CN103951775A - Cycloolefin copolymer and preparation method thereof - Google Patents
Cycloolefin copolymer and preparation method thereof Download PDFInfo
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- CN103951775A CN103951775A CN201410216477.3A CN201410216477A CN103951775A CN 103951775 A CN103951775 A CN 103951775A CN 201410216477 A CN201410216477 A CN 201410216477A CN 103951775 A CN103951775 A CN 103951775A
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Abstract
The invention provides a cycloolefin copolymer disclosed as Formula I, wherein x is polymerization degree and is greater than or equal to 300 and smaller than or equal to 1000. The cycloolefin copolymer provided by the invention simultaneously has favorable heat resistance and mechanical properties. The experimental result indicates that the glass transition temperature of the cycloolefin copolymer is 212-224 DEG C, so the cycloolefin copolymer has favorable heat resistance; the tensile strength is 21-55 MPa, the tensile modulus is 1400-1940 MPa, and the elongation at break is 1.7-2.7%, so the cycloolefin copolymer has favorable mechanical properties. Besides, the cycloolefin copolymer provided by the invention also has favorable transparency. The experimental result indicates that the light transmittance of the cycloolefin copolymer is greater than 90%.
Description
Technical field
The present invention relates to multipolymer technical field, relate in particular to a kind of cyclic olefine copolymer and preparation method thereof.
Background technology
Cyclic olefine copolymer is the thermoplastic engineering plastic of the high added value that formed by cyclic olefin polymerization of a class, and this multipolymer has high transparent, low-k, and good thermotolerance, chemical resistant properties, 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, cyclic olefine copolymer can be distorted and the variation of being out of shape in equidimension, thereby directly affects optical property and the mechanical property of cyclic olefine copolymer.Therefore the resistance toheat that, improves cyclic olefine copolymer is the use range of expanded ring olefin copolymer greatly.Weigh the second-order transition temperature that the stable on heating important indicator of cyclic olefine copolymer is cyclic olefine copolymer, second-order transition temperature is the temperature of multipolymer from vitreous state to rubbery transition, when envrionment temperature approaches or reaches the second-order transition temperature of multipolymer, can there is comparatively serious distortion in multipolymer, and mechanical property declines greatly, this has brought totally unfavorable impact to the application of copolymer material.Therefore the second-order transition temperature that improves 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, the ring-opening metathesis polymerization that another kind of method is Norbornene derivative (ROMP) hydrogenation.Utilize at present the commercialization cyclic olefine copolymer of ROMP method gained, 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 ℃,
second-order transition temperature be 170 ℃, 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 cyclic olefine copolymer that second-order transition temperature is higher, as trade names are
cyclic olefine copolymer, but the molecular chain rigidity of this cyclic olefine copolymer is stronger, the elongation at break of cyclic olefine copolymer is poor, 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 preparation method who the invention provides cyclic olefine copolymer described in a kind of technique scheme, comprises the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out to polyreaction in solvent, obtain polymeric reaction product;
2), described polymeric reaction product and hydrogen source are carried out to hydrogenation, obtain cyclic olefine copolymer;
formula II.
Preferably, described catalyzer is carbene catalyst.
Preferably, described catalyzer is ruthenium class carbene compound.
Preferably, described in, there is the compound of structure shown in formula II and the mol ratio of catalyzer for (300～1000): 1.
Preferably, described step 1), the temperature of polyreaction is 0 ℃～50 ℃;
Described step 1) in, the time of polyreaction is 60 minutes～180 minutes.
Preferably, described step 2), hydrogen source is hydrazine class compound.
Preferably, described step 2), the ratio of the two mole numbers of key of polymeric reaction product and the mole number of hydrazine class compound is 1:(3～6).
Preferably, described step 2), the temperature of hydrogenation is 110 ℃～150 ℃;
Described step 2) in, the time of hydrogenation is 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 ℃～224 ℃, 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 obtains of the embodiment of the present invention 1;
Fig. 2 be the product that obtains of the embodiment of the present invention 2 hydrogen nuclear magnetic resonance (
1h) spectrogram;
Fig. 3 be the product that obtains of the embodiment of the present invention 2 nucleus magnetic resonance phosphorus (
31p) spectrogram;
Fig. 4 is the carbon-13 nmr spectra figure of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3;
Fig. 5 is the polymeric reaction product that obtains of the embodiment of the present invention 3 and the hydrogen nuclear magnetic resonance spectrogram of cyclic olefine copolymer;
Fig. 6 is the differential scanning calorimetry curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3～embodiment 5;
Fig. 7 is the thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3;
Fig. 8 is the transmittance of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3.
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, preferred, 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 preparation method who the invention provides cyclic olefine copolymer described in a kind of technique scheme, comprises the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out to polyreaction in solvent, obtain polymeric reaction product;
2), described polymeric reaction product and hydrogen source are carried out to hydrogenation, obtain cyclic olefine copolymer;
formula II.
