CN112480374A - Polar cycloolefin copolymer and preparation method thereof - Google Patents

Polar cycloolefin copolymer and preparation method thereof Download PDF

Info

Publication number
CN112480374A
CN112480374A CN202011349360.4A CN202011349360A CN112480374A CN 112480374 A CN112480374 A CN 112480374A CN 202011349360 A CN202011349360 A CN 202011349360A CN 112480374 A CN112480374 A CN 112480374A
Authority
CN
China
Prior art keywords
present
cycloolefin copolymer
compound
formula
polymerization reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011349360.4A
Other languages
Chinese (zh)
Inventor
李百祥
龙映云
李彦国
曾宝华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN202011349360.4A priority Critical patent/CN112480374A/en
Publication of CN112480374A publication Critical patent/CN112480374A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1422—Side-chains containing oxygen containing OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3323—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other monocyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/60—Glass transition temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/62—Mechanical aspects
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/724—Hydrogenation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention provides a polar cycloolefin copolymer and a preparation method thereof, wherein the polar cycloolefin copolymer has a structure shown in a formula I. The side chain of the polar cycloolefin copolymer provided by the invention contains a formyl imine group and a benzene ring structure, so that the polar cycloolefin copolymer has polarity, better heat resistance and good mechanical property. In addition, the polar cycloolefin copolymer provided by the invention also has better transparency. The experimental result shows that the contact angle of the cycloolefin copolymer provided by the invention and the water surface is 84.5-103.0 degrees; the glass transition temperature is 130.4-205.9 ℃; the tensile strength is 17.7MPa to 31MPa, the tensile modulus is 1042MPa to 1780MPa, the elongation at break is 1.7 percent to 9.7 percent, and the light transmittance is more than 82 percent.

Description

Polar cycloolefin copolymer and preparation method thereof
Technical Field
The invention belongs to the technical field of copolymers, and particularly relates to a polar cycloolefin copolymer and a preparation method thereof.
Background
The cycloolefin copolymer is a high value-added thermoplastic engineering plastic polymerized by cycloolefin, and the copolymer has high transparency, excellent heat resistance, low dielectric constant, chemical resistance, and good melt fluidity, barrier property and dimensional stability. Therefore, the cycloolefin copolymer can be widely used for manufacturing various medical materials, optics, information, electric appliances, and the like.
In recent years, cyclic olefin copolymers containing polar functional groups have attracted much attention because of their advantages such as toughness, adhesion, coatability, printability and compatibility with other polymers. There are generally two methods for introducing polar groups: post-functionalization and direct initiation polar monomer polymerization. The former hydrocarbon polymers are difficult to functionalize again and are therefore difficult to achieve. The latter requires that the catalyst have a certain functional group tolerance. The advent of ruthenium catalysts has enabled the polymerization of many polar monomers to produce cyclic olefin copolymers due to the strong tolerance of ruthenium catalysts to polar monomers.
The cycloolefin copolymer provided by the prior art cannot meet the requirement of having good heat resistance and mechanical property while having polarity.
Disclosure of Invention
In view of the above, the present invention is directed to a polar cycloolefin copolymer having good heat resistance and good mechanical properties while having polarity, and a method for preparing the same.
The invention provides a polar cycloolefin copolymer, which has a structure shown in a formula I:
Figure BDA0002800820420000011
110≤a≤600；5≤b≤120。
preferably, 110 ≦ a ≦ 450; b is more than or equal to 10 and less than or equal to 110.
The invention provides a preparation method of the polar cycloolefin copolymer in the technical scheme, which comprises the following steps:
a) carrying out polymerization reaction on a compound with a structure shown in a formula II and a compound with a structure shown in a formula III in a solvent under a carbene type catalyst to obtain a polymerization product;
b) carrying out hydrogenation reaction on the polymerization product and a hydrogen source to obtain a polar cyclic olefin copolymer with a structure shown in a formula I;
Figure BDA0002800820420000021
preferably, the molar ratio of the compound with the structure of the formula II to the compound with the structure of the formula III is 0.5-15: 1;
the molar ratio of the total mole of the compound with the formula II and the compound with the formula III to the carbene-type catalyst is 220-500: 1;
the molar ratio of the polymerization product to the hydrogen source is 1: 3-6.
