CN103951775B - A kind of cyclic olefine copolymer and preparation method thereof - Google Patents
A kind of cyclic olefine copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, x is the polymerization degree, 300≤x≤1000.Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.Experimental result shows, the second-order transition temperature of cyclic olefine copolymer provided by the invention is 212 DEG C ~ 224 DEG C, has good thermotolerance; Tensile strength is 21MPa ~ 55MPa, and tensile modulus is 1400MPa ~ 1940MPa, and elongation at break is 1.7% ~ 2.7%, has good mechanical property.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.Experimental result shows, the transmittance > 90% of cyclic olefine copolymer provided by the invention.
Description
Technical field
The present invention relates to multipolymer technical field, particularly relate to a kind of cyclic olefine copolymer and preparation method thereof.
Background technology
Cyclic olefine copolymer is the thermoplastic engineering plastic of a class by the high added value of cyclic olefin polymerization, and this multipolymer has high transparent, low-k, excellent thermotolerance, chemical resistant properties, and the mobility of melt, barrier and dimensional stability are better.Therefore, cyclic olefine copolymer can be widely used in and manufactures various optics, information, electrical equipment, medical material.
The resistance toheat of cyclic olefine copolymer is the key property of this material.Under the environment for use of some comparatively high temps, if the resistance toheat of cyclic olefine copolymer is poor, then cyclic olefine copolymer can be distorted and the change of being out of shape in equidimension, thus directly affects optical property and the mechanical property of cyclic olefine copolymer.Therefore, the resistance toheat improving cyclic olefine copolymer can the use range of expanded ring olefin copolymer greatly.The important indicator weighing cyclic olefine copolymer thermotolerance is the second-order transition temperature of cyclic olefine copolymer, second-order transition temperature is that multipolymer is from vitreous state to the temperature of rubbery transition, when envrionment temperature close to or when reaching the second-order transition temperature of multipolymer, comparatively serious distortion can be there is in multipolymer, and mechanical property declines greatly, this brings totally unfavorable impact to the application of copolymer material.Therefore the second-order transition temperature improving multipolymer can improve the thermotolerance of multipolymer effectively.
The synthetic method of cyclic olefine copolymer has two kinds: a kind of method is the chain polymerization of ethene and Norbornene derivative, and another kind of method is the ring-opening metathesis polymerization (ROMP) of Norbornene derivative and hydrogenation.Utilize the commercialization cyclic olefine copolymer of ROMP method gained at present, as trade names are
with
cyclic olefine copolymer there is good mechanical property, but the second-order transition temperature of this cyclic olefine copolymer is lower, as
with
second-order transition temperature only have 140 DEG C,
second-order transition temperature be 170 DEG C, therefore the thermotolerance of this cyclic olefine copolymer is poor.
Adopt the method for the chain polymerization of ethene and Norbornene derivative can prepare the higher cyclic olefine copolymer of second-order transition temperature, as trade names are
cyclic olefine copolymer, but the molecular chain rigidity of this cyclic olefine copolymer is comparatively strong, the elongation at break of cyclic olefine copolymer is poor, and therefore the mechanical property of this cyclic olefine copolymer is poor.
The cyclic olefine copolymer that prior art provides cannot have good thermotolerance and mechanical property simultaneously.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of cyclic olefine copolymer, cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.
The invention provides a kind of cyclic olefine copolymer, there is the structure shown in formula I:
formula I;
In formula I, x is the polymerization degree, 300≤x≤1000.
Preferably, in described formula I, 400≤x≤700.
The invention provides the preparation method of cyclic olefine copolymer described in a kind of technique scheme, comprise the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out polyreaction in a solvent, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cyclic olefine copolymer;
formula II.
Preferably, described catalyzer is carbene catalyst.
Preferably, described catalyzer is ruthenium class carbene compound.
Preferably, the mol ratio of the compound and catalyzer described in structure shown in formula II is (300 ~ 1000): 1.
Preferably, described step 1) in the temperature of polyreaction be 0 DEG C ~ 50 DEG C;
Described step 1) in time of polyreaction be 60 minutes ~ 180 minutes.
Preferably, described step 2) in hydrogen source be hydrazine class compound.
Preferably, described step 2) in the ratio of the mole number of polymeric reaction product double bond and the mole number of hydrazine class compound be 1:(3 ~ 6).
Preferably, described step 2) in the temperature of hydrogenation be 110 DEG C ~ 150 DEG C;
Described step 2) in time of hydrogenation be 12 hours ~ 20 hours.
The invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, x is the polymerization degree, 300≤x≤1000.Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.Experimental result shows, the second-order transition temperature of cyclic olefine copolymer provided by the invention is 212 DEG C ~ 224 DEG C, has good thermotolerance; Tensile strength is 21MPa ~ 55MPa, and tensile modulus is 1400MPa ~ 1950MPa, and elongation at break is 1.7% ~ 2.7%, has good mechanical property.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.Experimental result shows, the transmittance > 90% of cyclic olefine copolymer provided by the invention.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 obtains;
Fig. 2 be the product that the embodiment of the present invention 2 obtains hydrogen nuclear magnetic resonance (
1h) spectrogram;
Fig. 3 be the product that the embodiment of the present invention 2 obtains nucleus magnetic resonance phosphorus (
31p) spectrogram;
Fig. 4 is the carbon-13 nmr spectra figure of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains;
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that obtains of the embodiment of the present invention 3 and cyclic olefine copolymer;
Fig. 6 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 3 ~ embodiment 5 obtains;
Fig. 7 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains;
Fig. 8 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains.
Embodiment
The invention provides a kind of cyclic olefine copolymer, there is the structure shown in formula I:
formula I;
In formula I, x is the polymerization degree, 300≤x≤1000.