The present invention preferably will have compound and the solvent of structure shown in formula II, in the mixture obtaining, adds catalyzer to carry out polyreaction, obtains polymeric reaction product.The present invention preferably under the condition stirring by described compound and the solvent with structure shown in formula II.The method that the present invention stirs during to described mix does not have special restriction, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the time of stirring during described mix is preferably 5 minutes～and 15 minutes, more preferably 8 minutes～12 minutes, most preferably be 10 minutes.
The present invention preferably carries out described polyreaction under the condition of dry, anaerobic.In the present invention, described polyreaction can be carried out in Braun (Mbraun) glove box, also can adopt Xi Laike (Schlenk) technology of standard to carry out under the protection of nitrogen.The present invention preferably carries out described polyreaction under the condition stirring, and the present invention does not have special restriction to the stirring means of described polyreaction, adopts stirring technique scheme well known to those skilled in the art.
In the present invention, the temperature of described polyreaction is preferably 0 ℃～50 ℃, more preferably 10 ℃～40 ℃, most preferably is 20 ℃～30 ℃.In the present invention, the time of described polyreaction is preferably 60min～120min, and more preferably 80min～110min, most preferably is 90min～100min.
In the present invention, described catalyzer is preferably carbene catalyst, more preferably ruthenium class carbene compound.In the present invention, described ruthenium class carbene compound is preferably the compound with 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, X Cl more preferably in described formula III; R
1ph more preferably; R is Cy more preferably.In the present invention, described ruthenium class carbene compound more preferably has the compound of 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, make the present invention in preparing the process of cyclic olefine copolymer without adding promotor; And this catalyzer can evenly cause above-mentioned polyreaction, make the molecular weight distribution of the cyclic olefine copolymer that obtains narrower, be conducive to regulate the number-average molecular weight of the cyclic olefine copolymer preparing; It is fast that this catalyzer causes the speed of above-mentioned polyreaction 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 hydrocar-bons compound or arene compounds; 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 and be obtained by market.
In the present invention, the volumetric molar concentration of described catalyst solution is preferably 3 μ mol/mL～6 μ mol/mL, and more preferably 4 μ mol/mL～5.5 μ mol/mL, most preferably are 4.5 μ mol/mL～5 μ mol/mL.For described catalyzer is fully dissolved in the solvent of catalyst solution, the present invention is preferably under ultrasonic condition, and the solvent by 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～and 5 minutes, more preferably 3 minutes～4 minutes.
The present invention does not have special restriction to the source of described catalyzer, adopts the preparation method of the carbene catalyst of mentioned kind well known to those skilled in the art to prepare.The preparation method in the present invention, with structural compounds shown in formula IV is preferably:
By phenyldiazomethane, dichloro three (triphenylphosphine) closes ruthenium and tricyclohexyl phosphine reacts in organic solvent, obtains having the compound of structure shown in formula IV.
The present invention more preferably closes phenyldiazomethane, organic solvent and dichloro three (triphenylphosphine) ruthenium and mixes, and in the mixture obtaining, adds tricyclohexyl phosphine to react, and obtains having the compound of structure shown in formula IV.In the present invention, the temperature that described phenyldiazomethane, organic solvent and dichloro three (triphenylphosphine) close ruthenium mixing is preferably-80 ℃～-50 ℃, more preferably-78 ℃～-55 ℃, most preferably is-75 ℃～-65 ℃.In the present invention, described in add the temperature of tricyclohexyl phosphine to be preferably-70 ℃～-50 ℃, more preferably-60 ℃～-55 ℃.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 stirring, dichloro three (triphenylphosphine) closes ruthenium and thricyclohexyl phosphine reaction.The method that the present invention closes ruthenium and the stirring of thricyclohexyl phosphine reaction to described phenyldiazomethane, dichloro three (triphenylphosphine) 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 ℃～30 ℃, more preferably-78 ℃～25 ℃, most preferably is-70 ℃～20 ℃.In the present invention, the time that described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction is preferably 30 minutes～and 50 minutes, more preferably 35 minutes～45 minutes, most preferably be 40 minutes.
The present invention does not have special restriction to the source of described phenyldiazomethane, can be bought and be obtained by market, can adopt the preparation method of phenyldiazomethane well known to those skilled in the art to prepare yet.In the present invention, the preparation method of described phenyldiazomethane is preferably:
By phenyl aldehyde-Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol are carried out to building-up reactions, 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 ℃～70 ℃, more preferably 55 ℃～65 ℃, most preferably is 60 ℃.In the present invention, the time of described building-up reactions is preferably 0.5 hour～and 1.5 hours, more preferably 1 hour.In the present invention, the described phenyl aldehyde-mass ratio of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol is preferably to 1:(2～3): (25～35), more preferably 1:(2.4～2.9): (27～32), most preferably are 1:2.8:25.The present invention, to the described phenyl aldehyde-source of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol is not had to special restriction, can be bought and be obtained by market.
