2020-11-26 | 2021-03-12 | 中国科学院长春应用化学研究所 | Polar cycloolefin copolymer and preparation method thereof |
| CN115819656A (en) * | 2021-09-16 | 2023-03-21 | 华为技术有限公司 | Cycloolefin copolymer, process for producing the same and use thereof |
| CN115073664B (en) * | 2022-07-04 | 2023-11-28 | 广东新华粤石化集团股份公司 | Cycloolefin polymer film with optical anisotropy and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849851A (en) * | 1992-04-03 | 1998-12-15 | California Institute Of Technology | Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes |
| CN1218449A (en) * | 1996-03-13 | 1999-06-02 | 奥普塔技术公司 | Method for preparing norbornene and substituted derivatives of norbornene |
| CN1554680A (en) * | 1998-12-09 | 2004-12-15 | ס�ѵ�ľ��ʽ���� | In mold addition polymerization composition of norbornene-type monomers and its crosslinking addition polymer |
| CN102066456A (en) * | 2008-06-20 | 2011-05-18 | 3M创新有限公司 | Molded microstructured articles and method of making same |
| CN103159914A (en) * | 2011-12-16 | 2013-06-19 | Jsr株式会社 | Cycloolefin-based ring-opening copolymer |
-
2015
- 2015-10-26 CN CN201510705195.4A patent/CN105348442B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849851A (en) * | 1992-04-03 | 1998-12-15 | California Institute Of Technology | Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes |
| CN1218449A (en) * | 1996-03-13 | 1999-06-02 | 奥普塔技术公司 | Method for preparing norbornene and substituted derivatives of norbornene |
| CN1554680A (en) * | 1998-12-09 | 2004-12-15 | ס�ѵ�ľ��ʽ���� | In mold addition polymerization composition of norbornene-type monomers and its crosslinking addition polymer |
| CN102066456A (en) * | 2008-06-20 | 2011-05-18 | 3M创新有限公司 | Molded microstructured articles and method of making same |
| CN103159914A (en) * | 2011-12-16 | 2013-06-19 | Jsr株式会社 | Cycloolefin-based ring-opening copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 含降冰片烯多脂环化合物在高聚物上的应用;蒋硕健，等;《湖南化工》;19991231;第29卷(第6期);第7-13页 * |
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