In the present invention, preferably, 400≤x≤700; Preferred, 500≤x≤600.Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
The invention provides the preparation method of cyclic olefine copolymer described in a kind of technique scheme, comprise the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out polyreaction in a solvent, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cyclic olefine copolymer;
formula II.
The present invention preferably will have compound and the solvent of structure shown in formula II, add catalyzer and will carry out polyreaction, obtain polymeric reaction product in the mixture obtained.The present invention preferably stir condition under by described compound and the solvent with structure shown in formula II.The present invention does not have special restriction to the method stirred during described mixing, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the time of stirring during described mixing is preferably 5 minutes ~ 15 minutes, is more preferably 8 minutes ~ 12 minutes, most preferably is 10 minutes.
The present invention preferably carries out described polyreaction under the condition of drying, anaerobic.In the present invention, described polyreaction can be carried out in Braun (Mbraun) glove box, and Xi Laike (Schlenk) technology of standard also can be adopted to carry out under the protection of nitrogen.The present invention preferably carries out described polyreaction under the condition stirred, and the stirring means of the present invention to described polyreaction does not have special restriction, adopts stirring technique scheme well known to those skilled in the art.
In the present invention, the temperature of described polyreaction is preferably 0 DEG C ~ 50 DEG C, is more preferably 10 DEG C ~ 40 DEG C, most preferably is 20 DEG C ~ 30 DEG C.In the present invention, the time of described polyreaction is preferably 60min ~ 120min, is more preferably 80min ~ 110min, most preferably is 90min ~ 100min.
In the present invention, described catalyzer is preferably carbene catalyst, is more preferably ruthenium class carbene compound.In the present invention, described ruthenium class carbene compound preferably has the compound of structure shown in formula III:
formula III,
In formula III, L is preferably PCy
3; X is preferably Cl, Br or I; R
1be preferably H, Ph or CH
2cH
3; R is preferably Cy, Cp or Ph.In the present invention, in described formula III, X is more preferably Cl; R
1be more preferably Ph; R is more preferably Cy.In the present invention, described ruthenium class carbene compound is more preferably the compound with structure shown in formula IV:
formula IV.
The present invention preferably adopts polyreaction described in carbene catalyst catalysis, and the activity of this catalyzer is high, polymerization better tolerance, makes the present invention in the process preparing cyclic olefine copolymer without the need to adding promotor; And this catalyzer can evenly cause above-mentioned polyreaction, make the molecular weight distribution of the cyclic olefine copolymer obtained narrower, be conducive to the number-average molecular weight regulating the cyclic olefine copolymer prepared; This catalyzer causes the speed of above-mentioned polyreaction soon in addition, makes above-mentioned polyreaction have higher polymerisation conversion.
In the present invention, described catalyzer is preferably catalyst solution.In the present invention, the solvent in described catalyst solution is preferably hydrocarbon compound, halogenated hydrocarbon compound, cyclic hydrocarbon composition or arene compounds; Be more preferably pentamethylene, hexane, hexanaphthene, decane, Permethyl 99A., benzene,toluene,xylene, ethylbenzene, methylene dichloride, chloroform or tetrahydrofuran (THF); Most preferably be benzene, toluene, methylene dichloride, hexanaphthene or tetrahydrofuran (THF).The present invention does not have special restriction to the source of solvent in described catalyst solution, adopts the solvent of mentioned kind well known to those skilled in the art, can be bought obtain by market.
In the present invention, the volumetric molar concentration of described catalyst solution is preferably 3 μm of ol/mL ~ 6 μm ol/mL, is more preferably 4 μm of ol/mL ~ 5.5 μm ol/mL, most preferably is 4.5 μm of ol/mL ~ 5 μm ol/mL.In order to make described catalyzer fully be dissolved in the solvent of catalyst solution, the present invention, preferably under ultrasonic condition, by the solvent of described catalyzer and catalyst solution, obtains catalyst solution.The present invention does not have special restriction to described ultrasonic method, adopts ultrasonic technique scheme well known to those skilled in the art.In the present invention, the described ultrasonic time is preferably 2 minutes ~ 5 minutes, is more preferably 3 minutes ~ 4 minutes.
The source of the present invention to described catalyzer does not have special restriction, adopts the preparation method of the carbene catalyst of mentioned kind well known to those skilled in the art to prepare.In the present invention, the preparation method described in structural compounds shown in formula IV is preferably:
By phenyldiazomethane, dichloro three (triphenylphosphine) closes ruthenium and tricyclohexyl phosphine reacts in organic solvent, obtains the compound with structure shown in formula IV.
Phenyldiazomethane, organic solvent and dichloro three (triphenylphosphine) is more preferably closed ruthenium mixing by the present invention, adds tricyclohexyl phosphine and reacts, obtain having the compound of structure shown in formula IV in the mixture obtained.In the present invention, the temperature that described phenyldiazomethane, organic solvent and dichloro three (triphenylphosphine) closes ruthenium mixing is preferably-80 DEG C ~-50 DEG C, is more preferably-78 DEG C ~-55 DEG C, most preferably is-75 DEG C ~-65 DEG C.In the present invention, described in add tricyclohexyl phosphine temperature be preferably-70 DEG C ~-50 DEG C, be more preferably-60 DEG C ~-55 DEG C.The present invention preferably carries out described phenyldiazomethane under the protection of nitrogen, dichloro three (triphenylphosphine) closes ruthenium and thricyclohexyl phosphine reaction.The present invention preferably carries out described phenyldiazomethane under the condition stirred, dichloro three (triphenylphosphine) closes ruthenium and thricyclohexyl phosphine reaction.The present invention closes to described phenyldiazomethane, dichloro three (triphenylphosphine) method that ruthenium and thricyclohexyl phosphine reaction stir does not have special restriction, adopts stirring technique scheme well known to those skilled in the art.