After described building-up reactions completes, the present invention preferably removes the methyl alcohol in the building-up reactions solution obtaining, and obtains building-up reactions product; Described building-up reactions product is extracted, is dried, obtain phenyldiazomethane.The present invention does not have special restriction to the method for described removal methyl alcohol, in embodiment in the present invention, can adopt mechanical pump that the methyl alcohol in described building-up reactions solution is extracted.The present invention preferably first carries out the first extraction with Skellysolve A by described building-up reactions product, then the first extraction product obtaining is carried out to the second extraction with sodium chloride aqueous solution.In the present invention, described sodium chloride aqueous solution is preferably saturated sodium-chloride water solution.In the present invention, the dry method of described building-up reactions product is preferably and is spin-dried for.In the present invention, the dry temperature of described building-up reactions product is preferably-35 ℃～-45 ℃, more preferably-40 ℃.
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, more preferably 94mg/mL～98mg/mL.
The source that the present invention closes ruthenium to described dichloro three (triphenylphosphine) does not have special restriction, can be bought and be obtained 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, more preferably 0.064g/mL～0.068g/mL.The present invention does not have special restriction to the source of described tricyclohexyl phosphine, can be bought and be obtained 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), 1:(4～5 more preferably): (2～3), most preferably are 1:4.6:2.6.
In the present invention, described organic solvent is preferably methylene dichloride.The present invention does not have special restriction to the consumption of described organic solvent, and described organic solvent can be for 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 to described organic solvent and processes.In the present invention, the number of times that described liquid nitrogen freezing-thawing is processed is preferably 3 times.The method that the present invention processes described liquid nitrogen freezing-thawing does not have special restriction, the technical scheme that adopts liquid nitrogen freezing well known to those skilled in the art-thawing to process.The present invention can carry out liquid nitrogen freezing-thawing to described organic solvent by the following method and process:
Described organic solvent is packed in Schlenk bottle, described Schlenk bottle is put into liquid nitrogen freezing;
After above-mentioned Schlenk bottle after freezing is vacuumized to processing, the organic solvent in described Schlenk bottle is thawed.
The present invention has bubble to overflow in the process that described organic solvent is thawed, thereby has removed the air in described organic solvent.
Described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine should complete after, the present invention preferably closes the phenyldiazomethane obtaining, dichloro three (triphenylphosphine) ruthenium and the filtration of tricyclohexyl phosphine reaction soln, dissolves, concentrates, precipitates, washs, is dried, and obtains having the compound of structure shown in formula IV.The present invention does not have special restriction to described filtration, dissolving, concentrated, precipitation, washing and dry method, adopts filtration well known to those skilled in the art, dissolving, concentrated, precipitation, washing and dry technical scheme.In the present invention, the reagent of described precipitation is preferably methyl alcohol.In the present invention, described phenyldiazomethane, dichloro three (triphenylphosphine) close the reagent washing after ruthenium and tricyclohexyl phosphine reaction soln precipitation and are preferably methyl alcohol and acetone.In the present invention, described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and the dry method of tricyclohexyl phosphine reaction soln is preferably vacuum-drying.In the present invention, described phenyldiazomethane, dichloro three (triphenylphosphine) close ruthenium and the dry time of tricyclohexyl phosphine reaction soln be preferably 2 hours～4 hours, more preferably 3 hours.
In the present invention, described in to have the steric hindrance of compound structure unit of structure shown in formula II larger, main chain rigidity is stronger, 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 that adopts preparation well known to those skilled in the art to have structural compounds shown in formula II prepares.The preparation method in the present invention, with the compound of structure shown in formula II is preferably:
Norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol are reacted, obtain 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 ℃～200 ℃, more preferably 170 ℃～190 ℃, most preferably is 180 ℃.In the present invention, the time of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction is preferably 25 hours～and 35 hours, 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, more preferably (1600～1800): (270～295): 1, most preferably be (1700～1760): (284～290): 1.The present invention does not have special restriction to the source of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol, can be bought and be obtained by market.
Described norbornadiene, anthracene and 2, after 6-di-t-butyl-p-cresol has reacted, the present invention preferably the norbornadiene obtaining, anthracene and 2,6-di-t-butyl-p-cresol reaction product is cooling, standing, filter, washing, obtain having the compound of structure shown in formula II.The present invention to described cooling, standing, filter and the method for washing does not have special restriction, adopt well known to those skilled in the art cooling, standing, filter and the technical scheme of washing.In the present invention, described cooling temperature is preferably 20 ℃～30 ℃, more preferably 24 ℃～28 ℃.In the present invention, the described standing time is preferably 10 hours～and 16 hours, more preferably 12 hours～14 hours.In the present invention, the reagent of described norbornadiene, anthracene and the washing of 2,6-di-t-butyl-p-cresol reaction product is preferably normal hexane.
In the present invention, described in there is the compound of structure shown in formula II and the mol ratio of catalyzer is preferably (300～1000): 1, more preferably (400～700): 1, most preferably be (500～600): 1.