Preferably, the temperature of the polymerization reaction is 5-60 ℃;
the polymerization reaction time is 60-120 min.
Preferably, the hydrogen source is selected from one or more of alcohol compounds, hydrocarbon compounds, hydrazine compounds and formic acid.
Preferably, the temperature of the hydrogenation reaction is 120-160 ℃;
the hydrogenation reaction time is 10-20 h.
Preferably, the carbene-type catalyst is selected from ruthenium-based carbene catalysts.
The invention provides a polar cycloolefin copolymer which has a structure shown in a formula I. The side chain of the polar cycloolefin copolymer provided by the invention contains a formyl imine group and a benzene ring structure, so that the polar cycloolefin copolymer has polarity, better heat resistance and good mechanical property. In addition, the polar cycloolefin copolymer provided by the invention also has better transparency. The experimental result shows that the contact angle of the cycloolefin copolymer provided by the invention and the water surface is 84.5-103.0 degrees; the glass transition temperature is 130.4-205.9 ℃; the tensile strength is 17.7MPa to 31MPa, the tensile modulus is 1042MPa to 1780MPa, the elongation at break is 1.7 percent to 9.7 percent, and the light transmittance is more than 82 percent.
Drawings
FIG. 1 shows the NMR spectrum of a compound having the structure of formula II prepared in example 1 of the present invention.
Detailed Description
The invention provides a polar cycloolefin copolymer, which has a structure shown in a formula I:
Figure BDA0002800820420000031
110≤a≤600；5≤b≤120。
in the invention, a is more than or equal to 110 and less than or equal to 450; b is more than or equal to 10 and less than or equal to 110.
The invention provides a preparation method of the polar cycloolefin copolymer in the technical scheme, which comprises the following steps:
a) carrying out polymerization reaction on a compound with a structure shown in a formula II and a compound with a structure shown in a formula III in a solvent under a carbene type catalyst to obtain a polymerization product;
b) carrying out hydrogenation reaction on the polymerization product and a hydrogen source to obtain a polar cyclic olefin copolymer with a structure shown in a formula I;
Figure BDA0002800820420000032
according to the invention, under the presence of a carbene-type catalyst, a compound with a structure of a formula II and a compound with a structure of a formula III are subjected to a polymerization reaction in a solvent to obtain a polymerization product. According to the invention, the compound with the structure of the formula II, the compound with the structure of the formula III and the solvent are preferably mixed under stirring. The stirring method in the mixing process is not particularly limited in the present invention, and a stirring technical scheme well known to those skilled in the art may be adopted. In the present invention, the stirring time during the mixing is preferably 5 to 15min, more preferably 8 to 12min, and most preferably 10 min.
The polymerization reaction is preferably carried out in the absence of dry oxygen. In the present invention, the polymerization can be carried out in a Braun glove box or under nitrogen using standard Schizoc (Schlenk) techniques. The polymerization reaction is preferably carried out under stirring conditions in the present invention, and the stirring method for the polymerization reaction is not particularly limited, and a stirring technical scheme well known to those skilled in the art can be adopted.
In the present invention, the polymerization reaction temperature is preferably 5 to 60 ℃, more preferably 10 to 40 ℃, and most preferably 20 to 30 ℃.
The present invention can control the transparency of the cycloolefin copolymer produced by controlling the time of the polymerization reaction. In the present invention, the reaction rate of the compound having the structure represented by formula II is higher than that of the compound having the structure represented by formula III, the polymerization time is controlled so that the compound having the structure represented by formula III is not completely polymerized, and the obtained cyclic olefin copolymer has fewer compounds having the structure represented by formula III, and the fewer compounds having the structure represented by formula III in the cyclic olefin copolymer obtained by the present invention, the better the transparency of the cyclic olefin copolymer. In the present invention, the time for the polymerization reaction is preferably 60 to 120min, more preferably 80 to 120min, and most preferably 100 to 120 min.