In the present invention, the temperature that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction is preferably-80 DEG C ~ 30 DEG C, is more preferably-78 DEG C ~ 25 DEG C, most preferably is-70 DEG C ~ 20 DEG C.In the present invention, the time that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction is preferably 30 minutes ~ 50 minutes, is more preferably 35 minutes ~ 45 minutes, most preferably is 40 minutes.
The source of the present invention to described phenyldiazomethane does not have special restriction, can be bought and obtain, the preparation method of phenyldiazomethane well known to those skilled in the art also can be adopted to prepare by market.In the present invention, the preparation method of described phenyldiazomethane is preferably:
By phenyl aldehyde-carry out building-up reactions to Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol, obtain phenyldiazomethane.
The present invention preferably carries out described building-up reactions under the condition of water-bath.In the present invention, the temperature of described building-up reactions is preferably 50 DEG C ~ 70 DEG C, is more preferably 55 DEG C ~ 65 DEG C, most preferably is 60 DEG C.In the present invention, the time of described building-up reactions is preferably 0.5 hour ~ 1.5 hours, is more preferably 1 hour.In the present invention, described phenyl aldehyde-1:(2 ~ 3 are preferably to the mass ratio of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol): (25 ~ 35), be more preferably 1:(2.4 ~ 2.9): (27 ~ 32), most preferably are 1:2.8:25.The present invention, to described phenyl aldehyde-do not have special restriction to the source of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol, can be bought by market and obtain.
After described building-up reactions completes, the methyl alcohol in the building-up reactions solution obtained preferably is removed by the present invention, obtains building-up reactions product; Described building-up reactions product is carried out extract, dry, obtain phenyldiazomethane.The method of the present invention to described removal methyl alcohol does not have special restriction, in embodiment in the present invention, mechanical pump can be adopted to be extracted by the methyl alcohol in described building-up reactions solution.Described building-up reactions product is preferably first carried out the first extraction with Skellysolve A by the present invention, then the first extraction product sodium chloride aqueous solution obtained is carried out the second extraction.In the present invention, described sodium chloride aqueous solution is preferably saturated sodium-chloride water solution.In the present invention, the method for described building-up reactions product drying is preferably spin-dried for.In the present invention, the temperature of described building-up reactions product drying is preferably-35 DEG C ~-45 DEG C, is more preferably-40 DEG C.
In the present invention, described phenyldiazomethane is preferably the pentane solution of phenyldiazomethane.In the present invention, the mass concentration of the pentane solution of described phenyldiazomethane is preferably 90mg/mL ~ 100mg/mL, is more preferably 94mg/mL ~ 98mg/mL.
The present invention does not have special restriction to the source that described dichloro three (triphenylphosphine) closes ruthenium, can be bought obtain by market.
In the present invention, described tricyclohexyl phosphine is preferably the dichloromethane solution of tricyclohexyl phosphine.In the present invention, the mass concentration of the dichloromethane solution of described tricyclohexyl phosphine is preferably 0.06g/mL ~ 0.07g/mL, is more preferably 0.064g/mL ~ 0.068g/mL.The source of the present invention to described tricyclohexyl phosphine does not have special restriction, can be bought obtain by market.
In the present invention, the mass ratio that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine is preferably 1:(3 ~ 6): (1 ~ 3.5), be more preferably 1:(4 ~ 5): (2 ~ 3), most preferably are 1:4.6:2.6.
In the present invention, described organic solvent is preferably methylene dichloride.The consumption of the present invention to described organic solvent does not have special restriction, and described organic solvent can be above-mentioned phenyldiazomethane, dichloro three (triphenylphosphine) closes ruthenium and thricyclohexyl phosphine reaction provides liquid environment.In order to get rid of the air in described organic solvent, the present invention preferably carries out liquid nitrogen freezing-thawing process to described organic solvent.In the present invention, the number of times of described liquid nitrogen freezing-thawing process is preferably 3 times.The method of the present invention to described liquid nitrogen freezing-thawing process does not have special restriction, adopts the technical scheme of liquid nitrogen freezing well known to those skilled in the art-thawing process.The present invention can carry out liquid nitrogen freezing-thawing process to described organic solvent by the following method:
Described organic solvent is loaded in Schlenk bottle, described Schlenk bottle is put into liquid nitrogen freezing;
By above-mentioned freezing after Schlenk bottle carry out vacuumizing process after the organic solvent in described Schlenk bottle is thawed.
The present invention has bubble to overflow in the process of being thawed by described organic solvent, thus eliminates the air in described organic solvent.
Described phenyldiazomethane, dichloro three (triphenylphosphine) close after ruthenium and tricyclohexyl phosphine should complete, the phenyldiazomethane obtained, dichloro three (triphenylphosphine) are preferably closed ruthenium by the present invention and tricyclohexyl phosphine reaction soln filters, dissolve, concentrated, precipitation, washing, dry, obtain having the compound of structure shown in formula IV.The method of the present invention to described filtration, dissolving, concentrated, precipitation, washing and drying does not have special restriction, adopts the technical scheme of filtration well known to those skilled in the art, dissolving, concentrated, precipitation, washing and drying.In the present invention, the reagent of described precipitation is preferably methyl alcohol.In the present invention, after described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine reaction soln precipitation, the reagent of washing is preferably methyl alcohol and acetone.In the present invention, the method that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and the drying of tricyclohexyl phosphine reaction soln is preferably vacuum-drying.In the present invention, the time that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and the drying of tricyclohexyl phosphine reaction soln is preferably 2 hours ~ 4 hours, is more preferably 3 hours.
