CN104910329A - Polar cycloolefin copolymer and preparation method thereof - Google Patents

Polar cycloolefin copolymer and preparation method thereof Download PDF

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CN104910329A
CN104910329A CN201510306010.2A CN201510306010A CN104910329A CN 104910329 A CN104910329 A CN 104910329A CN 201510306010 A CN201510306010 A CN 201510306010A CN 104910329 A CN104910329 A CN 104910329A
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cyclic olefine
olefine copolymer
formula
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CN104910329B (en
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李悦生
崔静
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Tianjin University
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Tianjin University
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Abstract

The invention provides a cycloolefin copolymer disclosed as Formula I, wherein m and n are polymerization degree, m is greater than or equal to 100 and smaller than or equal to 500, and n is greater than or equal to 5 and smaller than or equal to 150. The side chain of the cycloolefin copolymer contains ester group and benzene ring structures, and thus, simultaneously has polarity, favorable heat resistance and favorable mechanical properties. Besides, the cycloolefin copolymer provided by the invention also has favorable transparency. The experimental result indicates that the contact angle between the cycloolefin copolymer and water surface is 92-105 degrees, the glass transition temperature is 130-220 DEG C, the tensile strength is 18-30 MPa, the tensile modulus is 1200-1700 MPa, the elongation at break is 1.7-6.9%, and the light transmittance is greater than 80%.

Description

A kind of polar cyclic olefin multipolymer and preparation method thereof
Technical field
The present invention relates to multipolymer technical field, particularly relate to a kind of polar cyclic olefin multipolymer 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.
Cause the extensive concern of people in recent years containing the cyclic olefine copolymer of polar functional group, this base polymer has toughness, adhesion, can coating, printing and and the advantage such as consistency of other polymkeric substance.General has two kinds of methods to introduce polar group: rear functionalization method and directly initiation polar monomer polymerization.The former hydrocarbon polymer is difficult to carry out functionalization again, so be difficult to realize.The latter requires that catalyzer has certain functional group tolerance.The appearance of ruthenium catalyst, can make many polar monomers carry out polymerization and prepare cyclic olefine copolymer, and this is because the tolerance of ruthenium catalyst to polar monomer is strong.
Resistance toheat is the key property of cyclic olefine copolymer 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 cyclic olefine copolymer that prior art provides cannot meet have good thermotolerance and mechanical property while having polarity.
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 good mechanical property while having polarity.
The invention provides a kind of cyclic olefine copolymer, there is the structure shown in formula I:
In formula I, R is methyl, 3-heptyl or undecyl.
M, n are the polymerization degree, 100≤m≤500,5≤n≤150.
Preferably, in described formula I, 150≤m≤450,10≤n≤120.
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 with the compound with structure shown in formula III, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cyclic olefine copolymer;
In formula III, R is methyl, 3-heptyl or undecyl.
Preferably, described catalyzer is carbene catalyst.
Preferably, described catalyzer is ruthenium class carbene compound.
Preferably, the ratio of the mole number of the mole number that the compound described in structure shown in formula II is total with the compound with structure shown in formula III and catalyzer is (200 ~ 500): 1;
Described have the compound of structure shown in formula II and have the mol ratio of structural compounds shown in formula III for (0.5 ~ 20): 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 ~ 140min.
Preferably, described step 2) in hydrogen source be alcohol compound, hydrocarbon compound, hydrazine class compound or formic acid.
Preferably, 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).
Preferably, described step 2) in the temperature of hydrogenation be 110 DEG C ~ 150 DEG C;
Described step 2) in time of hydrogenation be 8 ~ 20 hours.
The invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, m, n are the polymerization degree, 100≤m≤500,5≤n≤150.Cyclic olefine copolymer provided by the invention has polarity and good thermotolerance and good mechanical property.In addition, cyclic olefine copolymer provided by the invention also has the good transparency.Experimental result shows, cyclic olefine copolymer provided by the invention and water surface contact angle are 92 ° ~ 105 °; Second-order transition temperature is 130 DEG C ~ 220 DEG C; Tensile strength is 18MPa ~ 30MPa, and tensile modulus is 1200MPa ~ 1700MPa, and elongation at break is 1.7% ~ 6.9%, transmittance > 80%.
Accompanying drawing explanation
Fig. 1 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. 2 is the gel permeation chromatography figure of the polymeric reaction product that obtains of the embodiment of the present invention 3 and cyclic olefine copolymer;
Fig. 3 is the embodiment of the present invention 3, embodiment 8, embodiment 15, comparative example 1 obtain and water contact angle figure.