In the present invention, the kind of described polymerization solvent is consistent with kind and the source of solvent in catalyst solution described in technique scheme with source, does not repeat them here.In the present invention, the solvent of described polyreaction can with catalyst solution described in technique scheme in solvent phase with, also can be different.
The present invention does not have special restriction to the consumption of described polymerization solvent, adopts the consumption of solvent in polyreaction well known to those skilled in the art.In the present invention, described in there is the compound of structure shown in formula II and the mass ratio of polymerization solvent is preferably 1:(10～25), 1:(15～20 more preferably).
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; Described precipitated product is filtered, washs, is dried, obtain polymeric reaction product.
The present invention does not have special restriction to the kind of described terminator and source, adopts the terminator adopting while 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, more preferably (200～400): 1, most preferably be 300:1.In the present invention, the time that stops described polyreaction is preferably 20 minutes～and 40 minutes, more preferably 25 minutes～35 minutes, most preferably be 30 minutes.
Obtain after polymeric reaction solution, the present invention preferably, by described polymeric reaction solution and precipitant mix, is precipitated product.The present invention does not have special restriction to precipitating the kind of the precipitation agent of described polymeric reaction solution, adopts the precipitation agent adopting while preparing cyclic olefine copolymer well known to those skilled in the art.In the present invention, the precipitation agent that precipitates described polymeric reaction solution is preferably methyl alcohol, more preferably anhydrous methanol.In the present invention, the temperature of described polymeric reaction solution and precipitant mix is preferably-10 ℃～0 ℃, more preferably-8 ℃～-5 ℃.
Be precipitated after product, the present invention preferably filters described precipitated product, washing, dry, obtains polymeric reaction product.The present invention does not have special restriction to described precipitated product filtration, washing and dry method, adopts filtration well known to those skilled in the art, washing and dry technical scheme.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, more preferably 3 times.In the present invention, the dry method of described precipitated product is preferably vacuum-drying.In the present invention, the dry temperature of described precipitated product is preferably 20 ℃～40 ℃, more preferably 25 ℃～35 ℃, most preferably is 30 ℃.In the present invention, the dry time of described precipitated product is preferably 12 hours～and 24 hours, more preferably 16 hours～20 hours, most preferably be 18 hours.
Obtain after polymeric reaction product, the present invention carries out hydrogenation by described polymeric reaction product and hydrogen source, obtains 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 present invention does not have special restriction to the method for described hydrogenation, adopts hydrogenation technical scheme well known to those skilled in the art.
The present invention does not have special restriction to the kind of described hydrogen source, and described hydrogen source is preferably hydrogen or hydrazine class compound, and 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 by the following method hydrogenation and prepares cyclic olefine copolymer:
Described polymeric reaction product and hydrazine class compound are carried out to hydrogenation in solvent, obtain cyclic olefine copolymer.
In the present invention, in described polymeric reaction product, the ratio of two mole numbers of key and the mole number of hydrazine class compound is preferably 1:(3～6), 1:(4～5 more preferably).In the present invention, described hydrogenation solvent is preferably toluene.The present invention does not have special restriction to the consumption of described hydrogenation solvent, 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 ℃～140 ℃, more preferably 125 ℃～135 ℃, most preferably is 130 ℃.In the present invention, reaction times when described polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 12 hours～and 20 hours, more preferably 16 hours～18 hours.
In order to prevent that above-mentioned polymeric reaction product and hydrazine class compound from carrying out, 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 and be obtained by market.In the present invention, described free radical scavenger is preferably 2,6 di tert butyl 4 methyl phenol.The present invention does not have special restriction to the consumption of described free radical scavenger, 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 with respect to the mole number 0.05eqv～3eqv of catalyzer described in technique scheme.
After described hydrogenation completes, the present invention preferably mixes the hydrogenation reaction product obtaining with ethanol, and the mix products obtaining is filtered, washs, is dried, and obtains cyclic olefine copolymer.In the present invention, the purity of described ethanol is preferably 97%～99%.The present invention does not have special restriction to described mix products filtration, washing and dry method, adopts filtration well known to those skilled in the art, washing and dry technical scheme.In the present invention, the drying means of described mix products is preferably vacuum-drying.In the present invention, be preferably 12 hours the time of drying of described mix products～24 hours, more preferably 16 hours～20 hours.In the present invention, the drying temperature of described mix products is preferably 40 ℃～70 ℃, more preferably 50 ℃～65 ℃, most preferably is 60 ℃.
Prepare after cyclic olefine copolymer, the cyclic olefine copolymer obtaining is carried out to carbon-13 nmr spectra detection in the present invention and proton nmr spectra detects, the detection method that described proton nmr spectra detects and carbon-13 nmr spectra detects is for adopting Varian Unity-400 type nuclear magnetic resonance spectrometer to measure at 25 ℃, tetramethylsilane (TMS) is interior mark, and deuterochloroform is solvent.Detected result is that cyclic olefine copolymer provided by the invention has the structure shown in formula I.