In the present invention, described in there is the compound structural unity of structure shown in formula II steric hindrance comparatively large, main chain rigidity is comparatively strong, makes cyclic olefine copolymer provided by the invention have higher second-order transition temperature.The present invention does not have special restriction to the described source with the compound of structure shown in formula II, and the method adopting preparation well known to those skilled in the art to have structural compounds shown in formula II prepares.In the present invention, the preparation method described in the compound of structure shown in formula II is preferably:
Norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol is reacted, obtains having the compound of structure shown in formula II.
The present invention preferably carries out described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction under the condition of vacuum.The present invention preferably carries out described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction under the condition of protective gas.In the present invention, in described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction, protective gas is preferably nitrogen.In the present invention, the temperature of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction is preferably 160 DEG C ~ 200 DEG C, is more preferably 170 DEG C ~ 190 DEG C, most preferably is 180 DEG C.In the present invention, the time of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction is preferably 25 hours ~ 35 hours, is more preferably 28 hours ~ 32 hours.
In the present invention, described norbornadiene, anthracene and 2, the mol ratio of 6-di-t-butyl-p-cresol is preferably (1500 ~ 2000): (260 ~ 300): 1, be more preferably (1600 ~ 1800): (270 ~ 295): 1, most preferably be (1700 ~ 1760): (284 ~ 290): 1.The source of the present invention to described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol does not have special restriction, can be bought obtain by market.
Described norbornadiene, anthracene and 2, after 6-di-t-butyl-p-cresol has reacted, norbornadiene, anthracene and 2, the 6-di-t-butyl-p-cresol reaction product obtained preferably cools, leaves standstill, filters, washs by the present invention, obtains having the compound of structure shown in formula II.The present invention does not have special restriction, the technical scheme adopt cooling well known to those skilled in the art, leaving standstill, filter and wash to described cooling, method that is standing, that filter and wash.In the present invention, the temperature of described cooling is preferably 20 DEG C ~ 30 DEG C, is more preferably 24 DEG C ~ 28 DEG C.In the present invention, the described standing time is preferably 10 hours ~ 16 hours, is more preferably 12 hours ~ 14 hours.In the present invention, the reagent of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction product washing is preferably normal hexane.
In the present invention, described in there is the compound of structure shown in formula II and catalyzer mol ratio be preferably (300 ~ 1000): 1, be more preferably (400 ~ 700): 1, most preferably be (500 ~ 600): 1.
In the present invention, the kind of the kind of described polymerization solvent and source and solvent in catalyst solution described in technique scheme with originate consistent, do not repeat them here.In the present invention, the solvent of described polyreaction can be same with the solvent phase in catalyst solution described in technique scheme, also can be different.
The consumption of the present invention to described polymerization solvent does not have special restriction, adopts the consumption of solvent in polyreaction well known to those skilled in the art.In the present invention, described in there is structure shown in formula II the mass ratio of compound and polymerization solvent be preferably 1:(10 ~ 25), be more preferably 1:(15 ~ 20).
After described polyreaction completes, the present invention preferably adopts terminator to stop described polyreaction, obtains polymeric reaction solution; By described polymeric reaction solution and precipitant mix, be precipitated product; By described precipitated product filtration, washing, drying, obtain polymeric reaction product.
The present invention does not have special restriction to the kind of described terminator and source, adopts the terminator adopted when preparing cyclic olefine copolymer well known to those skilled in the art, can buy acquisition by market.In the present invention, described terminator is preferably ethyl vinyl ether.In the present invention, the mol ratio of described terminator and catalyzer is preferably (100 ~ 500): 1, is more preferably (200 ~ 400): 1, most preferably is 300:1.In the present invention, the time stopping described polyreaction is preferably 20 minutes ~ 40 minutes, is more preferably 25 minutes ~ 35 minutes, most preferably is 30 minutes.
After obtaining polymeric reaction solution, the present invention preferably by described polymeric reaction solution and precipitant mix, is precipitated product.The kind of precipitation agent of the present invention to the described polymeric reaction solution of precipitation does not have special restriction, adopts the precipitation agent adopted when preparing cyclic olefine copolymer well known to those skilled in the art.In the present invention, the precipitation agent precipitating described polymeric reaction solution is preferably methyl alcohol, is more preferably anhydrous methanol.In the present invention, the temperature of described polymeric reaction solution and precipitant mix is preferably-10 DEG C ~ 0 DEG C, is more preferably-8 DEG C ~-5 DEG C.
After being precipitated product, the present invention preferably by described precipitated product filtration, washing, drying, obtains polymeric reaction product.The present invention filters described precipitated product, washing and the method for drying do not have special restriction, adopts the technical scheme of filtration well known to those skilled in the art, washing and drying.In the present invention, the reagent of described precipitated product washing is preferably acetone.In the present invention, the number of times of described precipitated product washing is preferably 2 times ~ 4 times, is more preferably 3 times.In the present invention, the method for described precipitated product drying is preferably vacuum-drying.In the present invention, the temperature of described precipitated product drying is preferably 20 DEG C ~ 40 DEG C, is more preferably 25 DEG C ~ 35 DEG C, most preferably is 30 DEG C.In the present invention, the time of described precipitated product drying is preferably 12 hours ~ 24 hours, is more preferably 16 hours ~ 20 hours, most preferably is 18 hours.
After obtaining polymeric reaction product, described polymeric reaction product and hydrogen source are carried out hydrogenation by the present invention, obtain cyclic olefine copolymer.The present invention preferably carries out described hydrogenation under the condition of protective gas.In the present invention, the protective gas of described hydrogenation is preferably nitrogen.The method of the present invention to described hydrogenation does not have special restriction, adopts hydrogenation technical scheme well known to those skilled in the art.
