CN103965402B - A kind of cyclic olefine copolymer and its preparation method - Google Patents

A kind of cyclic olefine copolymer and its preparation method Download PDF

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CN103965402B
CN103965402B CN201410216495.1A CN201410216495A CN103965402B CN 103965402 B CN103965402 B CN 103965402B CN 201410216495 A CN201410216495 A CN 201410216495A CN 103965402 B CN103965402 B CN 103965402B
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cyclic olefine
olefine copolymer
formula
obtains
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CN103965402A (en
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李悦生
杨继兴
李彦国
穆红亮
刘三荣
崔磊
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I, and in formula I, x, y are the polymerization degree, 250≤x≤500，20≤y≤144. Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously. Experimental result shows, the second-order transition temperature of cyclic olefine copolymer provided by the invention is 125℃～215℃, has good thermotolerance; Tensile strength is 23MPa～35MPa, and tensile modulus is 1000MPa～1650MPa, and elongation at break is 3.7％～4.9％, has good mechanical property. In addition, cyclic olefine copolymer provided by the invention also has the good transparency. Experimental result shows, the transmittance ＞90％ of cyclic olefine copolymer provided by the invention.

Description

A kind of cyclic olefine copolymer and its preparation method
Technical field
The present invention relates to multipolymer technical field, particularly relate to a kind of cyclic olefine copolymer and its preparation method.
Background technology
Cyclic olefine copolymer is the thermoplastic engineering plastic of the high added value that a class is become by cyclic olefin polymerization, and this kind of multipolymer has high transparent, low-k, excellent thermotolerance, chemical resistant properties, and the mobility of melt, barrier and dimensional stability are better. Therefore, cyclic olefine copolymer can be widely used in and manufactures various optics, information, electrical equipment, medical material.
The resistance toheat of cyclic olefine copolymer is the key property of this kind of 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 being out of shape in equidimension, thus directly affects optical property and the mechanical property of cyclic olefine copolymer. Therefore, it is to increase the resistance toheat of cyclic olefine copolymer can expand the use range of cyclic olefine 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 is close or reaches the second-order transition temperature of multipolymer, comparatively serious distortion can be there is in multipolymer, and mechanical property declines greatly, this brings totally unfavorable impact to the application of copolymer material. Therefore the second-order transition temperature improving multipolymer can improve the thermotolerance of multipolymer effectively.
The synthetic method of cyclic olefine copolymer has two kinds: a kind of method is the chain polymerization of ethene and Norbornene derivative, and another kind of method is the ring-opening metathesis polymerization (ROMP) of Norbornene derivative and hydrogenation. Utilize the commercialization cyclic olefine copolymer of ROMP method gained at present, as trade names are WithCyclic olefine copolymer there is good mechanical property, but the second-order transition temperature of this kind of cyclic olefine copolymer is lower, asWithSecond-order transition temperature only 140 DEG C,Second-order transition temperature be 170 DEG C, therefore the thermotolerance of this kind of cyclic olefine copolymer is poor.
Adopt the method for the chain polymerization of ethene and Norbornene derivative can prepare the higher cyclic olefine copolymer of second-order transition temperature, as trade names areCyclic olefine copolymer, but the molecular chain rigidity of this kind of cyclic olefine copolymer is relatively strong, the elongation at break of cyclic olefine copolymer is poor, and therefore the mechanical property of this kind of cyclic olefine copolymer is poor.
The cyclic olefine copolymer that prior art provides cannot have good thermotolerance and mechanical property simultaneously.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of cyclic olefine copolymer, cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously.
The present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I:
In formula I, x, y are the polymerization degree, 250��x��500,20��y��144.
Preferably, in described formula I, 325��x��475,30��y��125.
The present invention provides the preparation method of cyclic olefine copolymer described in a kind of technique scheme, comprises the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out 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;
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 (400��700): 1;
Described have the compound of structure shown in formula II and have the mol ratio of structural compounds shown in formula III for (1��19): 1.
Preferably, described step 1) in the temperature of polyreaction be 0 DEG C��50 DEG C;
Described step 1) in time of polyreaction be 60 minutes��180 minutes.
Preferably, described step 2) in hydrogen source be hydrazine class compound.
Preferably, described step 2) in the ratio of the mole number of polymeric reaction product double bond and the mole number in 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 12 hours��20 hours.
The present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I, and in formula I, x, y are the polymerization degree, 250��x��500,20��y��144. Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously. Experimental result shows, the second-order transition temperature of cyclic olefine copolymer provided by the invention is 125 DEG C��215 DEG C, has good thermotolerance; Tensile strength is 23MPa��35MPa, and tensile modulus is 1000MPa��1650MPa, and elongation at break is 3.7%��4.9%, has good mechanical property. In addition, cyclic olefine copolymer provided by the invention also has the good transparency. Experimental result shows, the transmittance > 90% of cyclic olefine copolymer provided by the invention.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 obtains;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 2 obtains;
Fig. 3 be the product that the embodiment of the present invention 3 obtains hydrogen nuclear magnetic resonance (1H) spectrogram;
Fig. 4 be the product that the embodiment of the present invention 3 obtains nucleus magnetic resonance phosphorus (31P) spectrogram;
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that obtains of the embodiment of the present invention 4 and cyclic olefine copolymer;
Fig. 6 is that the present invention prepares the compound in cyclic olefine copolymer process with structure shown in formula II and has the reactivity ratio curve of the compound of structure shown in formula III;
Fig. 7 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains;
Fig. 8 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains;
Fig. 9 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains;
Figure 10 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains;
Figure 11 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains;
Figure 12 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains;
Figure 13 is the thermogravimetric curve of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains;
Figure 14 is the variation relation curve in the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 4��embodiment 9 and comparative example 1 obtain and cyclic olefine copolymer with the content of structural compounds shown in formula II;
Figure 15 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 4��embodiment 8 obtains.
Embodiment
The present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I:
In formula I, x, y are the polymerization degree, 250��x��500,20��y��144.
In the present invention, it is preferable that, 325��x��475; Preferred, 336��x��420. In the present invention, it is preferable that, 30��y��125; Preferred, 50��y��100. Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously. In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
The present invention provides the preparation method of cyclic olefine copolymer described in a kind of technique scheme, comprises the following steps:
1), under the effect of catalyzer, the compound with structure shown in formula II is carried out 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;
The present invention preferably by having the compound of structure shown in formula II, the compound with structure shown in formula III and solvent mixing, adds catalyzer in the mixture obtained and carries out polyreaction, obtain polymeric reaction product. The present invention preferably has the compound of structure shown in formula II, the compound with structure shown in formula III and solvent mixing when stirring by described. The method stirred during described mixing is not had special restriction by the present invention, adopts stirring technique scheme well known to those skilled in the art. In the present invention, the time stirred during described mixing is preferably 5 minutes��15 minutes, it is more preferable to be 8 minutes��12 minutes, it is most preferred that be 10 minutes.