The differential calorimetry curve of the cyclic olefine copolymer that Fig. 4 is the embodiment of the present invention 3, embodiment 10, embodiment 15, comparative example 1 obtain;
The thermogravimetric curve of the cyclic olefine copolymer that Fig. 5 is the embodiment of the present invention 3, embodiment 5, embodiment 8, embodiment 11, embodiment 12, embodiment 14 obtain;
The transmittance of the cyclic olefine copolymer that Fig. 6 is the embodiment of the present invention 3, embodiment 9, embodiment 14, comparative example 1 obtain.
Embodiment
The invention provides a kind of cyclic olefine copolymer, there is the structure shown in formula I
In formula I, R is methyl, 3-heptyl or undecyl.
M, n are the polymerization degree, 100≤m≤500,5≤n≤150.
In the present invention, preferably, 150≤m≤450; Preferred, 200≤m≤400.In the present invention, preferably, 10≤n≤120; Preferred, 10≤n≤100.While cyclic olefine copolymer provided by the invention has polarity, there is good thermotolerance and excellent mechanical performances.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 with the compound with structure shown in formula III, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cyclic olefine copolymer;
In formula III, R is methyl, 3-heptyl or undecyl.
The present invention preferably will have the compound of structure shown in formula II, the compound with structure shown in formula III and solvent, adds catalyzer and carries out polyreaction, obtain polymeric reaction product in the mixture obtained.The present invention preferably has the compound of structure shown in formula II, the compound with structure shown in formula III and solvent by described under the condition stirred.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 ~ 15min, is more preferably 8 ~ 12min, most preferably is 10min.
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.
The transparency of the cyclic olefine copolymer that the present invention prepares by the time controling controlling described polyreaction.In the present invention, the described speed of reaction with the compound of structure shown in formula II is greater than the speed of reaction with structural compounds shown in formula III, the time controlling described polyreaction can make the compound with structure shown in formula III not exclusively be polymerized, the compound in the cyclic olefine copolymer obtained with structure shown in formula III is less, the compound in the cyclic olefine copolymer that the present invention obtains with structure shown in formula III is fewer, and the transparency of cyclic olefine copolymer is better.In the present invention, the time of described polyreaction is preferably 60 ~ 140min, is more preferably 80 ~ 130min, most preferably is 100 ~ 120min.
In the present invention, described catalyzer is preferably carbene catalyst, is more preferably ruthenium class carbene compound, most preferably is the compound with structure shown in formula IV:
In formula IV, L is preferably PCy 3; X is preferably Cl, Br or I; R 1be preferably H, Ph or CH2CH3; R 3be preferably Cy, Cp or Ph.In the present invention, in described formula IV, X is more preferably Cl; R 1be more preferably Ph; R 3be more preferably Cy.In the present invention, described catalyzer the most preferably has the compound of structure shown in formula V:
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.The present invention adopts α-tolylene dichloro two (tricyclohexyl phosphine) to close catalyzed by ruthenium complexes, and have trigger rate fast, catalytic conversion reaches 100%, and crosslinked grade for side reaction does not occur; Polymerization process of the present invention does not need promotor, and polymerization tolerance is fine, the advantages such as molecular weight distribution is adjustable.
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 2.5 μm of ol/mL ~ 4.5 μm ol/mL, is more preferably 3 μm of ol/mL ~ 4 μm ol/mL, most preferably is 3.3 μm of ol/mL ~ 3.7 μm ol/mL.In order to make described catalyzer fully be dissolved in the solvent of described 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 ~ 5min, is more preferably 3 ~ 4min.
The source of the present invention to described catalyzer does not have special restriction, adopts the preparation method of mentioned kind catalyzer well known to those skilled in the art to prepare.In the present invention, the preparation method described in structural compounds shown in formula V is preferably:
By phenyldiazomethane, dichloro three (triphenylphosphine) closes ruthenium and tricyclohexyl phosphine reacts in organic solvent, obtains the compound with structure shown in formula V.
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 V 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 ~ 50min, is more preferably 35 ~ 45min, most preferably is 40min.
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 ~ 1.5 hour, 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 test tube, described test tube is put into liquid nitrogen freezing;
By above-mentioned freezing after test tube carry out vacuumizing process after the organic solvent in described test tube 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 V.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 ~ 4 hours, is more preferably 3 hours.
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: reacted by norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol, 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 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 ~ 35 hours, is more preferably 28 ~ 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 ~ 16 hours, is more preferably 12 ~ 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.