The kind of the present invention to described hydrogen source does not have special restriction, and described hydrogen source is preferably hydrogen or hydrazine class compound, is more preferably hydrazine class compound, most preferably is p-toluene sulfonyl hydrazide.
In the present invention, when described hydrogen source is hydrazine class compound, the present invention preferably carries out hydrogenation by the following method and prepares cyclic olefine copolymer:
Described polymeric reaction product and hydrazine class compound are carried out hydrogenation in a solvent, obtains cyclic olefine copolymer.
In the present invention, in described polymeric reaction product, the ratio of the mole number of double bond and the mole number of hydrazine class compound is preferably 1:(3 ~ 6), be more preferably 1:(4 ~ 5).In the present invention, described hydrogenation solvent is preferably toluene.The consumption of the present invention to described hydrogenation solvent does not have special restriction, and the solvent of employing can provide liquid environment for above-mentioned hydrogenation.In the present invention, temperature of reaction when described polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 120 DEG C ~ 140 DEG C, is more preferably 125 DEG C ~ 135 DEG C, most preferably is 130 DEG C.In the present invention, reaction times when described polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 12 hours ~ 20 hours, is more preferably 16 hours ~ 18 hours.
Carry out to prevent above-mentioned polymeric reaction product and hydrazine class compound, in hydriding process, crosslinking reaction occurs, reaction raw materials when described polymeric reaction product and hydrazine class compound carry out hydrogenation preferably also comprises free radical scavenger.The present invention does not have special restriction to the kind of described free radical scavenger and source, adopts free radical scavenger well known to those skilled in the art, can be bought obtain by market.In the present invention, described free radical scavenger is preferably 2,6 di tert butyl 4 methyl phenol.The consumption of the present invention to described free radical scavenger does not have special restriction, adopts the consumption of free radical scavenger well known to those skilled in the art.In the present invention, the consumption of described free radical scavenger is preferably the consumption relative to the mole number 0.05eqv ~ 3eqv of catalyzer described in technique scheme.
After described hydrogenation completes, the hydrogenation reaction product obtained preferably mixes with ethanol by the present invention, is filtered the mix products that obtains, washing, dry, obtains cyclic olefine copolymer.In the present invention, the purity of described ethanol is preferably 97% ~ 99%.The present invention filters described mix products, washing and the method for drying do not have special restriction, adopts the technical scheme of filtration well known to those skilled in the art, washing and drying.In the present invention, the drying means of described mix products is preferably vacuum-drying.In the present invention, the time of drying of described mix products is preferably 12 hours ~ 24 hours, is more preferably 16 hours ~ 20 hours.In the present invention, the drying temperature of described mix products is preferably 40 DEG C ~ 70 DEG C, is more preferably 50 DEG C ~ 65 DEG C, most preferably is 60 DEG C.
After preparing cyclic olefine copolymer, the present invention carries out carbon-13 nmr spectra detection to the cyclic olefine copolymer obtained and proton nmr spectra detects, the detection method that described proton nmr spectra detects and carbon-13 nmr spectra detects measures at 25 DEG C for adopting VarianUnity-400 type nuclear magnetic resonance spectrometer, tetramethylsilane (TMS) is interior mark, and deuterochloroform is solvent.Detected result has the structure shown in formula I for cyclic olefine copolymer provided by the invention.
The present invention adopts differential thermal analysis and thermogravimetry to test the second-order transition temperature of the cyclic olefine copolymer obtained, detection method carries out differential thermal analysis mensuration for adopting Perkin-ElmerPyris1DSC differential scanning calorimeter, the speed of heating, cooling is 10 DEG C/min, carries out rescan.Adopt Perkin-ElmerPyris1 type Instrument measuring thermal weight loss.Detected result is the second-order transition temperature of cyclic olefine copolymer provided by the invention is 212 DEG C ~ 224 DEG C, has good thermostability.
The present invention is at INSTRON1121, Canton, MA instrument is tested the mechanical property of the cyclic olefine copolymer obtained, detect according to the standard of GB/T1040-1992 " plastic tensile performance test methods ", batten folder distance is 20.0mm, test rate is 5mm/min, and each sample at least tests 8 times to ensure the reliability of data.Test result is, the tensile strength of cyclic olefine copolymer provided by the invention is 21MPa ~ 55MPa, and tensile modulus is 1400MPa ~ 1940MPa, and elongation at break is 1.7% ~ 2.7%.
The present invention adopts ShimadzuUV-3600 ultraviolet-visible light-near infrared spectrometer to test the transparency of the cyclic olefine copolymer obtained, and test wavelength is 400nm ~ 800nm.Test result is the transmittance > 90% of the cyclic olefine copolymer that the present invention obtains.
The present invention adopts gel permeation chromatography to test molecular weight distribution and the number-average molecular weight of the cyclic olefine copolymer obtained, and detection method measures for adopting waters152 type gel permeation chromatograph; RI-Laser detector is adopted to detect; Detection solvent is tetrahydrofuran (THF), and detected temperatures is 35 DEG C; Flow rate of mobile phase is 1.0mL/min, and employing PLEasiCalPS-1 is standard specimen.Test result is the molecular weight distribution of cyclic olefine copolymer provided by the invention is 1.3 ~ 1.35, and number-average molecular weight is 9 × 10
4g/mol ~ 32 × 10
4g/mol.
The present invention adopts the method for Weighed product to test the polymerisation conversion of polyreaction described in technique scheme, and test result is the polymerisation conversion of above-mentioned polyreaction is 100%.
The invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, x is the polymerization degree, 300≤x≤1000.Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
In order to understand the present invention further; below in conjunction with embodiment, cyclic olefine copolymer provided by the invention and preparation method thereof is described in detail; but be to be understood that; these describe just in order 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 by following examples of the present invention is commercial goods.
Embodiment 1
In the stainless steel autoclaves of 2 liters, add 2, the 6-di-t-butyls-p-cresol of the norbornadiene of 800mL, the anthracene of 230 grams and 1 gram successively, the operation that 3 times vacuumize rear inflated with nitrogen is repeated to described autoclave; Described autoclave is heated to 180 DEG C, makes the reaction that the material in described autoclave carries out 30 hours under the condition stirred.
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, leaves standstill after 12 hours and filter, by the filtration product n-hexane that obtains 2 times, obtain 260 grams of products.The productive rate that the method that the embodiment of the present invention 1 provides prepares product is 75%.
Product obtained above is carried out proton nmr spectra detection, detected result as shown in Figure 1, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 obtains, and the product that obtains of the embodiment of the present invention 1 is for having the compound of structure shown in formula II as shown in Figure 1.
Embodiment 2
In the single port bottle of 100mL, add the phenyl aldehyde-to Methyl benzenesulfonyl hydrazone, the sodium methylate of 1.75 grams and the Triethylene glycol of 40mL of 4.96 grams, described single port bottle is placed in the water-bath of 60 DEG C the building-up reactions of carrying out 1 hour.
After described building-up reactions completes, the methyl alcohol water pump in the building-up reactions solution obtained is extracted, obtains building-up reactions product; Again with saturated NaCl aqueous solution extraction after described building-up reactions product is extracted with Skellysolve A in frozen water, the extraction product obtained is spin-dried for, obtains phenyldiazomethane; The productive rate of described phenyldiazomethane is 50%.
The dichloro three (triphenylphosphine) adding 4.0 grams in a mouth bottle of 250mL closes ruthenium, passes into the air in a mouth bottle described in nitrogen replacement, injects the methylene dichloride of 40mL through three liquid nitrogen freezing-thawing process in described mouth bottle; Described mouth bottle is placed in the cryostat of-78 DEG C, under the condition stirred, add-50 DEG C of mass concentrations is that the pentane solution 10mL of the phenyldiazomethane of 98.5mg/mL mixes, and the phenyldiazomethane in the pentane solution of described phenyldiazomethane is the above-mentioned phenyldiazomethane prepared; Add 40mL after the mixture obtained is stirred 10min at-70 DEG C, dichloromethane solution that the mass concentration of-50 DEG C is the tricyclohexyl phosphine of 0.064g/mL, at 25 DEG C, carry out the reaction of 30min.
After described reaction terminates, the reaction soln obtained is filtered to remove insolubles, again filter after reaction soln after filtration is concentrated into 10mL, in the filtration product obtained, adding 100mL through the methyl alcohol of three liquid nitrogen freezings-thawing process precipitates, the throw out obtained first is used methanol wash three times, use washing with acetone twice again, the throw out after washing is carried out the vacuum-drying of 3 hours, obtain the product of 2.1g.The productive rate that the method that the embodiment of the present invention 2 provides prepares product is 81%.
Product obtained above is carried out proton nmr spectra detect and nucleus magnetic resonance phosphorus spectrum detection, detected result as shown in Figures 2 and 3, Fig. 2 be the product that the embodiment of the present invention 2 obtains hydrogen nuclear magnetic resonance (
1h) spectrogram, Fig. 3 be the product that the embodiment of the present invention 2 obtains nucleus magnetic resonance phosphorus (
31p) spectrogram, from Fig. 2 and Fig. 3, the product that the embodiment of the present invention 2 obtains is for having the compound of structure shown in formula IV.
Embodiment 3
What the embodiment 1 adding 2g at 25 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that 20.3mg embodiment 2 prepares is added in little ampulla, the methylene dichloride adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined the polyreaction of carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 500eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.99g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 3 provides obtains is 99%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5.17g p-toluene sulfonyl hydrazide, relative to above-mentioned, there is 2 of the mole number 0.05eqv of structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 12 hours, obtains hydrogenation reaction product; The purity described hydrogenation reaction product being added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered after draining and again dissolve 30 minutes at 130 DEG C with the toluene of 40mL, the purity that solution after dissolving is joined 300mL is again in the ethanol of 98%, the mix products obtained is put into vacuum drying oven at 60 DEG C dry 12 hours, obtain 1.43g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 3 provides obtains cyclic olefine copolymer is 94.0%.
According to the method described in technique scheme, carbon-13 nmr spectra detection and proton nmr spectra detection are carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, detected result as shown in Figure 4, Fig. 4 is the cyclic olefine copolymer carbon-13 nmr spectra figure that the embodiment of the present invention 3 obtains, as shown in Figure 4, the cyclic olefine copolymer that the embodiment of the present invention 3 obtains has the structure shown in formula I, and in formula I, x is 300.The structure of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is clear and definite.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that obtains of the embodiment of the present invention 3 and cyclic olefine copolymer, in Fig. 5, curve 1 is the proton nmr spectra of the polymeric reaction product that the embodiment of the present invention 3 obtains, curve 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as seen from Figure 5, the polymeric reaction product that the embodiment of the present invention 3 obtains is the completely dissolve of double bond peak after hydrogenation, and hydrogenation effect is better.
Carry out gel permeation chromatography test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is 1.29, and number-average molecular weight is 9.25 × 10
4g/mol.