The present invention adopts differential thermal analysis and thermogravimetry to test the second-order transition temperature of the cyclic olefine copolymer obtaining, detection method is for adopting Perkin-ElmerPyris1DSC differential scanning calorimeter to carry out differential thermal analysis mensuration, the speed that heats up, lowers the temperature is 10 ℃/min, carries out rescan.Adopt Perkin-Elmer Pyris1 type Instrument measuring thermal weight loss.Detected result is that the second-order transition temperature of cyclic olefine copolymer provided by the invention is 212 ℃～224 ℃, has good thermostability.
The present invention is at INSTRON1121, Canton, the mechanical property of the cyclic olefine copolymer that on MA instrument, test obtains, standard according to GB/T1040-1992 < < plastic tensile performance test methods > > detects, batten folder distance is 20.0mm, test rate is 5mm/min, and each sample is at least tested 8 times to guarantee 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 Shimadzu UV-3600 ultraviolet-visible light-near infrared spectrometer to test the transparency of the cyclic olefine copolymer obtaining, and test wavelength is 400nm～800nm.Test result is the transmittance > 90% of the cyclic olefine copolymer that obtains of the present invention.
The present invention adopts gel permeation chromatography to test molecular weight distribution and the number-average molecular weight of the cyclic olefine copolymer obtaining, and detection method is for adopting waters152 type gel permeation chromatograph to measure; Adopt RI-Laser detector to detect; Detection solvent is tetrahydrofuran (THF), and detected temperatures is 35 ℃; Flow rate of mobile phase is 1.0mL/min, and adopting PL EasiCal PS-1 is standard specimen.Test result is that 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 polymerisation conversion of polyreaction described in the method test technique scheme that product weighs, and the polymerisation conversion that test result is 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 further to understand the present invention; 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 are described is in order to further illustrate the features and advantages of the present invention, and they can not be interpreted as to limiting the scope of the present invention.
Following examples of the present invention reaction raw materials used is commercial goods.
Embodiment 1
To adding successively 2 of the norbornadiene of 800mL, the anthracene of 230 grams and 1 gram in the stainless steel autoclave of 2 liters, 6-di-t-butyl-p-cresol, repeats to vacuumize for 3 times the operation of rear inflated with nitrogen to described autoclave; Described autoclave is heated to 180 ℃, makes the material in described autoclave carry out the reaction of 30 hours under the condition stirring.
After described reaction finishes, the reaction product obtaining is cooled to 25 ℃, after standing 12 hours, filters, by normal hexane washing 2 times for the filtration product obtaining, 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 to proton nmr spectra detection, detected result as shown in Figure 1, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that obtains of the embodiment of the present invention 1, and the product that the embodiment of the present invention 1 obtains is as shown in Figure 1 the compound with structure shown in formula II.
Embodiment 2
The phenyl aldehyde-to Methyl benzenesulfonyl hydrazone, the sodium methylate of 1.75 grams and the Triethylene glycol of 40mL that adds 4.96 grams in the single port bottle of 100mL, is placed on described single port bottle and in the water-bath of 60 ℃, carries out the building-up reactions of 1 hour.
After described building-up reactions completes, the methyl alcohol in the building-up reactions solution obtaining is extracted with water pump, obtain building-up reactions product; After described building-up reactions product is extracted with Skellysolve A in frozen water, use again saturated NaCl aqueous solution extraction, the extraction product obtaining is spin-dried for, obtain phenyldiazomethane; The productive rate of described phenyldiazomethane is 50%.
In a mouthful bottle of 250mL, add the dichloro three (triphenylphosphine) of 4.0 grams to close ruthenium, pass into the air in a mouthful bottle described in nitrogen replacement, in described mouth bottle, inject 40mL through the methylene dichloride of three liquid nitrogen freezing-thawings processing; Described mouth bottle is placed in to the cryostat of-78 ℃, under the condition stirring, add the pentane solution 10mL of-50 ℃ of phenyldiazomethanes that mass concentration is 98.5mg/mL to mix, the phenyldiazomethane in the pentane solution of described phenyldiazomethane is the above-mentioned phenyldiazomethane preparing; The dichloromethane solution that adds the tricyclohexyl phosphine that 40mL, the mass concentration of-50 ℃ are 0.064g/mL after the mixture obtaining is stirred to 10min at-70 ℃ carries out the reaction of 30min at 25 ℃.
After described reaction finishes, the reaction soln obtaining is filtered to remove insolubles, after being concentrated into 10mL, again filters reaction soln after filtering, in the filtration product obtaining, add 100mL to precipitate through the methyl alcohol of three liquid nitrogen freezing-thawing processing, the throw out obtaining is first used to methanol wash three times, use again washing with acetone twice, the throw out after washing is carried out to 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 to proton nmr spectra detects and the detection of nucleus magnetic resonance phosphorus spectrum, detected result as shown in Figures 2 and 3, Fig. 2 be the product that obtains of the embodiment of the present invention 2 hydrogen nuclear magnetic resonance (
1h) spectrogram, Fig. 3 be the product that obtains of the embodiment of the present invention 2 nucleus magnetic resonance phosphorus (
31p) spectrogram, from Fig. 2 and Fig. 3, the product that the embodiment of the present invention 2 obtains is the compound with structure shown in formula IV.