The present invention preferably carries out described polyreaction when drying, anaerobic. In the present invention, described polyreaction can carry out in Bu Laoen (Mbraun) glove box, it is also possible to adopts Xi Laike (Schlenk) technology of standard to carry out under the protection of nitrogen. The present invention preferably carries out described polyreaction when stirring, and the stirring means of described polyreaction is not had special restriction by the present invention, 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, it is more preferable to be 10 DEG C��40 DEG C, it is most preferred that be 25 DEG C��30 DEG C. In the present invention, the time of described polyreaction is preferably 60min��180min, it is more preferable to be 90min��120min, it is most preferred that be 100min��110min.
In the present invention, described catalyzer is preferably carbene catalyst; It is more preferably ruthenium class carbene compound. In the present invention, described ruthenium class carbene compound preferably has the compound of structure shown in formula IV:
In formula IV, L is preferably PCy3; X is preferably Cl, Br or I; R1It is preferably H, Ph or CH2CH3; R is preferably Cy, Cp or Ph. In the present invention, in described formula IV, X is more preferably Cl; R1It is more preferably Ph; R is more preferably Cy. In the present invention, described ruthenium class carbene compound is more preferably the compound with structure shown in formula V:
The present invention preferably adopts polyreaction described in carbene catalyst catalysis, and active high, the polymerization better tolerance of this kind of catalyzer, makes the present invention in the process preparing cyclic olefine copolymer without the need to adding promotor; And described carbene catalyst causes and has structural compounds shown in formula II and have the speed of the polymerization of structural compounds shown in formula III fast, above-mentioned polyreaction is made to have higher polymerisation conversion.
In the present invention, described catalyzer is preferably catalyst solution. In the present invention, the solvent in described catalyst solution is preferably hydrocarbon compound, halogenated hydrocarbon compound, cyclic hydrocar-bons compound or arene compounds; It is more preferably pentamethylene, hexane, hexanaphthene, decane, Permethyl 99A., benzene, toluene, dimethylbenzene, ethylbenzene, methylene dichloride, chloroform or tetrahydrofuran (THF); It most preferably is benzene, toluene, methylene dichloride, hexanaphthene or tetrahydrofuran (THF). The source of solvent in described catalyst solution is not had special restriction by the present invention, adopts the solvent of mentioned kind well known to those skilled in the art, can buy by market and obtain.
In the present invention, the volumetric molar concentration of described catalyst solution is preferably 2.5 ��m of ol/mL��4.5 ��m ol/mL, it is more preferable to be 3 ��m of ol/mL��4 ��m ol/mL, it is most preferred that be 3.4 ��m of ol/mL��3.8 ��m ol/mL. In order to make in solvent that described catalyzer is fully dissolved in described catalyst solution, the present invention, preferably ultrasonic when, by the solvent mixing of described catalyzer and catalyst solution, obtains catalyst solution. Described ultrasonic method is not had special restriction by the present invention, adopts ultrasonic technique scheme well known to those skilled in the art. In the present invention, the described ultrasonic time is preferably 2 minutes��5 minutes, it is more preferable to be 3 minutes��4 minutes.
The source of described catalyzer is not had special restriction by the present invention, adopts the preparation method of the catalyzer of mentioned kind well known to those skilled in the art to prepare. In the present invention, the preparation method described in structural compounds shown in formula V is preferably:
By phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine reacts in organic solvent, obtain having the compound of structure shown in formula V.
Phenyl diazomethane, organic solvent and two chlorine three (triphenylphosphine) are more preferably closed ruthenium mixing by the present invention, add tricyclohexyl phosphine and react, obtain having the compound of structure shown in formula V in the mixture obtained. In the present invention, described phenyl diazomethane, organic solvent and two chlorine three (triphenylphosphine) close the temperature preferably-80 DEG C��-50 DEG C of ruthenium mixing, it is more preferable to be-78 DEG C��-55 DEG C, it is most preferred that be-75 DEG C��-65 DEG C. In the present invention, the temperature adding tricyclohexyl phosphine described in is preferably-70 DEG C��-50 DEG C, it is more preferable to be-60 DEG C��-55 DEG C. The present invention preferably carries out described phenyl diazomethane under the protection of nitrogen, two chlorine three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction. The present invention preferably carries out described phenyl diazomethane when stirring, two chlorine three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction. The method that described phenyl diazomethane, two chlorine three (triphenylphosphine) are closed ruthenium by the present invention and thricyclohexyl phosphine reaction stirs 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 phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction is preferably-80 DEG C��30 DEG C, it is more preferable to be-78 DEG C��25 DEG C, it is most preferred that be-70 DEG C��20 DEG C. In the present invention, the time that described phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and thricyclohexyl phosphine reaction is preferably 30 minutes��50 minutes, it is more preferable to be 35 minutes��45 minutes, it is most preferred that be 40 minutes.
The source of described phenyl diazomethane is not had special restriction by the present invention, can buy by market and obtain, it is possible to adopt the preparation method of phenyl diazomethane well known to those skilled in the art to prepare. In the present invention, the preparation method of described phenyl diazomethane is preferably:
By phenyl aldehyde-Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol are carried out building-up reactions, obtain phenyl diazomethane.
The present invention preferably carries out described building-up reactions when water-bath. In the present invention, the temperature of described building-up reactions is preferably 50 DEG C��70 DEG C, it is more preferable to be 55 DEG C��65 DEG C, it is most preferred that be 60 DEG C. In the present invention, the time of described building-up reactions is preferably 0.5 hour��1.5 hours, it is more preferable to be 1 hour. In the present invention, described phenyl aldehyde-the mass ratio of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol is preferably 1:(2��3): (25��35), it is more preferably 1:(2.4��2.9): (27��32), it is most preferred that be 1:2.8:25. The present invention, to the described phenyl aldehyde-source of Methyl benzenesulfonyl hydrazone, sodium methylate and Triethylene glycol is not had special restriction, 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; Undertaken described building-up reactions product extracting, dry, obtain phenyl diazomethane. The method of described removal methyl alcohol is not had special restriction by the present invention, 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 2nd 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, it is more preferable to be-40 DEG C.
In the present invention, described phenyl diazomethane is preferably the pentane solution of phenyl diazomethane. In the present invention, the mass concentration of the pentane solution of described phenyl diazomethane is preferably 90mg/mL��100mg/mL, it is more preferable to be 94mg/mL��98mg/mL.
The source that described two chlorine three (triphenylphosphine) close ruthenium is not had special restriction by the present invention, can buy by market and obtain.
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, it is more preferable to be 0.064g/mL��0.068g/mL. The source of described tricyclohexyl phosphine is not had special restriction by the present invention, can buy by market and obtain.
In the present invention, the mass ratio that described phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine is preferably 1:(3��6): (1��3.5), it is more preferably 1:(4��5): (2��3), it is most preferred that be 1:4.6:2.6.
In the present invention, described organic solvent is preferably methylene dichloride. The consumption of described organic solvent is not had special restriction by the present invention, and described organic solvent can close ruthenium and thricyclohexyl phosphine reaction offer liquid environment for above-mentioned phenyl diazomethane, two chlorine three (triphenylphosphine). In order to the air got rid of in described organic solvent, described organic solvent is preferably carried out liquid nitrogen freezing-thawing process by the present invention. In the present invention, the number of times of described liquid nitrogen freezing-thawing process is preferably 3 times. The method of described liquid nitrogen freezing-thawing process is not had special restriction by the present invention, adopts the technical scheme of liquid nitrogen freezing well known to those skilled in the art-thawing process. Described organic solvent can be carried out liquid nitrogen freezing-thawing process by the present invention by the following method:
Described organic solvent is loaded in Schlenk bottle, described Schlenk bottle is put into liquid nitrogen freezing;
By above-mentioned freezing after Schlenk bottle carry out vacuumizing process after the organic solvent in described Schlenk bottle is thawed.