The present invention does not have special restriction to the described source with the compound of structure shown in formula III, and the method adopting preparation well known to those skilled in the art to have structural compounds shown in formula III prepares.In the present invention, the preparation method described in the compound of structure shown in formula III is preferably: A) under the preferred conditions, be dropwise added drop-wise to by thionyl chloride in isocaprylic acid (lauric acid) system and carry out stirring and refluxing reaction.The unreacted thionyl chloride of constant voltage distillation removing, underpressure distillation obtains isocaprylic acid acyl chlorides (lauric acid acyl chlorides) product.The present invention distills described constant voltage, the method for underpressure distillation does not have special restriction, adopts the technical scheme of constant voltage well known to those skilled in the art distillation, underpressure distillation.The ratio that this experiment is preferably thionyl chloride and isocaprylic acid (lauric acid) amount of substance is (1 ~ 5): 1, is more preferably (1.5 ~ 4): 1, most preferably is (2 ~ 3): 1.Preferable reaction temperature is 60 DEG C ~ 100 DEG C, is more preferably 65 DEG C ~ 90 DEG C, most preferably is 70 DEG C ~ 80 DEG C.Preferred stirring and refluxing is 2 ~ 6 hours, is more preferably 2.5 ~ 5 hours, most preferably is 3 ~ 4 hours.Preferred vacuum distillation temperature is 50 DEG C ~ 100 DEG C (100 DEG C ~ 150 DEG C), is more preferably 60 DEG C ~ 90 DEG C (110 DEG C ~ 140 DEG C), most preferably is 70 DEG C ~ 80 DEG C (120 DEG C ~ 130 DEG C).The present invention does not have special restriction to described thionyl chloride, isocaprylic acid, lauric source, can be bought obtain by market.
B) under the preferred conditions, 5-norbornylene-2-methyl alcohol and triethylamine are dissolved in methylene dichloride and are uniformly mixed, steps A) in the product isocaprylic acid acyl chlorides (moon silicic acid acyl chlorides) of gained or Acetyl Chloride 98Min. be dropwise added drop-wise in reaction system under the condition of ice-water bath and carry out stirring reaction.Then use water respectively, saturated sodium hydrogen carbonate solution, saturated sodium chloride solution extracts, and dry, suction filtration, column chromatography obtains having the compound of structure shown in formula III.The method of the present invention to described stirring, extraction, drying, suction filtration, column chromatography does not have special restriction, adopts the technical scheme of stirring well known to those skilled in the art, extraction, drying, suction filtration, column chromatography.This experiment is preferably triethylamine, isocaprylic acid acyl chlorides (moon silicic acid acyl chlorides, Acetyl Chloride 98Min.) and 5-norbornylene-2-methyl alcohol amount of substance than being (0.5 ~ 3): (0.5 ~ 3): 1, be more preferably (1 ~ 2.5): (1 ~ 2.5): 1, most preferably be (1.5 ~ 2): (1.5 ~ 2): 1.The preferred reaction times is 5 ~ 30 hours, is more preferably 10 ~ 25 hours, most preferably is 15 ~ 20 hours.The source of the present invention to described methylene dichloride, 5-norbornylene-2-methyl alcohol, triethylamine does not have special restriction, can be bought obtain by market.
In the present invention, the kind of the kind of described polymerization solvent and source and solvent in above-mentioned catalyst solution 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 cyclic olefine copolymer that the present invention prepares by the consumption controlling described polyreaction raw material and water surface contact angle and second-order transition temperature.The compound in the cyclic olefine copolymer that the present invention prepares with structure shown in formula II is more, cyclic olefine copolymer and water surface contact angle larger, the second-order transition temperature of gained is higher.In the present invention, the ratio of the described compound with structure shown in formula II and the mole number with the total mole number of structural compounds shown in formula III and catalyzer is preferably (50 ~ 600): 1, be more preferably (100 ~ 500): 1, most preferably be (150 ~ 450): 1, be the most preferably (200 ~ 400): 1.In the present invention, described in have structure shown in formula II compound and have structure shown in formula III compound mol ratio be preferably (2 ~ 30): 1, be more preferably (3 ~ 25): 1, most preferably be (4 ~ 20): 1.
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:(20 ~ 30), be more preferably 1:(24 ~ 28).
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 ~ 40min, is more preferably 25 ~ 35min, most preferably is 30min.
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 ~ 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 ~ 24 hours, is more preferably 16 ~ 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 both can be hydrogen can be also organic hydrogen source, and described organic hydrogen source can be specially alcohol compound, hydrocarbon compound, hydrazine class compound or formic acid.In the present invention, described hydrogen source is preferably alcohol compound, hydrocarbon compound, hydrazine class compound or formic acid, is more preferably alcohol compound, hydrazine class compound or formic acid, most preferably is Virahol or toluene sulfonyl hydrazide, is the most preferably benzol sulfohydrazide.Utilize p-toluene sulfonyl hydrazide to carry out hydrogenation, the main polymer chain obtained is completely saturated.
In the present invention, when described hydrogen source is alcohol compound, hydrocarbon compound, hydrazine class compound or formic acid, the present invention preferably carries out hydrogenation by the following method and prepares cyclic olefine copolymer:
Described polymeric reaction product and organic hydrogen source are carried out hydrogenation in a solvent, obtains cyclic olefine copolymer; Described organic hydrogen source is alcohol compound, hydrocarbon compound hydrazine class compound or formic acid.