In the invention, the carbene type catalyst is preferably selected from ruthenium carbene catalysts which have high activity and good polymerization tolerance, so that a cocatalyst is not required to be added in the preparation process of the cycloolefin copolymer; more preferably, the carbene-type catalyst is selected from compounds having a structure represented by formula IV:
Figure BDA0002800820420000041
in formula IV, L is preferably PCy 3; x is preferably Cl, Br or I; r1Preferably H, Ph or CH2CH3(ii) a R is preferably Cy, Cp or Ph. In the present invention, X in the formula IV is more preferably Cl; r1More preferably Ph; more preferably, R is Cy.
In the present invention, the catalyst is most preferably a compound having a structure represented by formula V:
Figure BDA0002800820420000042
the carbene-type catalyst preferably participates in the polymerization reaction in the form of a catalyst solution. In the present invention, the solvent in the catalyst solution is preferably selected from a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound; more preferably cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform or tetrahydrofuran; most preferred is benzene, toluene, dichloromethane, cyclohexane or tetrahydrofuran. The source of the solvent in the catalyst solution is not particularly limited in the present invention, and any solvent of the above kind known to those skilled in the art may be used, and may be commercially available.
In the present invention, the molar concentration of the catalyst solution is preferably 2.5. mu. mol/mL-4.5. mu. mol/mL, more preferably 3. mu. mol/mL-4. mu. mol/mL, and most preferably 3.3. mu. mol/mL-3.7. mu. mol/mL. In order to sufficiently dissolve the catalyst in the solvent of the catalyst solution, the present invention preferably mixes the catalyst and the solvent of the catalyst solution under ultrasonic conditions to obtain the catalyst solution. The method of the present invention is not particularly limited, and the ultrasonic technical scheme known to those skilled in the art can be adopted. In the invention, the time of the ultrasonic treatment is preferably 2-5 min, and more preferably 3-4 min.
The source of the carbene-based catalyst is not particularly limited in the present invention, and the carbene-based catalyst can be prepared by a preparation method of the above-mentioned catalyst, which is well known to those skilled in the art. In the present invention, the preparation method of the compound having the structure represented by formula V is preferably:
phenyl diazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine are reacted in an organic solvent to obtain a compound with a structure shown in a formula V.
More preferably, the present invention comprises mixing phenyldiazomethane, an organic solvent and dichlorotris (triphenylphosphine) ruthenium, and adding tricyclohexylphosphine to the resulting mixture to carry out a reaction to obtain a compound having a structure represented by formula V. In the present invention, the temperature at which the phenyldiazomethane, the organic solvent and the dichlorotris (triphenylphosphine) ruthenium are mixed is preferably-80 ℃ to-50 ℃, more preferably-78 ℃ to-55 ℃, and most preferably-75 ℃ to-65 ℃. In the present invention, the temperature of the addition of tricyclohexylphosphine is preferably-70 ℃ to-50 ℃, more preferably-60 ℃ to-55 ℃. The reaction of the phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably carried out under the protection of nitrogen. The present invention preferably performs the phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine reactions under stirring. The method for stirring the phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine in the reaction is not particularly limited, and a stirring technical scheme well known to those skilled in the art can be adopted.
In the present invention, the reaction temperature of the phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably-80 ℃ to 30 ℃, more preferably-78 ℃ to-25 ℃, and most preferably-70 ℃ to-20 ℃. In the present invention, the reaction time of the phenyldiazomethane, the dichlorotris (triphenylphosphine) ruthenium and the tricyclohexylphosphine is preferably 30 to 50min, more preferably 35 to 45min, and most preferably 40 min.