The present invention has bubble to overflow in the process thawed by described organic solvent, thus eliminates the air in described organic solvent.
After described phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine should complete, the phenyl diazomethane obtained, two chlorine 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 described filtration, dissolving, concentrated, precipitation, washing and drying is not had special restriction by the present invention, 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, the reagent that described phenyl diazomethane, two chlorine three (triphenylphosphine) wash after closing ruthenium and tricyclohexyl phosphine reaction soln precipitation is preferably methyl alcohol and acetone. In the present invention, the method that described phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine reaction soln drying is preferably vacuum-drying. In the present invention, the time that described phenyl diazomethane, two chlorine three (triphenylphosphine) close ruthenium and tricyclohexyl phosphine reaction soln drying is preferably 2 hours��4 hours, it is more preferable to be 3 hours.
The source of the described compound with structure shown in formula II is not had special restriction by the present invention, 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 of the compound described in structure shown in formula II is preferably:
Norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol are reacted, obtains having the compound of structure shown in formula II.
The present invention preferably carries out described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction when vacuum. The present invention preferably carries out described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction when protectiveness gas. In the present invention, during described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol react, protectiveness 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, it is more preferable to be 170 DEG C��190 DEG C, it is most preferred that be 180 DEG C. In the present invention, the time of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction is preferably 25 hours��35 hours, it is more preferable to be 28 hours��32 hours.
In the present invention, described norbornadiene, anthracene and 2, the mol ratio of 6-di-t-butyl-p-cresol is preferably (1500��2000): (260��300): 1, it is more preferably (1600��1800): (270��295): 1, it is most preferred that be (1700��1760): (284��290): 1. The source of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol is not had special restriction by the present invention, can buy by market and obtain.
Described norbornadiene, anthracene and 2, after 6-di-t-butyl-p-cresol has reacted, the norbornadiene obtained, anthracene and 2,6-di-t-butyl-p-cresol reaction product are preferably cooled, leave standstill, filter, wash by the present invention, obtain having the compound of structure shown in formula II. Described cooling, method standing, that filter and wash are not had special restriction by the present invention, adopt cooling well known to those skilled in the art, the technical scheme leaving standstill, filtering and wash. In the present invention, the temperature of described cooling is preferably 20 DEG C��30 DEG C, it is more preferable to be 24 DEG C��28 DEG C. In the present invention, the described standing time is preferably 10 hours��16 hours, it is more preferable to be 12 hours��14 hours. In the present invention, the reagent of described norbornadiene, anthracene and 2,6-di-t-butyl-p-cresol reaction product washing is preferably normal hexane.
The described source with structural compounds shown in formula III is not had special restriction by the present invention, 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 of the compound described in structure shown in formula III is preferably:
Dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol are reacted, obtains having the compound of structure shown in formula III.
The present invention preferably carries out described dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol reaction when vacuum. The present invention preferably carries out described dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol reaction when protectiveness gas. In the present invention, during described dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol react, protectiveness gas is preferably nitrogen. In the present invention, the temperature of dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol reaction is preferably 220 DEG C��260 DEG C, it is more preferable to be 230 DEG C��250 DEG C, it is most preferred that be 240 DEG C. In the present invention, the time of described dicyclopentadiene, positive octene and 2,6-di-t-butyl-p-cresol reaction is preferably 6 hours��10 hours, it is more preferable to be 7 hours��9 hours, it is most preferred that be 8 hours.
In the present invention, described dicyclopentadiene, positive octene and 2, the mol ratio of 6-di-t-butyl-p-cresol is preferably (1500��2000): (500��1000): 1, it is more preferably (1600��1800): (550��750): 1, it is most preferred that be (1700��1750): (600��650): 1. The source of described dicyclopentadiene, positive octene alkene and 2,6-di-t-butyl-p-cresol is not had special restriction by the present invention, can buy by market and obtain.
Described dicyclopentadiene, positive octene and 2, after 6-di-t-butyl-p-cresol has reacted, the present invention preferably by the dicyclopentadiene obtained, positive octene and 2,6-di-t-butyl-p-cresol reaction product cooling, leave standstill, compound that air distillation, underpressure distillation obtain having structure shown in formula III. The method of described cooling, standing, air distillation and underpressure distillation is not had special restriction by the present invention, adopts cooling well known to those skilled in the art, leaves standstill the technical scheme of air distillation and distillation. In the present invention, the temperature of described cooling is preferably 20 DEG C��30 DEG C, it is more preferable to be 25 DEG C��28 DEG C. In the present invention, the described standing time is preferably 10 hours��16 hours, it is more preferable to be 12 hours��14 hours. In the present invention, the temperature of described air distillation is preferably 120 DEG C��180 DEG C, it is more preferable to be 150 DEG C��160 DEG C. In the present invention, the temperature of described underpressure distillation is preferably 60 DEG C��150 DEG C, it is more preferable to be 70 DEG C��130 DEG C. 60 DEG C��80 DEG C evaporate point when the present invention preferably collects described underpressure distillation, described in evaporate and point be the compound with structure shown in formula III.
In the present invention, the kind of described polymerization solvent is consistent with kind and the source of solvent in above-mentioned catalyst solution with source, does not repeat them here. In the present invention, the solvent of described polyreaction can be identical with the solvent in catalyst solution described in technique scheme, it is also possible to different.
The second-order transition temperature of the cyclic olefine copolymer that the present invention prepares by controlling the consumption of described polyreaction raw material. The compound in the cyclic olefine copolymer that the present invention prepares with structure shown in formula II is more many, and the second-order transition temperature of cyclic olefine copolymer is more high. In the present invention, the ratio of the described compound and the mole number with the total mole number of structural compounds shown in formula III and catalyzer with structure shown in formula II is preferably (400��700): 1, it is more preferably (500��600): 1, it is most preferred that be (520��580): 1. In the present invention, the compound described in structure shown in formula II is preferably (1��19) with the mol ratio of the compound with structure shown in formula III: 1, it is more preferable to be (4��18): 1, it is most preferred that be (5��7): 1.
The consumption of described polymerization solvent is not had special restriction by the present invention, adopts the consumption of solvent in polyreaction well known to those skilled in the art. In the present invention, the mass ratio of the compound and polymerization solvent described in structure shown in formula II is preferably 1:(15��30), it is more preferable to be 1:(17��26).
After described polyreaction completes, the present invention preferably adopts terminator to terminate described polyreaction, obtains polymeric reaction solution; By described polymeric reaction solution and precipitant mix, it is precipitated product; By the filtration of described precipitated product, washing, drying, obtain polymeric reaction product.