In the present invention, in described polymeric reaction product, the ratio of the mole number of double bond and the mole number of organic hydrogen source 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 organic hydrogen source 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 organic hydrogen source carry out hydrogenation is preferably 10 ~ 16 hours, is more preferably 12 ~ 14 hours.
Carry out to prevent above-mentioned polymeric reaction product and organic hydrogen source, in hydriding process, crosslinking reaction occurs, reaction raw materials when described polymeric reaction product and organic hydrogen source 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 0.05eqv ~ 7eqv.
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 ~ 24 hours, is more preferably 16 ~ 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 proton nmr spectra detection to the cyclic olefine copolymer obtained, detection method measures at 25 DEG C for adopting Varian Unity-400 type nuclear magnetic resonance spectrometer, and 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.There is in the cyclenes copolymer that the present invention calculates according to formula VI the content of structural compounds shown in formula II:
There is compound mol%=[I6.8 ~ 7.3/ (4*I3.9 ~ 4.3)] × 100% formula VI of structure shown in formula II,
In formula VI, I3.9 ~ 4.3 be in proton nmr spectra chemical shift at the peak area at 3.9 ~ 4.3 places, I6.8 ~ 7.3 be in proton nmr spectra chemical shift at the peak area at 6.8 ~ 7.3 places.Calculation result is, the molar content in cyclic olefine copolymer provided by the invention with structural compounds shown in formula II is 60% ~ 95%.
The present invention obtains the polarity of cyclic olefine copolymer by Static water contact angles test, and the hydrophilicity on test membrane surface under employing DSA KRUSS GMBH ' Hamburg 100 ' contact angle tester room temperature, water droplet amount is 10 μ l.Test result be cyclic olefine copolymer provided by the invention with water contact angle 92 ° ~ 105 °, there is good wetting ability.
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-Elmer Pyris 1 type Instrument measuring thermal weight loss.Detected result is the second-order transition temperature of cyclic olefine copolymer provided by the invention is 140 DEG C ~ 220 DEG C, has good thermostability.
The present invention is at INSTRON 1121, 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 18MPa ~ 30MPa, and tensile modulus is 1200MPa ~ 1700MPa, and elongation at break is 1.7% ~ 6.9%.
The present invention adopts Shimadzu UV-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 > 80% 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, adopts PL EasiCal PS-1 to be standard specimen.Test result is the molecular weight distribution of cyclic olefine copolymer provided by the invention is 1.20 ~ 2.0, and number-average molecular weight is 5.0 × 10 4g/mol ~ 12.0 × 10 4g/mol.
The invention provides a kind of cyclic olefine copolymer, have the structure shown in formula I, in formula I, m, n are the polymerization degree, 100≤m≤500,5≤n≤150.There is while cyclic olefine copolymer provided by the invention has polarity good thermotolerance and good mechanical property.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, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Reaction raw materials used by following examples of the present invention is commercial goods.
In embodiment, A1:5-norbornylene-2-methyl acetate.
A2:5-norbornylene-2-isocaprylic acid methyl esters.
A3:5-norbornylene-2-Laurate methyl.
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 material in described autoclave under the condition stirred, carry out the reaction of 30min.
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, and detected result is, the product that the embodiment of the present invention 1 obtains is for having the compound of structure shown in formula II.
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 and the detection of phosphorus spectrum, detected result is, the product that the embodiment of the present invention 2 obtains is for having the compound of structure shown in formula V.
Embodiment 3
The methylene dichloride of the compound with structure shown in formula II that the embodiment 1 adding 1.396g at 25 DEG C in the polyreaction bottle of drying prepares and 0.090g A1 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 15.9mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 15min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.41g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 3 provides obtains is 94.0%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 5eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.05g 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 80.7%.
According to the method described in technique scheme, the polymeric reaction product obtain the embodiment of the present invention 3 and cyclic olefine copolymer carry out proton nmr spectra detection, detected result as shown in Figure 1, Fig. 1 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. 1, curve 1 is the proton nmr spectra of the polymeric reaction product that the embodiment of the present invention 3 obtains, and curve 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains.From curve 1, the cyclic olefine copolymer that the embodiment of the present invention 3 obtains has the structure shown in formula I, and in formula I, m is 184, n is 22.Calculate according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 3 obtains with structural compounds shown in formula II is 90.8%.As seen from Figure 1, 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.