Embodiment 3
What at 25 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare has the compound of structure shown in formula II and a methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; To the compound with structure shown in formula IV that adds 20.3mg embodiment 2 to prepare in little ampulla, to the methylene dichloride that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined to the polyreaction of carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 500eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain 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 dry polyreaction bottle, add successively the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 5.17g, with respect to 2 of the above-mentioned mole number 0.05eqv with structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 ℃, return stirring carries out hydrogenation in 12 hours, obtains hydrogenation reaction product; Described hydrogenation reaction product is added drop-wise in the ethanol that the purity of 300mL is 98%, after being drained, the mix products filtration obtaining again with the toluene of 40mL, at 130 ℃, dissolves 30 minutes, solution after dissolving is joined in the ethanol that the purity of 300mL is 98% again, the mix products obtaining is put into vacuum drying oven and at 60 ℃, be dried 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, the cyclic olefine copolymer that the embodiment of the present invention 3 is obtained carries out carbon-13 nmr spectra detection and proton nmr spectra detects, 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 polymeric reaction product that obtains of the embodiment of the present invention 3 and the hydrogen nuclear magnetic resonance spectrogram of cyclic olefine copolymer, the proton nmr spectra of the polymeric reaction product that in Fig. 5, curve 1 obtains for the embodiment of the present invention 3, the proton nmr spectra of the cyclic olefine copolymer that curve 2 obtains for the embodiment of the present invention 3, as seen from Figure 5, the polymeric reaction product that the embodiment of the present invention 3 obtains is two key peak completely dissolves after hydrogenation, and hydrogenation effect is better.
The cyclic olefine copolymer embodiment of the present invention 3 being obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is that the molecular weight distribution of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3 is 1.29, and number-average molecular weight is 9.25 * 10
4g/mol.
The cyclic olefine copolymer embodiment of the present invention 3 being obtained according to the method described in technique scheme carries out differential thermal analysis test, test result as shown in Figure 6, Fig. 6 is the differential scanning calorimetry curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3～embodiment 5, in Fig. 6, the poor scanning calorimetric curve of the cyclic olefine copolymer that curve 1 obtains for the embodiment of the present invention 3, the second-order transition temperature of the cyclic olefine copolymer that as shown in Figure 6, the embodiment of the present invention 3 obtains is 212.6 ℃.The cyclic olefine copolymer embodiment of the present invention 3 being obtained according to method described in technique scheme carries out thermogravimetry test, test result as shown in Figure 7, Fig. 7 is the thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3, in Fig. 7, curve 1 is tested the thermogravimetric curve of the cyclic olefine copolymer obtaining for the embodiment of the present invention 3 in air, in Fig. 7, curve 2 is tested the thermogravimetric curve of the cyclic olefine copolymer obtaining for the embodiment of the present invention 3 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 in the time of 350 ℃ is 10%, there is good thermostability.
According to the mechanical property of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 3 obtains, test result is that the elongation at break of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3 is 1.7%, tensile strength is 21.2MPa, and tensile modulus is 1415MPa.
According to the transparency of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 3 obtains, test result as shown in Figure 8, Fig. 8 is the transmittance of the cyclic olefine copolymer that obtains of the embodiment of the present invention 3, the transmittance > 90% of the cyclic olefine copolymer that as shown in Figure 8, the embodiment of the present invention 3 obtains.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 3 described in technique scheme, test result is that the polymerisation conversion of polyreaction in the embodiment of the present invention 3 is 100%.
Embodiment 4
What at 25 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare has the compound of structure shown in formula II and a methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV preparing to the embodiment 2 that adds 15.3mg in little ampulla, to the methylene dichloride that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined and in above-mentioned polyreaction bottle, carries out the polyreaction of 2 hours;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 500eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain 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 dry polyreaction bottle, add successively the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 5.17g, with respect to 2 of the above-mentioned mole number 1eqv with structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 ℃, return stirring carries out hydrogenation in 16 hours, obtains hydrogenation reaction product; Described hydrogenation reaction product is added drop-wise in the ethanol that the purity of 300mL is 98%, after being drained, the mix products filtration obtaining again with the toluene of 40mL, at 130 ℃, dissolves 30 minutes, solution after dissolving is joined in the ethanol that the purity of 300mL is 98% again, the mix products obtaining is put into vacuum drying oven and at 60 ℃, be dried 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%.
The cyclic olefine copolymer structure embodiment of the present invention 4 being obtained according to the method described in embodiment 3 detects, and 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.
The cyclic olefine copolymer embodiment of the present invention 4 being obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is that the molecular weight distribution of the cyclic olefine copolymer that obtains of the embodiment of the present invention 4 is 1.35, and number-average molecular weight is 11.7 * 10
4g/mol.