The kind of described terminator and source are not had special restriction by the present invention, adopt 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, it is more preferable to be (200��400): 1, it is most preferred that be 300:1. In the present invention, the time terminating described polyreaction is preferably 20 minutes��40 minutes, it is more preferable to be 25 minutes��35 minutes, it is most preferred that be 30 minutes.
After obtaining polymeric reaction solution, the present invention preferably by described polymeric reaction solution and precipitant mix, is precipitated product. The kind of precipitation agent of the described polymeric reaction solution of precipitation is not had special restriction by the present invention, 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, it is more preferable to be anhydrous methanol. In the present invention, the temperature of described polymeric reaction solution and precipitant mix is preferably-10 DEG C��0 DEG C, it is more preferable to be-8 DEG C��-5 DEG C.
After being precipitated product, the present invention preferably by the filtration of described precipitated product, washing, drying, obtains polymeric reaction product. Described precipitated product filters by the present invention, wash and the method for drying does not have special restriction, adopts the technical scheme of filtration well known to those skilled in the art, washing and drying. In the present invention, the reagent of described precipitated product washing is preferably acetone. In the present invention, the number of times of described precipitated product washing is preferably 2 times��4 times, it is more preferable to be 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, it is more preferable to be 25 DEG C��35 DEG C, it is most preferred that be 30 DEG C. In the present invention, the time of described precipitated product drying is preferably 12 hours��24 hours, it is more preferable to be 16 hours��20 hours, it is most preferred that be 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 when protectiveness gas. In the present invention, the protectiveness gas of described hydrogenation is preferably nitrogen. The method of described hydrogenation is not had special restriction by the present invention, adopts hydrogenation technical scheme well known to those skilled in the art.
The kind in described hydrogen source is not had special restriction by the present invention, and described hydrogen source is preferably hydrogen or hydrazine class compound, it is more preferable to be hydrazine class compound, it is most preferred that be p-toluene sulfonyl hydrazide.
In the present invention, when described hydrogen source is hydrazine class compound, the present invention preferably carries out hydrogenation by the following method and prepares cyclic olefine copolymer:
Described polymeric reaction product and hydrazine class compound are carried out hydrogenation in a solvent, obtains cyclic olefine copolymer.
In the present invention, in described polymeric reaction product, the ratio of the mole number of double bond and the mole number of hydrazine class compound is preferably 1:(3��6), it is more preferable to be 1:(4��5). In the present invention, described hydrogenation solvent is preferably toluene. The consumption of described hydrogenation solvent is not had special restriction by the present invention, and the solvent of employing can provide liquid environment for above-mentioned hydrogenation. In the present invention, temperature of reaction when described polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 110 DEG C��150 DEG C, it is more preferable to be 120 DEG C��140 DEG C, it is most preferred that be 130 DEG C. In the present invention, reaction times when described polymeric reaction product and hydrazine class compound carry out hydrogenation is preferably 12 hours��20 hours, it is more preferable to be 14 hours��19 hours, it is most preferred that be 16 hours��18 hours.
Carrying out to prevent above-mentioned polymeric reaction product and hydrazine class compound, in hydriding process, crosslinking reaction occurs, reaction raw materials when described polymeric reaction product and hydrazine class compound carry out hydrogenation preferably also comprises free radical scavenger. The kind of described free radical scavenger and source are not had special restriction by the present invention, adopt free radical scavenger well known to those skilled in the art, can buy by market and obtain. In the present invention, described free radical scavenger is preferably 2,6 di tert butyl 4 methyl phenol. The consumption of described free radical scavenger is not had special restriction by the present invention, adopts the consumption of free radical scavenger well known to those skilled in the art. In the present invention, the consumption of described free radical scavenger is preferably the consumption of the mole number 0.05eqv��3eqv relative to catalyzer described in technique scheme.
After described hydrogenation completes, the hydrogenation reaction product obtained preferably is mixed by the present invention with ethanol, 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%. Described mix products filters by the present invention, wash and the method for drying does 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, it is preferably 12 hours��24 hours the time of drying of described mix products, it is more preferable to be 16 hours��20 hours. In the present invention, the drying temperature of described mix products is preferably 40 DEG C��70 DEG C, it is more preferable to be 50 DEG C��65 DEG C, it is most preferred that be 60 DEG C.
After preparing cyclic olefine copolymer, the cyclic olefine copolymer obtained is carried out proton nmr spectra detection and carbon-13 nmr spectra detection by the present invention, the detection method of the detection of described proton nmr spectra and carbon-13 nmr spectra detection measures at 25 DEG C for adopting VarianUnity-400 type nuclear magnetic resonance spectrometer, tetramethylsilane (TMS) is interior mark, and deuterochloroform is solvent. Detected result is that cyclic olefine copolymer provided by the invention has the structure shown in formula I. The cyclenes copolymer that present invention formula VI calculates has the content of structural compounds shown in formula II:
There is the compound mol%=(I of structure shown in formula II3.9��4.3/I5.42) �� 100% formula VI,
In formula VI, I3.9��4.3For chemical shift in proton nmr spectra is at the peak area at 3.9��4.3 places, I5.42For chemical shift in proton nmr spectra is at the peak area at 5.42 places. Calculation result is, the molar content in cyclic olefine copolymer provided by the invention with structural compounds shown in formula II is 64%��95%.
The present invention adopts differential thermal analysis and thermogravimetry to test the second-order transition temperature of the cyclic olefine copolymer obtained, detection method carries out differential thermal analysis mensuration for adopting Perkin-ElmerPyris1DSC differential scanning calorimeter, the speed of heating, cooling is 10 DEG C/min, carries out rescan. Adopt Perkin-ElmerPyris1 type Instrument measuring thermal weight loss. Detected result is the second-order transition temperature of cyclic olefine copolymer provided by the invention is 125 DEG C��215 DEG C, has good thermostability.
The present invention is at INSTRON1121, Canton, MA instrument is tested the mechanical property of the cyclic olefine copolymer obtained, detect according to the standard of GB/T1040-1992 " plastic tensile performance test methods ", batten folder distance is 20.0mm, test rate is 5mm/min, and each sample at least tests 8 times to ensure the reliability of data. Test result is, the tensile strength of cyclic olefine copolymer provided by the invention is 23MPa��35MPa, and tensile modulus is 1000MPa��1650MPa, and elongation at break is 3.7%��4.9%.
The present invention adopts ShimadzuUV-3600 ultraviolet-visible light-near infrared spectrometer to test the transparency of the cyclic olefine copolymer obtained, and test wavelength is 400nm��800nm. Test result is the transmittance > 90% of the cyclic olefine copolymer that the present invention obtains.
The present invention adopts gel permeation chromatography to test molecular weight distribution and the number-average molecular weight of the cyclic olefine copolymer obtained, and detection method measures for adopting waters152 type gel permeation chromatograph; Adopt the detection of RI-Laser detector; Detection solvent is tetrahydrofuran (THF), and detected temperatures is 35 DEG C; Flow rate of mobile phase is 1.0mL/min, and employing PLEasiCalPS-1 is standard specimen. Test result is the molecular weight distribution of cyclic olefine copolymer provided by the invention is 1.20��1.32, and number-average molecular weight is 10 �� 104G/mol��15 �� 104g/mol��
The method that the present invention adopts product to weigh tests the polymerisation conversion of polyreaction described in technique scheme, and test result is the polymerisation conversion of above-mentioned polyreaction is 100%.