According to method described in technique scheme, gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result as shown in Figure 3, Fig. 3 is the gel permeation chromatography figure of the polymeric reaction product that obtains of the embodiment of the present invention 3 and cyclic olefine copolymer, in Fig. 3, curve 1 is the gel permeation chromatography of the polymeric reaction product that the embodiment of the present invention 3 obtains, curve 2 is the gel permeation chromatography of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as seen from Figure 3, the polymeric reaction product that the embodiment of the present invention 3 obtains peak shape after hydrogenation is constant, hydrodynamic volume change is little, detected known by gel permeation chromatography, the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is 1.48, and number-average molecular weight is 5.7 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result as shown in Figure 2, the water contact angle test pattern of the cyclic olefine copolymer that Fig. 3 is the embodiment of the present invention 3, embodiment 8, embodiment 15, comparative example 1 obtain, in Fig. 3, the figure being labeled as 1 be the cyclic olefine copolymer that obtains of the embodiment of the present invention 3 with water contact angle test pattern, as shown in Figure 3, the cyclic olefine copolymer that obtains of the embodiment of the present invention 3 and water contact angle are 103.0 °.
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 4, Fig. 4 is the embodiment of the present invention 3, embodiment 10, embodiment 15, the differential calorimetry curve of the cyclic olefine copolymer that comparative example 1 obtains, in Fig. 4, curve 2 is the poor scanning calorimetric curve of the cyclic olefine copolymer 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 does not have melt temperature, for non-crystalline state, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains is 203.6 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 5, the thermogravimetric curve of the cyclic olefine copolymer that Fig. 5 is the embodiment of the present invention 3, embodiment 5, embodiment 8, embodiment 11, embodiment 12, embodiment 14 obtain, in Fig. 5, curve 1 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains 350 DEG C time is 10%, has 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 2.8%, tensile strength is 24.4MPa, and tensile modulus is 1193MPa.
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 6, the transmittance of the cyclic olefine copolymer that Fig. 6 is the embodiment of the present invention 3, embodiment 9, embodiment 14, comparative example 1 obtain, in Fig. 6, curve 1 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, as shown in Figure 6, the transmittance > 80% of cyclic olefine copolymer that obtains of the embodiment of the present invention 3.
Embodiment 4
What the embodiment 1 adding 1.31g 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 0.19gA1 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that 16.7mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 50 DEG C, drying 12 hours, obtains the polymeric reaction product of 1.48g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 4 provides obtains is 98.6%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 5.37g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.26g 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 96.9%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 4 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, in formula I, m is 245, n is 55, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 81.8%.
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 1.45, and number-average molecular weight is 9.8 × 10 4g/mol.
Carry out Static water contact angles 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 cyclic olefine copolymer that obtains of the embodiment of the present invention 4 and water contact angle is 100.3 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is 188.3 DEG C.Carry out thermogravimetry 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 that the cyclic olefine copolymer that the embodiment of the present invention 4 obtains has good thermostability.
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 3.6%, tensile strength is 23.6MPa, and tensile modulus is 1140MPa.
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 > 80% of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains.
Embodiment 5
What the embodiment 1 adding 1.20g 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 0.296gA1 and 20mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 17.6mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.44g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 5 provides obtains is 96.0%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 2.26g, 2 of 7eqv successively, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 150 DEG C, return stirring carries out hydrogenation in 8 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 30min with the toluene of 40mL at 120 DEG C, 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 1.03g 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 79.2%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 5 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, in formula I, m is 131, n is 50, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 72.5%.
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 1.56, and number-average molecular weight is 5.0 × 10 4g/mol.
Carry out Static water contact angles 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 cyclic olefine copolymer that obtains of the embodiment of the present invention 5 and water contact angle is 96.7 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 171.6 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 5 obtains, test result as shown in Figure 5, curve 2 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains 350 DEG C time is 10%, has good thermostability.
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 4.5%, tensile strength is 23.4MPa, and tensile modulus is 1102MPa.
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 > 80% of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains.
Embodiment 6
What the embodiment 1 adding 1.08g at 20 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the methylene dichloride of 0.415gA1 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 18.3mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 140min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.08g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 6 provides obtains is 89.5%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 2.69g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.19g 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 91.5%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 6 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, in formula I, m is 306, n is 183, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 62.5%.
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 6 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 1.29, and number-average molecular weight is 9.7 × 10 4g/mol.
Carry out Static water contact angles test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, test result is the cyclic olefine copolymer that obtains of the embodiment of the present invention 6 and water contact angle is 94.4 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 150.5 DEG C.Carry out thermogravimetry test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, test result is that the cyclic olefine copolymer that the embodiment of the present invention 6 obtains has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 6 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 6.9%, tensile strength is 21.7MPa, and tensile modulus is 1042MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 6 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains.