The cyclic olefine copolymer embodiment of the present invention 4 being obtained according to the method described in technique scheme carries out differential thermal analysis test, test result as shown in Figure 6, the poor scanning calorimetric curve of the cyclic olefine copolymer that in Fig. 6, curve 2 obtains for the embodiment of the present invention 6, the second-order transition temperature of the cyclic olefine copolymer that as shown in Figure 6, the embodiment of the present invention 4 obtains is 214.2 ℃.
According to the mechanical property of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 4 obtains, test result is that the elongation at break of the cyclic olefine copolymer that obtains of the embodiment of the present invention 4 is 2.0%, tensile strength is 35MPa, and tensile modulus is 1520MPa.
According to the transparency of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 4 obtains, test result is the transmittance > 90% of the cyclic olefine copolymer that obtains of the embodiment of the present invention 4.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 4 described in technique scheme, test result is that the polymerisation conversion of polyreaction in the embodiment of the present invention 4 is 100%.
Embodiment 5
What at 25 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare has the compound of structure shown in formula II and a methylene dichloride of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV preparing to the embodiment 2 that adds 12.2mg in little ampulla, to the methylene dichloride that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined and in above-mentioned polyreaction bottle, carries out the polyreaction of 2 hours;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 300eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain 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 dry polyreaction bottle, add successively the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 4.14g, with respect to 2 of the above-mentioned mole number 2eqv with structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 ℃, return stirring carries out hydrogenation in 16 hours, obtains hydrogenation reaction product; Described hydrogenation reaction product is added drop-wise in the ethanol that the purity of 300mL is 98%, after being drained, the mix products filtration obtaining again with the toluene of 40mL, at 130 ℃, dissolves 30 minutes, solution after dissolving is joined in the ethanol that the purity of 300mL is 98% again, the mix products obtaining is put into vacuum drying oven and at 60 ℃, be dried 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%.
The cyclic olefine copolymer structure embodiment of the present invention 5 being obtained according to the method described in embodiment 3 detects, and 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.
The cyclic olefine copolymer embodiment of the present invention 5 being obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is that the molecular weight distribution of the cyclic olefine copolymer that obtains of the embodiment of the present invention 5 is 1.25, and number-average molecular weight is 14 * 10
4g/mol.
The cyclic olefine copolymer embodiment of the present invention 5 being obtained according to the method described in technique scheme carries out differential thermal analysis test, test result as shown in Figure 6, the poor scanning calorimetric curve of the cyclic olefine copolymer that in Fig. 6, curve 3 obtains for the embodiment of the present invention 5, the second-order transition temperature of the cyclic olefine copolymer that as shown in Figure 6, the embodiment of the present invention 5 obtains is 223.6 ℃.
According to the mechanical property of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 5 obtains, test result is that the elongation at break of the cyclic olefine copolymer that obtains of the embodiment of the present invention 5 is 2.7%, tensile strength is 53.2MPa, and tensile modulus is 1940MPa.
According to the transparency of the cyclic olefine copolymer that described in technique scheme, the method test embodiment of the present invention 5 obtains, test result is the transmittance > 90% of the cyclic olefine copolymer that obtains of the embodiment of the present invention 5.
According to the polymerisation conversion of polyreaction in the method test embodiment of the present invention 5 described in technique scheme, test result is that the polymerisation conversion of polyreaction in the embodiment of the present invention 5 is 100%.
Embodiment 6
What at 0 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare has the compound of structure shown in formula II and a tetrahydrofuran (THF) of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV preparing to the embodiment 2 that adds 10.2mg in little ampulla, to the tetrahydrofuran (THF) that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined to the polyreaction of carrying out 180min in above-mentioned polyreaction bottle;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 100eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain 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 dry polyreaction bottle, add successively the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 3.10g, with respect to 2 of the above-mentioned mole number 1eqv with structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 110 ℃, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; Described hydrogenation reaction product is added drop-wise in the ethanol that the purity of 300mL is 98%, after being drained, the mix products filtration obtaining again with the toluene of 40mL, at 130 ℃, dissolves 30 minutes, solution after dissolving is joined in the ethanol that the purity of 300mL is 98% again, the mix products obtaining is put into vacuum drying oven and at 60 ℃, be dried 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%.
Structure and the performance of the cyclic olefine copolymer obtaining according to the method test embodiment of the present invention 6 described in embodiment 3, test result is that the cyclic olefine copolymer that the embodiment of the present invention 6 obtains has the structure shown in formula I, 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 ℃, 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 at 50 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare 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 preparing to the embodiment 2 that adds 8.7mg in little ampulla, to the toluene that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined to the polyreaction of carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 300eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain the polymeric reaction product of 1.98g.
In dry polyreaction bottle, add successively the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 6.21g, with respect to 2 of the above-mentioned mole number 3eqv with structural compounds shown in formula IV, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 150 ℃, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; Described hydrogenation reaction product is added drop-wise in the ethanol that the purity of 300mL is 98%, after being drained, the mix products filtration obtaining again with the toluene of 40mL, at 130 ℃, dissolves 30 minutes, solution after dissolving is joined in the ethanol that the purity of 300mL is 98% again, the mix products obtaining is put into vacuum drying oven and at 60 ℃, be dried 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%.