The present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I, and in formula I, x, y are the polymerization degree, 250��x��500,20��y��144. Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously. In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
In order to understand the present invention further; below in conjunction with embodiment, cyclic olefine copolymer provided by the invention and its preparation method are described in detail; it is to be understood that; these describe just in order to the features and advantages of the present invention are described further, and they can not be interpreted as limiting the scope of the present invention.
Reaction raw materials used by following examples of the present invention is commercial goods.
Embodiment 1
In the stainless steel autoclaves of 2 liters, add the 2,6-di-t-butyl-p-cresol of the norbornadiene of 800mL, the anthracene of 230 grams and 1 gram successively, described autoclave is repeated the operation that 3 times vacuumize rear inflated with nitrogen; Described autoclave is heated to 180 DEG C, makes the reaction that the material in described autoclave carries out when stirring 30 hours.
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, leaves standstill and filter after 12 hours, by the filtration product n-hexane that obtains 2 times, obtain 260 grams of products. It is 75% that the method that the embodiment of the present invention 1 provides prepares the product rate of product.
Product obtained above is carried out proton nmr spectra detection, detected result is as shown in Figure 1, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 obtains, and as shown in Figure 1, the product that the embodiment of the present invention 1 obtains is the compound with structure shown in formula II.
Embodiment 2
In the stainless steel autoclaves of 2 liters, add the 2,6-di-t-butyl-p-cresol of the positive octene of 300mL, the dicyclopentadiene of 108mL and 1 gram successively, described autoclave is repeated the operation that 3 times vacuumize rear inflated with nitrogen; Described autoclave is heated to 240 DEG C, makes the reaction that the material in described autoclave carries out when stirring 8 hours.
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, leaves standstill after 12 hours 120 DEG C of air distillations, collect unreacted positive octene, then at 80 DEG C, the air distillation product obtained being carried out underpressure distillation, evaporating point when collecting 68 DEG C��80 DEG C, obtains 108 grams of products. It is 38.9% that the method that the embodiment of the present invention 2 provides prepares the product rate of product.
Product obtained above is carried out proton nmr spectra detection, detected result is as shown in Figure 2, Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 2 obtains, and as shown in Figure 2, the product that the embodiment of the present invention 2 obtains is the compound with structure shown in formula III.
Embodiment 3
The single port bottle of 100mL adds the phenyl aldehyde-to Methyl benzenesulfonyl hydrazone, the sodium methylate of 1.75 grams and the Triethylene glycol of 40mL of 4.96 grams, is placed in the water-bath of 60 DEG C by described single port bottle to carry out the building-up reactions of 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 phenyl diazomethane; The product rate of described phenyl diazomethane is 50%.
Two chlorine three (triphenylphosphine) adding 4.0 grams in a mouth bottle of 250mL close ruthenium, lead to the air in the described mouth bottle of nitrogen displacement, inject 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, adding the pentane solution 10mL of phenyl diazomethane that-50 DEG C of mass concentrations are 98.5mg/mL to mix when stirring, the phenyl diazomethane in the pentane solution of described phenyl diazomethane is the above-mentioned phenyl diazomethane prepared; Add 40mL after the mixture obtained is stirred 10min at-70 DEG C, the dichloromethane solution of tricyclohexyl phosphine that the mass concentration of-50 DEG C is 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, reaction soln after filtration is concentrated and again filters to 10mL, adding 100mL in the filtration product obtained through the methyl alcohol of three liquid nitrogen freezings-thawing process precipitates, by the throw out that obtains first by methanol wash three times, again with washing with acetone twice, the throw out after washing is carried out the vacuum-drying of 3 hours, obtains the product of 2.1g. It is 81% that the method that the embodiment of the present invention 3 provides prepares the product rate of product.
Product obtained above is carried out proton nmr spectra detection and nucleus magnetic resonance phosphorus spectrum detection, detected result as shown in Figure 3 and Figure 4, Fig. 3 be the product that embodiment 3 obtains hydrogen nuclear magnetic resonance (1H) spectrogram, Fig. 4 be the product that the embodiment of the present invention 3 obtains nucleus magnetic resonance phosphorus (31P) spectrogram, by Fig. 3 and Fig. 4 it will be seen that the product that the embodiment of the present invention 3 obtains is the compound with structure shown in formula V.
Embodiment 4
What the compound with structure shown in formula II that the embodiment 1 adding 1.933g at 25 DEG C in the polyreaction bottle of drying prepares and 0.067g embodiment 2 prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that 15.5mg embodiment 3 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 500eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate of the polymeric reaction product that the polymerization process that the embodiment of the present invention 4 provides obtains is 100%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5g p-toluene sulfonyl hydrazide, relative to the above-mentioned compound with structure shown in formula V mole number 0.1eqv 2, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 12 hours, obtains hydrogenation reaction product; The purity that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.41g cyclic olefine copolymer. It is 93.6% that the method for the hydrogenation that the embodiment of the present invention 4 provides obtains the product rate of cyclic olefine copolymer.
The polymeric reaction product and the cyclic olefine copolymer that the embodiment of the present invention 4 are obtained according to the method described in technique scheme carry out proton nmr spectra detection, detected result is as shown in Figure 5, Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the polymeric reaction product that obtains of the embodiment of the present invention 4 and cyclic olefine copolymer, in Fig. 5, curve 1 is the proton nmr spectra of the polymeric reaction product that the embodiment of the present invention 4 obtains, curve 2 is the proton nmr spectra of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, as seen from Figure 5, the polymeric reaction product that the embodiment of the present invention 4 obtains is the completely dissolve of double bond peak after hydrogenation, hydrogenation effect is better. by curve in Fig. 52 it will be seen that the cyclic olefine copolymer that the embodiment of the present invention 4 obtains has the structure shown in formula I, in formula I, x is 380, y is 20.
Calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 4 obtains with structural compounds shown in formula II is 95.23%.
The cyclic olefine copolymer embodiment of the present invention 4 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is 1.27, and number-average molecular weight is 10.6 �� 104g/mol��
The cyclic olefine copolymer embodiment of the present invention 4 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in Figure 7, Fig. 7 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, as shown in Figure 7, the cyclic olefine copolymer that the embodiment of the present invention 4 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 4 obtains is 214.7 DEG C. The cyclic olefine copolymer embodiment of the present invention 4 obtained according to method described in technique scheme carries out thermogravimetry test, and test result is the rate of decomposition of the cyclic olefine copolymer that obtains of the embodiment of the present invention 4 when 360 DEG C is 10%, has good thermostability.
The mechanical property of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is tested according to method 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 3.8%, tensile strength is 31.8MPa, and tensile modulus is 1650MPa.
The transparency of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains is tested according to method described in technique scheme, test result is as shown in figure 15, Figure 15 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 4��embodiment 8 obtains, in Figure 15, curve 1 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains, as shown in Figure 15, the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 4 obtains.
Testing the polymerisation conversion of the embodiment of the present invention 4 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 4 when carrying out above-mentioned polyreaction is 100%.