According to the method described in technique scheme, differential thermal analysis test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result as shown in Figure 6, Fig. 6 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 3 ~ embodiment 5 obtains, in Fig. 6, curve 1 is the poor scanning calorimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as shown in Figure 6, the second-order transition temperature of cyclic olefine copolymer that the embodiment of the present invention 3 obtains is 212.6 DEG C.According to method described in technique scheme, thermogravimetry test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result as shown in Figure 7, Fig. 7 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, in Fig. 7, curve 1 is the thermogravimetric curve that the embodiment of the present invention 3 tests the cyclic olefine copolymer obtained in atmosphere, in Fig. 7, curve 2 is the thermogravimetric curve that the embodiment of the present invention 3 tests the cyclic olefine copolymer obtained in nitrogen, as shown in Figure 7, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains 350 DEG C time is 10%, there is good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 3 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is 1.7%, tensile strength is 21.2MPa, and tensile modulus is 1415MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 3 described in technique scheme, test result as shown in Figure 8, Fig. 8 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as shown in Figure 8, the transmittance > 90% of cyclic olefine copolymer that obtains of the embodiment of the present invention 3.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 3 described in technique scheme, test result is the polymerisation conversion of polyreaction in the embodiment of the present invention 3 is 100%.
Embodiment 4
What the embodiment 1 adding 2g at 25 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that the embodiment 2 adding 15.3mg in little ampulla prepares, the methylene dichloride adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined in above-mentioned polyreaction bottle the polyreaction of carrying out 2 hours;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 500eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.99g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 4 provides obtains is 99%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5.17g p-toluene sulfonyl hydrazide, relative to above-mentioned, there is 2 of the mole number 1eqv of structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 16 hours, obtains hydrogenation reaction product; The purity described hydrogenation reaction product being added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered after draining and again dissolve 30 minutes at 130 DEG C with the toluene of 40mL, the purity that solution after dissolving is joined 300mL is again in the ethanol of 98%, the mix products obtained is put into vacuum drying oven at 60 DEG C dry 12 hours, obtain 1.46g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 4 provides obtains cyclic olefine copolymer is 94.8%.
Detect the cyclic olefine copolymer structure that the embodiment of the present invention 4 obtains according to the method described in embodiment 3, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 4 obtains has the structure shown in formula I, and in formula I, x is 400.
Carry out gel permeation chromatography test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is 1.35, and number-average molecular weight is 11.7 × 10
4g/mol.
According to the method described in technique scheme, differential thermal analysis test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, test result as shown in Figure 6, in Fig. 6, curve 2 is the poor scanning calorimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, as shown in Figure 6, the second-order transition temperature of cyclic olefine copolymer that the embodiment of the present invention 4 obtains is 214.2 DEG C.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 4 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is 2.0%, tensile strength is 35MPa, and tensile modulus is 1520MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 4 described in technique scheme, test result is the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 4 described in technique scheme, test result is the polymerisation conversion of polyreaction in the embodiment of the present invention 4 is 100%.
Embodiment 5
What the embodiment 1 adding 2g at 25 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that the embodiment 2 adding 12.2mg in little ampulla prepares, the methylene dichloride adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined in above-mentioned polyreaction bottle the polyreaction of carrying out 2 hours;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 300eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.99g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 5 provides obtains is 99%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 4.14g p-toluene sulfonyl hydrazide, relative to above-mentioned, there is 2 of the mole number 2eqv of structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 16 hours, obtains hydrogenation reaction product; The purity described hydrogenation reaction product being added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered after draining and again dissolve 30 minutes at 130 DEG C with the toluene of 40mL, the purity that solution after dissolving is joined 300mL is again in the ethanol of 98%, the mix products obtained is put into vacuum drying oven at 60 DEG C dry 12 hours, obtain 1.45g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 5 provides obtains cyclic olefine copolymer is 94.5%.
Detect the cyclic olefine copolymer structure that the embodiment of the present invention 5 obtains according to the method described in embodiment 3, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 5 obtains has the structure shown in formula I, and in formula I, x is 500.
Carry out gel permeation chromatography test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 1.25, and number-average molecular weight is 14 × 10
4g/mol.
According to the method described in technique scheme, differential thermal analysis test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, test result as shown in Figure 6, in Fig. 6, curve 3 is the poor scanning calorimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, as shown in Figure 6, the second-order transition temperature of cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 223.6 DEG C.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 5 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 2.7%, tensile strength is 53.2MPa, and tensile modulus is 1940MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 5 described in technique scheme, test result is the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 5 described in technique scheme, test result is the polymerisation conversion of polyreaction in the embodiment of the present invention 5 is 100%.
Embodiment 6
What the embodiment 1 adding 2g at 0 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the tetrahydrofuran (THF) of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that the embodiment 2 adding 10.2mg in little ampulla prepares, the tetrahydrofuran (THF) adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in tetrahydrofuran (THF), obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined the polyreaction of carrying out 180min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 100eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.99g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 6 provides obtains is 99.2%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 3.10g p-toluene sulfonyl hydrazide, relative to above-mentioned, there is 2 of the mole number 1eqv of structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 110 DEG C, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; The purity described hydrogenation reaction product being added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered after draining and again dissolve 30 minutes at 130 DEG C with the toluene of 40mL, the purity that solution after dissolving is joined 300mL is again in the ethanol of 98%, the mix products obtained is put into vacuum drying oven at 60 DEG C dry 12 hours, obtain 1.46g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 6 provides obtains cyclic olefine copolymer is 95.1%.
According to the stuctures and properties of cyclic olefine copolymer that the method test embodiment of the present invention 6 described in embodiment 3 obtains, test result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, and in formula I, x is 600.The second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 223.8 DEG C, and the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 1.35, and number-average molecular weight is 15.6 × 10
4g/mol.The elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 2.6%, and tensile strength is 53.5MPa, and tensile modulus is 1850MPa.The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains.In the embodiment of the present invention 6, the polymerisation conversion of polyreaction is 100%.The cyclic olefine copolymer that the embodiment of the present invention 6 obtains has higher second-order transition temperature, mechanical property and the transparency.