The source of the phenyldiazomethane is not particularly limited in the present invention, and the phenyldiazomethane can be obtained from the market, and can also be prepared by the preparation method of the phenyldiazomethane known to the skilled person. In the present invention, the process for producing the phenyldiazomethane is preferably:
and (3) performing a synthetic reaction on benzaldehyde-p-toluenesulfonylhydrazone, sodium methoxide and triethylene glycol to obtain the phenyldiazomethane.
The synthesis reaction is preferably carried out in a water bath. In the present invention, the temperature of the synthesis reaction is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and most preferably 60 ℃. In the present invention, the time of the synthesis reaction is preferably 0.5 to 1.5 hours, and more preferably 1 hour. In the invention, the mass ratio of the benzaldehyde-p-toluenesulfonylhydrazone, the sodium methoxide and the triethylene glycol is preferably 1 (2-3) to (25-35), more preferably 1 (2.4-2.9) to (27-32), and most preferably 1:2.8: 25. The sources of the benzaldehyde-p-toluenesulfonylhydrazone, the sodium methoxide and the triethylene glycol are not particularly limited, and the benzaldehyde-p-toluenesulfonylhydrazone, the sodium methoxide and the triethylene glycol can be purchased from the market.
After the synthesis reaction is finished, the methanol in the obtained synthesis reaction solution is preferably removed to obtain a synthesis reaction product; and extracting and drying the synthetic reaction product to obtain the phenyl diazomethane. The method for removing methanol is not particularly limited, and in the embodiment of the present invention, a mechanical pump may be used to extract methanol from the synthesis reaction solution. According to the invention, the synthetic reaction product is preferably subjected to first extraction by using n-pentane, and then the obtained first extraction product is subjected to second extraction by using a sodium chloride aqueous solution. In the present invention, the aqueous sodium chloride solution is preferably a saturated aqueous sodium chloride solution. In the present invention, the method of drying the synthesis reaction product is preferably spin drying. In the present invention, the temperature at which the synthesis reaction product is dried is preferably-35 ℃ to-45 ℃, more preferably-40 ℃.
In the present invention, the phenyldiazomethane is preferably a pentane solution of phenyldiazomethane. In the present invention, the pentane solution of the phenyldiazomethane preferably has a mass concentration of 90mg/mL to 100mg/mL, more preferably 94mg/mL to 98 mg/mL.
The source of the dichlorotris (triphenylphosphine) ruthenium is not particularly limited in the present invention and may be commercially available.
In the present invention, the tricyclohexylphosphine is preferably a solution of tricyclohexylphosphine in methylene chloride. In the present invention, the concentration by mass of the methylene chloride solution of tricyclohexylphosphine is preferably 0.06 to 0.07g/mL, more preferably 0.064 to 0.068 g/mL. The source of the tricyclohexylphosphine is not particularly limited in the present invention, and it can be commercially available.
In the invention, the mass ratio of the phenyldiazomethane, the dichlorotris (triphenylphosphine) ruthenium and the tricyclohexylphosphine is preferably 1 (3-6) to (1-3.5), more preferably 1 (4-5) to (2-3), and most preferably 1:4.6 to 2.6.
In the present invention, the organic solvent is preferably dichloromethane. The amount of the organic solvent used is not particularly limited, and the organic solvent can provide a liquid environment for the reaction of the phenyldiazomethane, the dichlorotris (triphenylphosphine) ruthenium and the tricyclohexylphosphine. In order to exclude air from the organic solvent, the present invention preferably subjects the organic solvent to liquid nitrogen freeze-thaw treatment. In the present invention, the number of times of the liquid nitrogen freeze-thaw treatment is preferably 3 times. The method for the liquid nitrogen freezing-thawing treatment is not particularly limited, and the technical scheme of the liquid nitrogen freezing-thawing treatment, which is well known to those skilled in the art, can be adopted. The liquid nitrogen freezing-thawing treatment of the organic solvent can be carried out according to the following method:
filling the organic solvent into a test tube, and putting the test tube into liquid nitrogen for freezing;
and vacuumizing the frozen test tube, and then unfreezing the organic solvent in the test tube.