Embodiment 5
What the compound with structure shown in formula II that the embodiment 1 adding 1.892g at 25 DEG C in the polyreaction bottle of drying prepares and 0.108g embodiment 2 prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 15.6mg 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 500eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate of the polymeric reaction product that the polymerization process that the embodiment of the present invention 5 provides obtains is 100%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5g p-toluene sulfonyl hydrazide, relative to the 2 of the above-mentioned mole number 0.05eqv with structural compounds shown in formula V, 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 that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.35g cyclic olefine copolymer. It is 92.4% that the method for the hydrogenation that the embodiment of the present invention 5 provides obtains the product rate of cyclic olefine copolymer.
The cyclic olefine copolymer structure embodiment of the present invention 5 obtained according to the method described in embodiment 4 detects, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 5 obtains has the structure shown in formula I, in formula I, x is 370, y is 30, calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 5 obtains with structural compounds shown in formula II is 92.59%.
The cyclic olefine copolymer embodiment of the present invention 5 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 1.22, and number-average molecular weight is 9.8 �� 104g/mol��
The cyclic olefine copolymer embodiment of the present invention 5 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in Figure 8, Fig. 8 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, as shown in Figure 8, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is 195.6 DEG C. The cyclic olefine copolymer embodiment of the present invention 5 obtained according to method described in technique scheme carries out thermogravimetry test, and test result is that the cyclic olefine copolymer that the embodiment of the present invention 5 obtains has good thermostability.
The mechanical property of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is tested according to method 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 3.7%, tensile strength is 31MPa, and tensile modulus is 1590MPa.
The transparency of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains is tested according to method described in technique scheme, test result is as shown in figure 15, in Figure 15, curve 2 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains, as shown in Figure 15, the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 5 obtains.
Testing the polymerisation conversion of the embodiment of the present invention 5 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 5 when carrying out above-mentioned polyreaction is 100%.
Embodiment 6
What the embodiment 2 of the compound with structure shown in formula II that the embodiment 1 adding 1.835g at 25 DEG C in the polyreaction bottle of drying prepares and 0.165g prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 15.9mg 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 300eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate of the polymeric reaction product that the polymerization process that the embodiment of the present invention 6 provides obtains is 100%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5.8g p-toluene sulfonyl hydrazide, relative to the 2 of the above-mentioned mole number 2eqv with structural compounds shown in formula V, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; The purity that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.44g cyclic olefine copolymer. It is 93.8% that the method for the hydrogenation that the embodiment of the present invention 6 provides obtains the product rate of cyclic olefine copolymer.
The cyclic olefine copolymer structure embodiment of the present invention 6 obtained according to the method described in embodiment 4 detects, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 6 obtains has the structure shown in formula I, in formula I, x is 350, y is 50, calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 6 obtains with the compound of structure shown in formula II is 87.7%.
The cyclic olefine copolymer embodiment of the present invention 6 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 1.21, and number-average molecular weight is 11.9 �� 104g/mol��
The cyclic olefine copolymer embodiment of the present invention 6 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in Figure 9, Fig. 9 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, as shown in Figure 9, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is 190.9 DEG C. The cyclic olefine copolymer embodiment of the present invention 6 obtained according to method described in technique scheme carries out thermogravimetry test, and 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 that the embodiment of the present invention 6 obtains is tested according to method 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 4.1%, tensile strength is 30.7MPa, and tensile modulus is 1240MPa.
The transparency of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains is tested according to method described in technique scheme, test result is as shown in figure 15, in Figure 15, curve 3 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains, as shown in Figure 15, the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 6 obtains.
Testing the polymerisation conversion of the embodiment of the present invention 6 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 6 when carrying out above-mentioned polyreaction is 100%.
Embodiment 7
What the compound with structure shown in formula II that the embodiment 1 adding 1.78g at 25 DEG C in the polyreaction bottle of drying prepares and 0.22g embodiment 2 prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 16.1mg 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 180min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 500eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate of the polymeric reaction product that the polymerization process that the embodiment of the present invention 7 provides obtains is 100%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5.0g p-toluene sulfonyl hydrazide, relative to the 2 of the above-mentioned mole number 3eqv with structural compounds shown in formula V, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 18 hours, obtains hydrogenation reaction product; The purity that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.46g cyclic olefine copolymer. It is 94.1% that the method for the hydrogenation that the embodiment of the present invention 7 provides obtains the product rate of cyclic olefine copolymer.
The cyclic olefine copolymer structure embodiment of the present invention 7 obtained according to the method described in embodiment 4 detects, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 7 obtains has the structure shown in formula I, in formula I, x is 336, y is 64, calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 7 obtains with the compound of structure shown in formula II is 84.03%.
The cyclic olefine copolymer embodiment of the present invention 7 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 1.32, and number-average molecular weight is 11 �� 104g/mol��
The cyclic olefine copolymer embodiment of the present invention 7 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in Figure 10, Figure 10 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains, as shown in Figure 10, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is 179.6 DEG C. The cyclic olefine copolymer embodiment of the present invention 7 obtained according to method described in technique scheme carries out thermogravimetry test, and 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 that the embodiment of the present invention 7 obtains is tested according to method 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 4.5%, tensile strength is 32.8MPa, and tensile modulus is 1350MPa.
The transparency of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains is tested according to method described in technique scheme, as shown in figure 15, in Figure 15, curve 4 is the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 7 obtains to test result.
Testing the polymerisation conversion of the embodiment of the present invention 7 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 7 when carrying out above-mentioned polyreaction is 100%.
Embodiment 8
What the compound with structure shown in formula II that the embodiment 1 adding 1.73g at 50 DEG C in the polyreaction bottle of drying prepares and 0.268g embodiment 2 prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 16.3mg 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 300eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate of the polymeric reaction product that the polymerization process that the embodiment of the present invention 8 provides obtains is 100%.
In the polyreaction bottle of drying, add successively the above-mentioned polymeric reaction product of 1.5g, 5.0g p-toluene sulfonyl hydrazide, relative to the 2 of the above-mentioned mole number 2eqv with structural compounds shown in formula V, 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 that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.35g cyclic olefine copolymer. It is 92% that the method for the hydrogenation that the embodiment of the present invention 8 provides obtains the product rate of cyclic olefine copolymer.
The cyclic olefine copolymer structure embodiment of the present invention 8 obtained according to the method described in embodiment 4 detects, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 8 obtains has the structure shown in formula I, in formula I, x is 325, y is 75, calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 8 obtains with the compound of structure shown in formula II is 81.3%.