Embodiment 7
What the embodiment 1 adding 0.80g at 50 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the methylene dichloride of 0.694gA1 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 20.7mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.45g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 7 provides obtains is 96.7%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 5.376g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.26g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 7 provides obtains cyclic olefine copolymer is 96.9%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 7 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, in formula I, m is 228, n is 325, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 41.3%.
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 7 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 1.31, and number-average molecular weight is 10.8 × 10 4g/mol.
Carry out Static water contact angles test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, test result is the cyclic olefine copolymer that obtains of the embodiment of the present invention 7 and water contact angle is 84.5 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 106.4 DEG C.Carry out thermogravimetry test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, test result is that the cyclic olefine copolymer that the embodiment of the present invention 7 obtains has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 7 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 9.7%, tensile strength is 17.7MPa, and tensile modulus is 1190MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 7 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains.
Embodiment 8
What the embodiment 1 adding 1.397g 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 0.0698gA2 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.47g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 8 provides obtains is 98.0%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 2.69g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.05g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 8 provides obtains cyclic olefine copolymer is 70.0%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 8 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, in formula I, m is 225, n is 9, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 96.3%.
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 8 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 1.41, and number-average molecular weight is 6.6 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, test result as shown in Figure 3, the figure being labeled as 2 be the cyclic olefine copolymer that obtains of the embodiment of the present invention 8 with water contact angle test pattern, as shown in Figure 3, the cyclic olefine copolymer that obtains of the embodiment of the present invention 8 and water contact angle are 95.4 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 205.9 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 8 obtains, test result as shown in Figure 5, curve 3 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains 350 DEG C time is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 8 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 1.7%, tensile strength is 22.4MPa, and tensile modulus is 1580MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 8 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains.
Embodiment 9
What the embodiment 1 adding 1.365g 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 0.14gA2 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 14.1mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 9 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.2g, the p-toluene sulfonyl hydrazide of 4.13g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.12g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 9 provides obtains cyclic olefine copolymer is 86.2%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 9 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 9 obtains, in formula I, m is 339, n is 38, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 90.0%.
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 9 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is 1.26, and number-average molecular weight is 10.3 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 9 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 9 and water contact angle is 94.5 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 9 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is 189.7 DEG C.Carry out thermogravimetry test according to method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 9 obtains, the rate of decomposition of the cyclic olefine copolymer obtained for the embodiment of the present invention 9 350 DEG C time is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 9 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is 1.8%, tensile strength is 22.0MPa, and tensile modulus is 1350MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 9 described in technique scheme, test result as shown in Figure 6, curve 2 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains, as shown in Figure 6, the transmittance > 80% of cyclic olefine copolymer that obtains of the embodiment of the present invention 9.
Embodiment 10
What the embodiment 1 adding 1.31g 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 0.19gA2 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 10 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.12g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 10 provides obtains cyclic olefine copolymer is 86.2%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 10 obtains is detected, detected result has the structure shown in formula I for the cyclic olefine copolymer that the embodiment of the present invention 10 obtains, in formula I, m is 310, n is 48, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 86.5%.
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 10 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 1.28, and number-average molecular weight is 9.7 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 10 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 10 and water contact angle is 94.1 °.
According to the method described in technique scheme, differential thermal analysis test is carried out to the cyclenes combustion multipolymer that the embodiment of the present invention 10 obtains, test result as shown in Figure 4, curve 3 is the poor scanning calorimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains, as shown in Figure 4, the cyclic olefine copolymer that the embodiment of the present invention 10 obtains does not have melt temperature, for non-crystalline state, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 172.5 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 10 obtains, test result is the rate of decomposition of cyclic olefine copolymer 350 DEG C time that the embodiment of the present invention 10 obtains is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 10 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 2.0%, tensile strength is 20.4MPa, and tensile modulus is 1320MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 10 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains.
Embodiment 11
The methylene dichloride of the compound with structure shown in formula II that the embodiment 1 adding 1.22g at 25 DEG C in the polyreaction bottle of drying prepares and 0.28g A2 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 14.6mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 11 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.22g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 11 provides obtains cyclic olefine copolymer is 93.8%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 11 obtains is detected, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 11 obtains has the structure shown in formula I, in formula I, m is 336, n is 81, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 80.5%.
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 11 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 1.29, and number-average molecular weight is 9.7 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 11 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 11 and water contact angle is 91.4 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 11 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 145.5 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 11 obtains, test result as shown in Figure 5, curve 4 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains 350 DEG C time is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 11 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 2.8%, tensile strength is 18.8MPa, and tensile modulus is 1170MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 11 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains.
Embodiment 12
What the embodiment 1 adding 1.42g 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 0.084gA3 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 12 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.12g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 12 provides obtains cyclic olefine copolymer is 86.2%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 12 obtains is detected, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 12 obtains has the structure shown in formula I, in formula I, m is 240, n is 13, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 94.8%.