Structure and the performance of the cyclic olefine copolymer obtaining according to the method test embodiment of the present invention 7 described in embodiment 3, test result is that the cyclic olefine copolymer that the embodiment of the present invention 7 obtains has the structure shown in formula I, 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 ℃, 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 at 25 ℃, to the embodiment 1 that adds 2g in dry polyreaction bottle, prepare has the compound of structure shown in formula II and a tetrahydrofuran (THF) of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula IV preparing to the embodiment 2 that adds 6.1mg in little ampulla, to the tetrahydrofuran (THF) that adds 5mL in described little ampulla, carry out again 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 stirring, the described compound solution with structure shown in formula IV is joined to the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, under the condition stirring, to adding with respect to the above-mentioned ethyl vinyl ether with the mole number 400eqv of structural compounds shown in formula IV in above-mentioned polyreaction bottle, stop described polyreaction; After 30min, the polymeric reaction solution obtaining is poured in anhydrous methanol, be precipitated product; After described precipitated product is filtered, use washing with acetone 3 times, in the vacuum drying oven of 40 ℃, be dried 12 hours, obtain 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 the above-mentioned polymeric reaction product preparing of 1g, the hexanaphthene of 300mL, the Pd/Al of 0.5g
2o
3catalyzer, carries out described autoclave the hydrogen that is filled with 30MPa in the backward described autoclave of gas operation of substituting of 3 times, at 150 ℃ of hydrogenations that carry out 24h, by the hydrogenation solution filter obtaining to reclaim Pd/Al wherein
2o
3catalyzer, obtains hydrogenation reaction product; Described hydrogenation reaction product is poured in ethanol and precipitated, after the precipitated product obtaining is filtered, put into vacuum drying oven and be dried 12 hours at 60 ℃, obtain the cyclic olefine copolymer of 0.90g.
Structure and the performance of the cyclic olefine copolymer obtaining according to the method test embodiment of the present invention 8 described in embodiment 3, test result is that the cyclic olefine copolymer that the embodiment of the present invention 8 obtains has the structure shown in formula I, 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 ℃, 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 is just for helping to understand method of the present invention and core concept thereof.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 improvement and modification also fall in the protection domain of the claims in the present invention.To the multiple modification of these embodiment, be apparent for those skilled in the art, General Principle as defined herein can realize in other embodiments in the situation that not departing from the spirit or scope of the present invention.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a cyclic olefine copolymer, has the structure shown in formula I:
formula I;
In formula I, x is the polymerization degree, 300≤x≤1000.
2. cyclic olefine copolymer according to claim 1, is characterized in that, in described formula I, and 400≤x≤700.
3. a preparation method for cyclic olefine copolymer 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 to polyreaction in solvent, obtain polymeric reaction product;
2), described polymeric reaction product and hydrogen source are carried out to hydrogenation, obtain cyclic olefine copolymer;
formula II.
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 compound of structure shown in formula II and the mol ratio of 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 ℃～50 ℃;
Described step 1) in, the time of polyreaction is 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 two mole numbers of key of polymeric reaction product 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 ℃～150 ℃;
Described step 2) in, the time of hydrogenation is 12 hours～20 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910329A (en) * | 2015-06-04 | 2015-09-16 | 天津大学 | Polar cycloolefin copolymer and preparation method thereof |
| WO2015176588A1 (en) * | 2014-05-21 | 2015-11-26 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method therefor |
| CN105254807A (en) * | 2015-10-26 | 2016-01-20 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115850581A (en) * | 2022-12-01 | 2023-03-28 | 无锡阿科力科技股份有限公司 | Cycloolefin copolymer and preparation method and application thereof |
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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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015176588A1 (en) * | 2014-05-21 | 2015-11-26 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method therefor |
| JP2017515943A (en) * | 2014-05-21 | 2017-06-15 | 中国科学院▲長▼春▲応▼用化学研究所Ｃｈａｎｇｃｈｕｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Cycloolefin copolymer and method for preparing the same |
| CN104910329A (en) * | 2015-06-04 | 2015-09-16 | 天津大学 | Polar cycloolefin copolymer and preparation method thereof |
| CN105254807A (en) * | 2015-10-26 | 2016-01-20 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN105254807B (en) * | 2015-10-26 | 2017-09-29 | 中国科学院长春应用化学研究所 | Cyclic olefine copolymer and preparation method thereof |
| CN115850581A (en) * | 2022-12-01 | 2023-03-28 | 无锡阿科力科技股份有限公司 | Cycloolefin copolymer and preparation method and application thereof |
| CN115850581B (en) * | 2022-12-01 | 2024-03-19 | 无锡阿科力科技股份有限公司 | Cycloolefin copolymer and preparation method and application thereof |
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