In the invention, air bubbles escape in the process of unfreezing the organic solvent, so that the air in the organic solvent is removed.
After the phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine are finished, the invention preferably filters, dissolves, concentrates, precipitates, washes and dries the obtained reaction solution of phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine to obtain the compound with the structure shown in formula V. The method of filtration, dissolution, concentration, precipitation, washing and drying is not particularly limited in the present invention, and the technical scheme of filtration, dissolution, concentration, precipitation, washing and drying known to those skilled in the art can be adopted. In the present invention, the precipitating agent is preferably methanol. In the present invention, the reagents to be washed after the precipitation of the reaction solution of phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine are preferably methanol and acetone. In the present invention, the method for drying the reaction solution of phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably vacuum drying. In the present invention, the drying time of the reaction solution of phenyldiazomethane, dichlorotris (triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably 2 to 4 hours, and more preferably 3 hours.
The source of the compound having the structure shown in formula II is not particularly limited in the present invention, and the compound can be obtained from the market, or can be prepared by a method for preparing the compound having the structure shown in formula II, which is well known to those skilled in the art. The compound with the structure shown in the formula II is preferably prepared according to the following method:
reacting the norbornadiene, the anthracene and the 2, 6-di-tert-butyl-p-cresol to obtain the compound with the structure shown in the formula II.
The reaction temperature of norbornadiene, anthracene and 2, 6-di-tert-butyl-p-cresol is preferably 180-200 ℃, and the reaction time is preferably 12 hours. According to the invention, the reaction product of norbornadiene, anthracene and 2, 6-di-tert-butyl-p-cresol is preferably cooled, stood, filtered and washed to obtain the compound with the structure shown in the formula II. The method of cooling, standing, filtering and washing is not particularly limited in the present invention, and the technical scheme of cooling, standing, filtering and washing known to those skilled in the art can be adopted. In the present invention, the cooling temperature is preferably 20 to 30 ℃, more preferably 24 to 28 ℃. In the invention, the standing time is preferably 10 to 16 hours, and more preferably 12 to 14 hours. In the present invention, the reagent for washing the reaction product of norbornadiene, anthracene and 2, 6-di-tert-butyl-p-cresol is preferably n-hexane.
The source of the compound with the structure shown in the formula III is not particularly limited in the invention, and the compound can be prepared by adopting a method for preparing the compound with the structure shown in the formula III, which is well known to a person skilled in the art. In the present invention, the compound having the structure represented by the formula III is commercially available. The name of the compound with the structure shown in the formula III is as follows: 5-norbornene-2-methanol.
In the present invention, the kind and source of the polymerization solvent are the same as those of the solvent in the catalyst solution, and thus, the details thereof are not repeated. In the present invention, the solvent for the polymerization reaction may be the same as or different from the solvent in the catalyst solution described in the above technical solution.
The invention can control the contact angle of the prepared cycloolefin copolymer with water and the glass transition temperature by controlling the dosage of the polymerization reaction raw materials. The more the compounds with the structure shown in formula II in the cycloolefin copolymer prepared by the invention are, the larger the contact angle between the cycloolefin copolymer and the water surface is, and the higher the obtained glass transition temperature is. In the invention, the ratio of the total mole number of the compound having the structure shown in formula II and the compound having the structure shown in formula III to the mole number of the catalyst is preferably (50-600): 1, more preferably (100 to 500):1, most preferably (150-450): 1, most preferably (200-400): 1. in the invention, the molar ratio of the compound having the structure shown in the formula II to the compound having the structure shown in the formula III is preferably (2-30): 1, more preferably (3 to 25): 1, most preferably (4-20): 1.
the amount of the polymerization solvent used in the present invention is not particularly limited, and may be any amount known to those skilled in the art. In the invention, the mass ratio of the compound having the structure shown in the formula II to the solvent for the polymerization reaction is preferably 1 (20-30), and more preferably 1 (24-28).