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 12 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains is 1.39, and number-average molecular weight is 9.9 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 12 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 12 and water contact angle is 96.8 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 12 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains is 194.7 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 12 obtains, test result as shown in Figure 5, curve 5 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains 350 DEG C time is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 12 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains is 2.1%, tensile strength is 30.8MPa, and tensile modulus is 1630MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 12 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 12 obtains.
Embodiment 13
What the embodiment 1 adding 1.23g 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 0.168gA3 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.48g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 13 provides obtains is 98.7%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.25g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 13 provides obtains cyclic olefine copolymer is 96.2%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 13 obtains is detected, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 13 obtains has the structure shown in formula I, in formula I, m is 333, n is 39, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 89.5%.
According to method described in technique scheme, gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 13 obtains, test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 13 obtains is 1.31, and number-average molecular weight is 10.1 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 13 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 13 and water contact angle is 93.9 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 13 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 13 obtains is 176.4 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 13 obtains, test result is the rate of decomposition of cyclic olefine copolymer 350 DEG C time that the embodiment of the present invention 13 obtains is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 13 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 13 obtains is 2.8%, tensile strength is 28.5MPa, and tensile modulus is 1557MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 13 described in technique scheme, test result is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 13 obtains
Embodiment 14
What the embodiment 1 adding 1.28g 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 0.227gA3 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 14.5mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 14 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.2g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 14 provides obtains cyclic olefine copolymer is 92.3%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 14 obtains is detected, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 14 obtains has the structure shown in formula I, in formula I, m is 186, n is 32, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 85.3%.
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 1.42, and number-average molecular weight is 8.8 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles is carried out to the cyclic olefine copolymer that the embodiment of the present invention 14 obtains and test the cyclic olefine copolymer that obtains for the embodiment of the present invention 14 and water contact angle is 92.4 °.
Carry out differential thermal analysis test according to the method described in technique scheme to the cyclic olefine copolymer that the embodiment of the present invention 14 obtains, test result is the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 14 obtains is 164.1 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 14 obtains, test result as shown in Figure 5, curve 6 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 14 obtains, as shown in Figure 5, the rate of decomposition of the cyclic olefine copolymer that the embodiment of the present invention 14 obtains 350 DEG C time is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 14 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 14 obtains is 3.2%, tensile strength is 19.2MPa, and tensile modulus is 1077MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 14 described in technique scheme, test result as shown in Figure 6, curve 3 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 14 obtains, as shown in Figure 6, the transmittance > 80% of cyclic olefine copolymer that obtains of the embodiment of the present invention 14.
Embodiment 15
What the embodiment 1 adding 1.17g 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 0.33gA3 and 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 2 adding 14.5mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 1.5g.The yield of the polymeric reaction product that the polymerization process that the embodiment of the present invention 15 provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 1.3g, the p-toluene sulfonyl hydrazide of 4.48g, 2 of 7eqv successively, 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 30min with the toluene of 40mL at 120 DEG C, 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 1.11g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that the embodiment of the present invention 15 provides obtains cyclic olefine copolymer is 85.4%.
According to the method described in embodiment 3, the cyclic olefine copolymer structure that the embodiment of the present invention 15 obtains is detected, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 15 obtains has the structure shown in formula I, in formula I, m is 275, n is 78, and the molar content of compound in cyclic olefine copolymer with structure shown in formula II is 78.0%.
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 1.31, and number-average molecular weight is 9.8 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 15 obtains, test result as shown in Figure 2, the figure being labeled as 3 be the cyclic olefine copolymer that obtains of the embodiment of the present invention 15 with water contact angle test pattern, as shown in Figure 3, the cyclic olefine copolymer that obtains of the embodiment of the present invention 15 and water contact angle are 92.1 °.
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 15 obtains, test result as shown in Figure 4, curve 4 is the poor scanning calorimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 15 obtains, as shown in Figure 4, the cyclic olefine copolymer that the embodiment of the present invention 15 obtains does not have melt temperature, for non-crystalline state, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 15 obtains is 134.1 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 15 obtains, test result is the rate of decomposition of cyclic olefine copolymer 350 DEG C time that the embodiment of the present invention 15 obtains is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 15 described in technique scheme, test result is the elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 15 obtains is 3.2%, tensile strength is 19.2MPa, and tensile modulus is 1077MPa.
The transparency of the cyclic olefine copolymer obtained according to the method test embodiment of the present invention 15 described in technique scheme is the transmittance > 80% of the cyclic olefine copolymer that the embodiment of the present invention 15 obtains.