Embodiment 7
What the embodiment 1 adding 2g at 50 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the toluene of 35mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that the embodiment 2 adding 8.7mg in little ampulla prepares, the toluene adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in toluene, obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined the polyreaction of carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 300eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.98g.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 6.21g p-toluene sulfonyl hydrazide, relative to above-mentioned, there is 2 of the mole number 3eqv of structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 150 DEG C, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; The purity described hydrogenation reaction product being added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered after draining and again dissolve 30 minutes at 130 DEG C with the toluene of 40mL, the purity that solution after dissolving is joined 300mL is again in the ethanol of 98%, the mix products obtained is put into vacuum drying oven at 60 DEG C dry 12 hours, obtain 1.47 cyclic olefine copolymers.The productive rate that the method for the hydrogenation that the embodiment of the present invention 7 provides obtains cyclic olefine copolymer is 96.2%.
According to the stuctures and properties of cyclic olefine copolymer that the method test embodiment of the present invention 7 described in embodiment 3 obtains, test result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, and in formula I, x is 700.The second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 221.5 DEG C, and the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 1.33, and number-average molecular weight is 18.6 × 10
4g/mol.The elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 2.5%, and tensile strength is 55.0MPa, and tensile modulus is 1880MPa.The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains.In the embodiment of the present invention 7, the polymerisation conversion of polyreaction is 100%.The cyclic olefine copolymer that the embodiment of the present invention 7 obtains has higher second-order transition temperature, mechanical property and the transparency.
Embodiment 8
What the embodiment 1 adding 2g at 25 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the tetrahydrofuran (THF) of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV that the embodiment 2 adding 6.1mg in little ampulla prepares, the tetrahydrofuran (THF) adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula IV is fully dissolved in tetrahydrofuran (THF), obtains having the compound solution of structure shown in formula IV; Under the condition stirred, the described compound solution with structure shown in formula IV is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle under the condition stirred and stop described polyreaction relative to the above-mentioned ethyl vinyl ether with the mole number 400eqv of structural compounds shown in formula IV; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, be precipitated product; Use washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.98g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 6 provides obtains is 99.0%.
By in autoclave under the condition of vacuum predrying 5 hours, in described autoclave, add above-mentioned polymeric reaction product, the hexanaphthene of 300mL, the Pd/Al of 0.5g prepared of 1g
2o
3catalyzer, described autoclave is carried out 3 times take out the hydrogen being filled with 30MPa in the backward described autoclave of ventilation operation, carry out the hydrogenation of 24h at 150 DEG C, the hydrogenation solution that obtains filtered with the Pd/Al reclaimed wherein
2o
3catalyzer, obtains hydrogenation reaction product; Described hydrogenation reaction product is poured in ethanol and precipitates, put into vacuum drying oven after being filtered by the precipitated product obtained at 60 DEG C dry 12 hours, obtain the cyclic olefine copolymer of 0.90g.
According to the stuctures and properties of cyclic olefine copolymer that the method test embodiment of the present invention 8 described in embodiment 3 obtains, test result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, and in formula I, x is 1000.The second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 224.0 DEG C, and the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 1.34, and number-average molecular weight is 32.1 × 10
4g/mol.The elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 2.7%, and tensile strength is 54.1MPa, and tensile modulus is 1820MPa.The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains.In the embodiment of the present invention 8, the polymerisation conversion of polyreaction is 100%.The cyclic olefine copolymer that the embodiment of the present invention 8 obtains has higher second-order transition temperature, mechanical property and the transparency.
As seen from the above embodiment, the invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, x is the polymerization degree, 300≤x≤1000.Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.Be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a cycloolefin homopolymers, has the structure shown in formula I:
In formula I, x is the polymerization degree, 300≤x≤1000.
2. cycloolefin homopolymers according to claim 1, is characterized in that, in described formula I, and 400≤x≤700.
3. a preparation method for cycloolefin homopolymers described in claim 1 or 2, comprises the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out polyreaction in a solvent, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cycloolefin homopolymers;
4. method according to claim 3, is characterized in that, described catalyzer is carbene catalyst.
5. method according to claim 3, is characterized in that, described catalyzer is ruthenium class carbene compound.
6. method according to claim 3, is characterized in that, described in there is the mol ratio of the compound of structure shown in formula II and catalyzer for (300 ~ 1000): 1.
7. method according to claim 3, is characterized in that, described step 1) in the temperature of polyreaction be 0 DEG C ~ 50 DEG C;
Described step 1) in time of polyreaction be 60 minutes ~ 180 minutes.
8. method according to claim 3, is characterized in that, described step 2) in hydrogen source be hydrazine class compound.
9. method according to claim 8, is characterized in that, described step 2) in the ratio of the mole number of polymeric reaction product double bond and the mole number of hydrogen source be 1:(3 ~ 6).
10. method according to claim 8, is characterized in that, described step 2) in the temperature of hydrogenation be 110 DEG C ~ 150 DEG C;
Described step 2) in time of hydrogenation be 12 hours ~ 20 hours.
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|---|---|---|---|---|
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN101889029A (en) * | 2007-12-05 | 2010-11-17 | Lg化学株式会社 | Non-metallocene catalysts having tetrazol group for olefin polymerization and polymerizing method of olefin using the same |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN101889029A (en) * | 2007-12-05 | 2010-11-17 | Lg化学株式会社 | Non-metallocene catalysts having tetrazol group for olefin polymerization and polymerizing method of olefin using the same |
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