After the polymerization reaction is finished, the polymerization reaction is preferably terminated by adopting a terminator to obtain a polymerization reaction solution; mixing the polymerization reaction solution with a precipitating agent to obtain a precipitated product; and filtering, washing and drying the precipitation product to obtain a polymerization product.
The present invention is not particularly limited in kind and source of the terminator, and any terminator known to those skilled in the art to be used in the preparation of cycloolefin copolymers can be used and commercially available. In the present invention, the terminator is preferably vinyl ethyl ether. In the present invention, the molar ratio of the terminating agent to the catalyst is preferably (100 to 500):1, more preferably (200 to 400):1, and most preferably 300: 1. In the present invention, the time for terminating the polymerization reaction is preferably 20 to 40min, more preferably 25 to 35min, and most preferably 30 min.
After obtaining the polymerization reaction solution, the present invention preferably mixes the polymerization reaction solution with a precipitant to obtain a precipitated product. The kind of the precipitant used in the present invention is not particularly limited, and precipitants known to those skilled in the art for preparing cycloolefin copolymers can be used. In the present invention, the precipitating agent for precipitating the polymerization reaction solution is preferably methanol, more preferably anhydrous methanol. In the present invention, the temperature at which the polymerization reaction solution and the precipitant are mixed is preferably-10 ℃ to 0 ℃, more preferably-8 ℃ to-5 ℃.
After obtaining the precipitated product, the present invention preferably filters, washes, and dries the precipitated product to obtain the polymerization product. The method for filtering, washing and drying the precipitated product is not particularly limited in the present invention, and the technical scheme of filtering, washing and drying, which is well known to those skilled in the art, can be adopted. In the present invention, the agent for washing the precipitated product is preferably acetone. In the present invention, the number of washing times of the precipitated product is preferably 2 to 4, and more preferably 3. In the present invention, the method of drying the precipitated product is preferably vacuum drying. In the present invention, the temperature at which the precipitated product is dried is preferably 20 to 40 ℃, more preferably 25 to 35 ℃, and most preferably 30 ℃. In the present invention, the time for drying the precipitated product is preferably 12 to 24 hours, more preferably 16 to 20 hours, and most preferably 18 hours.
After obtaining the polymerization reaction product, the invention carries out hydrogenation reaction on the polymerization reaction product and a hydrogen source to obtain the polar cycloolefin copolymer. The present invention preferably performs the hydrogenation reaction under protective gas conditions. In the present invention, the protective gas for the hydrogenation reaction is preferably nitrogen. The method of the hydrogenation reaction is not particularly limited in the present invention, and a hydrogenation reaction scheme well known to those skilled in the art may be employed.
The hydrogen source is not particularly limited in kind, and may be hydrogen or an organic hydrogen source, and the organic hydrogen source may be an alcohol compound, a hydrocarbon compound, a hydrazine compound or formic acid. In the present invention, the hydrogen source is preferably an alcohol compound, a hydrocarbon compound, a hydrazine compound or formic acid, more preferably an alcohol compound, a hydrazine compound or formic acid, most preferably isopropanol or tosylhydrazide, most preferably tosylhydrazide; in a particular embodiment, the hydrogen source is selected from p-toluenesulfonyl hydrazide.
In the present invention, when the hydrogen source is an alcohol compound, a hydrocarbon compound, a hydrazine compound or formic acid, the polar cyclic olefin copolymer is preferably prepared by performing the hydrogenation reaction according to the following method:
carrying out hydrogenation reaction on the polymerization reaction product and an organic hydrogen source in a solvent to obtain a polar cyclic olefin copolymer; the organic hydrogen source is an alcohol compound, a hydrocarbon compound, a hydrazine compound or formic acid.