Comparative example 1
Prepare the cycloolefin homopolymers containing structure shown in formula II according to the preparation method of the cyclic olefine copolymer of method described in above-described embodiment, detailed process is:
What the embodiment 1 adding 2.0g 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 V that the embodiment 2 adding 20.32mg 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 V is fully dissolved in methylene dichloride, obtains having the compound solution of structure shown in formula V; Under the condition stirred, the described compound solution with structure shown in formula V is joined the polyreaction of carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, the ethyl vinyl ether adding 300eqv under the condition stirred in above-mentioned polyreaction bottle stops described polyreaction; 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 2.0g.The yield of the polymeric reaction product that the polymerization process that comparative example 1 of the present invention provides obtains is 100%.
In the polyreaction bottle of drying, add the above-mentioned polymeric reaction product of 2.0g, the p-toluene sulfonyl hydrazide of 6.8g, 2 of 7eqv successively, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 60mL, 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 30min with the toluene of 60mL at 120 DEG C, 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 1.88g cyclic olefine copolymer.The productive rate that the method for the hydrogenation that comparative example 1 of the present invention provides obtains cyclic olefine copolymer is 94.0%.
Carry out gel permeation chromatography test according to method described in technique scheme to the cycloolefin homopolymers that comparative example 1 of the present invention obtains, test result is the molecular weight distribution of the cycloolefin homopolymers that comparative example 1 of the present invention obtains is 1.34, and number-average molecular weight is 12.6 × 10 4g/mol.
According to method described in technique scheme, Static water contact angles test is carried out to the cycloolefin homopolymers that comparative example 1 of the present invention obtains, test result as shown in Figure 2, the figure being labeled as 4 be the cycloolefin homopolymers that obtains of comparative example 1 of the present invention with water contact angle test pattern, as shown in Figure 3, the cycloolefin homopolymers that obtains of comparative example 1 of the present invention and water contact angle are 103.2 °.
According to the method described in technique scheme, differential thermal analysis test is carried out to the cycloolefin homopolymers that comparative example 1 of the present invention obtains, test result as shown in Figure 4, curve 1 is the poor scanning calorimetric curve of the cycloolefin homopolymers that comparative example 1 of the present invention obtains, as shown in Figure 4, the cycloolefin homopolymers that comparative example 1 of the present invention obtains does not have melt temperature, for non-crystalline state, the second-order transition temperature of the cycloolefin homopolymers that comparative example 1 of the present invention obtains is 216.3 DEG C.
The elongation at break of the cycloolefin homopolymers that comparative example 1 of the present invention obtains is 1.9%, and tensile strength is 28.8MPa, and tensile modulus is 1910MPa.
The transparency of the cycloolefin homopolymers that comparative example 1 of the present invention obtains is tested according to method described in technique scheme, test result as shown in Figure 6, curve 4 is the transmittance of the cycloolefin homopolymers that comparative example 1 of the present invention obtains, as shown in Figure 6, the transmittance > 80% of cycloolefin homopolymers that obtains of comparative example 1 of the present invention.
The stuctures and properties of the cycloolefin homopolymers that comparative example 1 of the present invention obtains is tested according to the method described in embodiment 3, can show that the cycloolefin homopolymers that comparative example 1 of the present invention obtains is poorer than the wetting ability in above embodiment, the comparatively above embodiment of second-order transition temperature wants high, and elongation at break wants more lower slightly.
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, m, n are the polymerization degree, 100≤m≤500,5≤n≤150.While cyclic olefine copolymer provided by the invention has polarity, there is good thermotolerance and mechanical property.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 cyclic olefine copolymer, is characterized in that the structure had shown in formula I:
In formula I, m, n are the polymerization degree, 100≤m≤500,5≤n≤150;
R is methyl, 3-heptyl or undecyl.
2. cyclic olefine copolymer according to claim 1, is characterized in that, in described formula I, and 150≤m≤450,10≤n≤120.
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 polyreaction in a solvent with the compound with structure shown in formula III, obtains polymeric reaction product;
2), by described polymeric reaction product and hydrogen source carry out hydrogenation, obtain cyclic olefine copolymer;
In formula III, R is methyl, 3-heptyl or undecyl.
4. method according to claim 3, is characterized in that, described catalyzer is carbene catalyst.
5. method according to claim 4, 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 structure shown in formula II compound and the ratio of the mole number with the total mole number of the compound of structure shown in formula III and catalyzer be (200 ~ 500): 1;
Described have the compound of structure shown in formula II and have the mol ratio of structural compounds shown in formula III for (0.5 ~ 20): 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; The time of polyreaction is 60 ~ 140min.
8. method according to claim 3, is characterized in that, described step 2) in hydrogen source be alcohol compound, hydrocarbon compound, hydrazine class compound or formic acid.
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; The time of hydrogenation is 8 ~ 20 hours.
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CN106800639A (en) * 2017-01-23 2017-06-06 天津大学 A kind of high-strength and high ductility ion self-healing polymers material and preparation method
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