The cyclic olefine copolymer embodiment of the present invention 8 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 1.22, and number-average molecular weight is 10.7 �� 104g/mol��
The Fineman-Ross method test of employing obtains the present invention and prepares the compound in cyclic olefine copolymer process with structure shown in formula II and have the reactivity ratio curve of the compound of structure shown in formula III, test result is as shown in Figure 6, Fig. 6 is that the present invention prepares the compound in cyclic olefine copolymer process with structure shown in formula II and has the reactivity ratio curve of the compound of structure shown in formula III, and in Fig. 6, X-coordinate is f/F2Ordinate zou is (f-1)/F, wherein f has the compound of structure shown in formula II and has the amount of substance ratio of component of the compound of structure shown in formula III in polymkeric substance, F is the compound being polymerized and having structure shown in formula II when not starting and the amount of substance feed ratio of the compound with structure shown in formula III, controls two kinds of monomer conversions lower than 10%. Relational expression can be obtained: (f-1) F=-1.61 �� f/F by Fig. 62+ 0.54, the reactivity ratio of the known compound with structure shown in formula II is 0.54, the reactivity ratio with the compound of structure shown in formula III is 1.61, show due to steric hindrance reason, the rate of polymerization with the compound of structure shown in formula II is significantly lower than the compound with structure shown in formula III, the reactivity ratio of compound with structure shown in formula II is 0.87 with the product of the reactivity ratio of the compound with structure shown in formula III, this numerical value is less than 1, illustrate that the polymkeric substance that the compound with structure shown in formula II and the compound random copolymerization with structure shown in formula III obtain is typical random copolymers.
The cyclic olefine copolymer embodiment of the present invention 8 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in figure 11, Figure 11 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, as shown in Figure 11, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is 166.8 DEG C.
The cyclic olefine copolymer embodiment of the present invention 8 obtained according to method described in technique scheme carries out thermogravimetry test, and as shown in figure 13, in Figure 13, curve 1 is the thermogravimetric curve of the cyclic olefine copolymer that obtains of the embodiment of the present invention 8 in nitrogen to test result; In Figure 13, curve 2 is the aerial thermogravimetric curve of cyclic olefine copolymer that the embodiment of the present invention 8 obtains. As shown in Figure 13, the cyclic olefine copolymer that the embodiment of the present invention 8 obtains has good thermostability.
The mechanical property of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is tested according to method 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 4.6%, tensile strength is 26MPa, and tensile modulus is 1200MPa.
The transparency of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains is tested according to method described in technique scheme, test result is as shown in figure 15, in Figure 15, curve 5 is the transmittance of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains, as shown in Figure 15, the transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 8 obtains.
Testing the polymerisation conversion of the embodiment of the present invention 8 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 8 when carrying out above-mentioned polyreaction is 100%.
Embodiment 9
What the compound with structure shown in formula II that the embodiment 1 adding 1.48g at 25 DEG C in the polyreaction bottle of drying prepares and 0.52g embodiment 2 prepared has the compound of structure shown in formula III and the methylene dichloride of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 17.4mg 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; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 500eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2g. The receipts rate 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 successively the above-mentioned polymeric reaction product of 1.5g, 5.0g p-toluene sulfonyl hydrazide, relative to the 2 of the above-mentioned mole number 1eqv with structural compounds shown in formula V, the toluene of 6-di-tert-butyl-4-methy phenol (BHT) and 40mL, at 130 DEG C, return stirring carries out hydrogenation in 12 hours, obtains hydrogenation reaction product; The purity that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains 1.34g cyclic olefine copolymer. It is 92.1% that the method for the hydrogenation that the embodiment of the present invention 9 provides obtains the product rate of cyclic olefine copolymer.
The cyclic olefine copolymer structure embodiment of the present invention 9 obtained according to the method described in embodiment 4 detects, detected result is, the cyclic olefine copolymer that the embodiment of the present invention 9 obtains has the structure shown in formula I, in formula I, x is 256, y is 144, calculating according to above-mentioned formula VI, the molar content in the cyclic olefine copolymer that the embodiment of the present invention 9 obtains with the compound of structure shown in formula II is 64.1%.
The cyclic olefine copolymer embodiment of the present invention 9 obtained according to method described in technique scheme carries out gel permeation chromatography test, and test result is the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is 1.23, and number-average molecular weight is 9.5 �� 104g/mol��
The cyclic olefine copolymer embodiment of the present invention 9 obtained according to the method described in technique scheme carries out differential thermal analysis test, test result is as shown in figure 12, Figure 12 is the differential calorimetry curve of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains, as shown in Figure 12, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is 125.8 DEG C. Figure 14 is the variation relation curve in the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 4��embodiment 9 and comparative example 1 obtain and cyclic olefine copolymer with the content of structural compounds shown in formula II, as shown in Figure 14, the compound in the cyclic olefine copolymer that the present invention obtains with structure shown in formula II is more many, and the second-order transition temperature of cyclic olefine copolymer is more high.
The cyclic olefine copolymer embodiment of the present invention 9 obtained according to method described in technique scheme carries out thermogravimetry test, and test result is that the cyclic olefine copolymer that the embodiment of the present invention 9 obtains has good thermostability.
The mechanical property of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains is tested according to method 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 4.9%, tensile strength is 23.4MPa, and tensile modulus is 1030MPa. The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 9 obtains. The cyclic olefine copolymer that the embodiment of the present invention 9 obtains has higher second-order transition temperature, mechanical property and the transparency.
Testing the polymerisation conversion of the embodiment of the present invention 9 when carrying out above-mentioned polyreaction according to method described in technique scheme, test result is the polymerisation conversion of the embodiment of the present invention 9 when carrying out above-mentioned polyreaction is 100%.
Embodiment 10
What the compound with structure shown in formula II that the embodiment 1 adding 1.78g at 0 DEG C in the polyreaction bottle of drying prepares and 0.22g embodiment 2 prepared has the compound of structure shown in formula III and the hexane of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 10.7mg prepares is added in little ampulla, the toluene adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula V is fully dissolved in toluene, obtains having the compound solution of structure shown in formula V; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 180min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 300eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 1.99g.
By in autoclave when vacuum pre-dry 5 hours, add in described autoclave 1g above-mentioned prepare polymeric reaction product, the hexanaphthene of 300mL, the Pd/Al of 0.5g2O3Catalyzer, the gas of substituting that described autoclave carries out 3 times operates the hydrogen being filled with 30MPa in backward described autoclave, carries out the hydrogenation of 24h at 130 DEG C, filters the hydrogenation solution obtained to reclaim Pd/Al wherein2O3Catalyzer, obtains hydrogenation reaction product; Described hydrogenation reaction product is poured in ethanol and precipitate, put into vacuum drying oven drying 12 hours at 60 DEG C after being filtered by the precipitated product obtained, obtain the cyclic olefine copolymer of 0.85g.
According to the stuctures and properties of the cyclic olefine copolymer that the method test embodiment of the present invention 10 described in embodiment 4 obtains, test result is that the cyclic olefine copolymer that the embodiment of the present invention 10 obtains has the structure shown in formula I, and in formula I, x is 500, y is 100. The molar content of the compound in the cyclic olefine copolymer that the embodiment of the present invention 10 obtains with structure shown in formula II in cyclic olefine copolymer is 84.6%, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 180.3 DEG C, the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 1.30, and number-average molecular weight is 14.9 �� 104G/mol. The elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains is 4.1%, and tensile strength is 35.8MPa, and tensile modulus is 1360MPa. The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 10 obtains. The polymerisation conversion when embodiment of the present invention 10 carries out above-mentioned polyreaction is 100%. The cyclic olefine copolymer that the embodiment of the present invention 10 obtains has higher second-order transition temperature, mechanical property and the transparency.