In the invention, the ratio of the number of moles of the double bond in the polymerization reaction product to the number of moles of the organic hydrogen source is preferably 1 (3-6), and more preferably 1 (4-5). In the present invention, the solvent for the hydrogenation reaction is preferably toluene. The amount of the solvent used in the hydrogenation reaction is not particularly limited, and the solvent used may be one that provides a liquid environment for the hydrogenation reaction. In the present invention, the reaction temperature when the polymerization product and the organic hydrogen source are subjected to hydrogenation reaction is preferably 120 to 140 ℃, more preferably 125 to 135 ℃, and most preferably 130 ℃. In the present invention, the reaction time of the hydrogenation reaction of the polymerization product and the organic hydrogen source is preferably 10 to 16 hours, and more preferably 12 to 14 hours.
In order to prevent the cross-linking reaction during the hydrogenation reaction of the polymerization product and the organic hydrogen source, the reaction raw materials during the hydrogenation reaction of the polymerization product and the organic hydrogen source preferably further include a radical scavenger. The present invention is not particularly limited in kind and source of the radical scavenger, and a radical scavenger known to those skilled in the art may be used, and may be commercially available. In the present invention, the radical scavenger is preferably 2, 6-di-tert-butyl-4-methylphenol. The amount of the radical scavenger used in the present invention is not particularly limited, and may be any amount known to those skilled in the art. In the present invention, the amount of the radical scavenger used is preferably 0.05eqv to 7 eqv.
After the hydrogenation reaction is completed, the invention preferably mixes the obtained hydrogenation reaction product with ethanol, and filters, washes and dries the obtained mixed product to obtain the polar cycloolefin copolymer. In the present invention, the purity of the ethanol is preferably 97% to 99%. The method for filtering, washing and drying the mixed product is not particularly limited in the present invention, and the technical scheme of filtering, washing and drying which is well known to those skilled in the art can be adopted. In the present invention, the method for drying the mixed product is preferably vacuum drying. In the invention, the drying time of the mixed product is preferably 12-24 hours, and more preferably 16-20 hours. In the present invention, the drying temperature of the mixed product is preferably 40 to 70 ℃, more preferably 50 to 65 ℃, and most preferably 60 ℃.
The polarity of the polar cycloolefin copolymer is obtained by a static water contact angle test, the hydrophilic performance of the surface of the membrane is tested at room temperature by adopting a DSAKRUSS GMBH 'Hamburg 100' contact angle tester, and the water drop amount is 10 mu l. The test result shows that the polar cycloolefin copolymer provided by the invention has a water contact angle of 92-105 degrees and has better hydrophilicity.
The glass transition temperature of the cycloolefin copolymer is obtained by adopting a differential thermal analysis method and a thermal weight loss method, the detection method is to adopt a Perkin-ElmerPyris1 DSC differential scanning calorimeter to carry out differential thermal analysis and measurement, the rates of temperature rise and temperature reduction are both 10 ℃/min, and secondary scanning is carried out. The weight loss on heating was determined using a Perkin-Elmer Pyris type 1 instrument. The detection result shows that the glass transition temperature of the polar cycloolefin copolymer provided by the invention is 140-220 ℃, and the polar cycloolefin copolymer has better thermal stability.
The mechanical property of the cycloolefin copolymer obtained by the invention is tested on an INSTRON 1121, Canton and MA instrument according to the standard of GB/T1040-1992, Plastic tensile Property test method, the sample strip clamping distance is 20.0mm, the test speed is 5mm/min, and each sample is tested for at least 8 times to ensure the reliability of data. The test result shows that the tensile strength of the polar cycloolefin copolymer provided by the invention is 18MPa to 30MPa, the tensile modulus is 1250MPa to 1780MPa, and the elongation at break is 1.8 percent to 7.1 percent.
The invention adopts Shimadzu UV-3600 ultraviolet-visible light-near infrared spectrophotometer to test the transparency of the obtained cycloolefin copolymer, and the test wavelength is 400 nm-800 nm. The test result shows that the light transmittance of the polar cycloolefin copolymer obtained by the invention is more than 82%.