Embodiment 11
What the compound with structure shown in formula II that the embodiment 1 adding 1.78g at 50 DEG C in the polyreaction bottle of drying prepares and 0.22g embodiment 2 prepared has the compound of structure shown in formula III and the benzene of 25mL, it is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 12.8mg prepares is added in little ampulla, the hexanaphthene 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 hexanaphthene, obtains having the compound solution of structure shown in formula V; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 60min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 300eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 2.0g.
In the polyreaction bottle of drying, adding the above-mentioned polymeric reaction product of 1.5g, the p-toluene sulfonyl hydrazide of 5.2g and the toluene of 40mL successively, at 150 DEG C, return stirring carries out hydrogenation in 20 hours, obtains hydrogenation reaction product; The purity that described hydrogenation reaction product is added drop-wise to 300mL is in the ethanol of 98%, the mix products obtained is filtered and again dissolves 30 minutes at 130 DEG C with the toluene of 40mL after draining, it is in the ethanol of 98% by the purity that the solution after dissolving joins 300mL again, the mix products obtained is put into vacuum drying oven drying 12 hours at 60 DEG C, obtains the cyclic olefine copolymer of 1.40g.
According to the stuctures and properties of the cyclic olefine copolymer that the method test embodiment of the present invention 11 described in embodiment 4 obtains, test result is that the cyclic olefine copolymer that the embodiment of the present invention 11 obtains has the structure shown in formula I, and in formula I, x is 420, y is 80. The molar content of the compound in the cyclic olefine copolymer that the embodiment of the present invention 11 obtains with structure shown in formula II in cyclic olefine copolymer is 84.1%, the second-order transition temperature of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 181.3 DEG C, the molecular weight distribution of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 1.23, and number-average molecular weight is 13.5 �� 104G/mol. The elongation at break of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains is 4.2%, and tensile strength is 33.5MPa, and tensile modulus is 1420MPa. The transmittance > 90% of the cyclic olefine copolymer that the embodiment of the present invention 11 obtains. The polymerisation conversion when embodiment of the present invention 11 carries out above-mentioned polyreaction is 100%. The cyclic olefine copolymer that the embodiment of the present invention 11 obtains has higher second-order transition temperature, mechanical property and the transparency.
Comparative example 1
What the embodiment 1 adding 2g at 25 DEG C in the polyreaction bottle of drying prepared has the compound of structure shown in formula II and the tetrahydrofuran (THF) of 25mL, is uniformly mixed 10min, obtains mixture; The compound with structure shown in formula V that the embodiment 3 of 6.1mg prepares is added in little ampulla, the tetrahydrofuran (THF) adding 5mL again in described little ampulla carries out the supersound process of 3min, the compound described in making with structure shown in formula V is fully dissolved in tetrahydrofuran (THF), obtains having the compound solution of structure shown in formula V; When stirring, the described compound solution with structure shown in formula V is joined the polyreaction carrying out 120min in above-mentioned polyreaction bottle;
After described polyreaction completes, add in above-mentioned polyreaction bottle when stirring and terminate described polyreaction relative to the ethyl vinyl ether of the above-mentioned mole number 400eqv with structural compounds shown in formula V; After 30min, the polymeric reaction solution obtained is poured in anhydrous methanol, it is precipitated product; With washing with acetone 3 times after being filtered by described precipitated product, in the vacuum drying oven of 40 DEG C dry 12 hours, obtain the polymeric reaction product of 1.98g. The receipts rate of the polymeric reaction product that the polymerization process that comparative example 1 of the present invention provides obtains is 99.0%.
By in autoclave when vacuum pre-dry 5 hours, add in described autoclave 1g above-mentioned prepare polymeric reaction product, the hexanaphthene of 300mL, the Pd/Al of 0.5g2O3Catalyzer, the gas of substituting that described autoclave carries out 3 times operates the hydrogen being filled with 30MPa in backward described autoclave, carries out the hydrogenation of 24h at 150 DEG C, filters the hydrogenation solution obtained to reclaim Pd/Al wherein2O3Catalyzer, obtains hydrogenation reaction product; Described hydrogenation reaction product is poured in ethanol and precipitate, put into vacuum drying oven drying 12 hours at 60 DEG C after being filtered by the precipitated product obtained, obtain the cyclic olefine copolymer of 0.90g.
Test the stuctures and properties of the cyclic olefine copolymer that comparative example 1 of the present invention obtains according to the method described in embodiment 4, the structural formula that test result is the cyclic olefine copolymer that comparative example 1 of the present invention obtains is:
In formula VII, x is 1000. The second-order transition temperature of the cyclic olefine copolymer that comparative example 1 of the present invention obtains is 224.0 DEG C, and the molecular weight distribution of the cyclic olefine copolymer that comparative example 1 of the present invention obtains is 1.34, and number-average molecular weight is 32.1 �� 104G/mol. The elongation at break of the cyclic olefine copolymer that comparative example 1 of the present invention obtains is 2.7%, and tensile strength is 54.1MPa, and tensile modulus is 1820MPa. The transmittance > 90% of the cyclic olefine copolymer that comparative example 1 of the present invention obtains. In comparative example 1 of the present invention, the polymerisation conversion of polyreaction is 100%.
As seen from the above embodiment, the present invention provides a kind of cyclic olefine copolymer, has the structure shown in formula I, and in formula I, x, y are the polymerization degree, 250��x��500,20��y��144. Cyclic olefine copolymer provided by the invention has good thermotolerance and mechanical property simultaneously. In addition, cyclic olefine copolymer provided by the invention also has the good transparency.
Illustrating just for helping the method understanding the present invention and core concept thereof of above embodiment. , it is also possible to the present invention carries out some improvement and modification, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention these improve and modify in the protection domain also falling into the claims in the present invention. Being 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 limited in these embodiments shown in this article, but be met the widest scope consistent with principle disclosed herein and features of novelty.

Claims (10)

1. a cyclic olefine copolymer, has the structure shown in formula I:
In formula I, x, y are the polymerization degree, 250��x��500,20��y��144.
2. cyclic olefine copolymer according to claim 1, it is characterised in that, in described formula I, 325��x��475,30��y��125.
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;
4. method according to claim 3, it is characterised in that, described catalyzer is carbene catalyst.
5. method according to claim 3, it is characterised in that, described catalyzer is ruthenium class carbene compound.
6. method according to claim 3, it is characterised in that, described in there is structure shown in formula II compound and the ratio with the mole number of the total mole number of the compound of structure shown in formula III and catalyzer be (400��700): 1;
Described have the compound of structure shown in formula II and have the mol ratio of structural compounds shown in formula III for (1��19): 1.
7. method according to claim 3, it is characterised in that, described step 1) in the temperature of polyreaction be 0 DEG C��50 DEG C;
Described step 1) in time of polyreaction be 60 minutes��180 minutes.
8. method according to claim 3, it is characterised in that, described step 2) in hydrogen source be hydrazine class compound.
9. method according to claim 8, it is characterised in that, described step 2) in the ratio of the mole number of polymeric reaction product double bond and the mole number in hydrogen source be 1:(3��6).
10. method according to claim 8, it is characterised in that, described step 2) in the temperature of hydrogenation be 110 DEG C��150 DEG C;
Described step 2) in time of hydrogenation be 12 hours��20 hours.
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