The invention adopts the molecular weight distribution and the number average molecular weight of the polar cycloolefin copolymer obtained by the gel permeation chromatography test, and the detection method adopts a waters152 type gel permeation chromatograph for determination; detecting by an RI-Laser detector; detecting with tetrahydrofuran as solventThe temperature is 35 ℃; the flow rate of the mobile phase is 1.0mL/min, and PLEasiCalPS-1 is used as a standard sample. The test result shows that the molecular weight distribution of the polar cycloolefin copolymer provided by the invention is 1.20-2.0, and the number average molecular weight is 5.0 multiplied by 104g/mol～12.0×104g/mol。
In order to further illustrate the present invention, a polar cycloolefin copolymer and a method for preparing the same according to the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Sequentially adding 800mL of norbornadiene, 230 g of anthracene and 1g of 2, 6-di-tert-butyl-p-cresol into a 2L stainless steel autoclave, and repeatedly vacuumizing the autoclave for 3 times and then filling nitrogen into the autoclave; the autoclave was heated to 180 ℃ and the contents of the autoclave were allowed to react for 30min with stirring.
After the reaction is finished, the obtained reaction product is cooled to 25 ℃, is kept stand for 12 hours and then is filtered, and the obtained filtered product is washed by normal hexane for 2 times to obtain 260 g of product. The yield of the product prepared by the method provided in example 1 of the invention was 75%.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum detection, as shown in fig. 1, and the detection result shows that the product obtained in the embodiment 1 of the invention is a compound with a structure shown in a formula II.
Example 2
4.96 g of benzaldehyde-p-toluenesulfonylhydrazone, 1.75 g of sodium methoxide and 40mL of triethylene glycol were put into a 100mL single-neck flask, and the single-neck flask was placed in a water bath at 60 ℃ to perform a synthesis reaction for 1 hour.
After the synthesis reaction is finished, pumping out methanol in the obtained synthesis reaction solution by using a water pump to obtain a synthesis reaction product; extracting the synthetic reaction product in ice water by using n-pentane, extracting by using a saturated NaCl aqueous solution, and spin-drying the obtained extraction product to obtain phenyl diazomethane; the yield of the phenyldiazomethane was 50%.
Adding 4.0 g of dichlorotris (triphenylphosphine) ruthenium into a 250mL branched bottle, introducing nitrogen to replace the air in the branched bottle, and injecting 40mL of dichloromethane subjected to three times of liquid nitrogen freezing-thawing treatment into the branched bottle; placing the mouth-branched bottle in a cooling bath at the temperature of minus 78 ℃, adding 10mL of pentane solution of phenyldiazomethane with the mass concentration of 98.5mg/mL at the temperature of minus 50 ℃ under the condition of stirring, and mixing, wherein the phenyldiazomethane in the pentane solution of the phenyldiazomethane is the phenyldiazomethane prepared above; the resulting mixture was stirred at-70 ℃ for 10min, and then 40mL of a solution of tricyclohexylphosphine in methylene chloride at-50 ℃ and a mass concentration of 0.064g/mL were added to conduct a reaction at 25 ℃ for 30 min.
After the reaction is finished, filtering the obtained reaction solution to remove insoluble substances, concentrating the filtered reaction solution to 10mL, filtering again, adding 100mL of methanol subjected to liquid nitrogen freeze-thaw treatment for three times into the obtained filtered product for precipitation, washing the obtained precipitate with methanol for three times, then washing with acetone for two times, and carrying out vacuum drying on the washed precipitate for 3 hours to obtain 2.3g of a product. The yield of the product prepared by the method provided by the embodiment 2 of the invention is 82%.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum and phosphorus spectrum detection, and the detection result shows that the product obtained in the embodiment 2 of the invention is a compound with a structure shown in the formula V.
Example 3
1.396g of the compound having the structure represented by the formula II prepared in example 1, 0.090g of the compound having the structure of the formula III and 25mL of dichloromethane were added to a dry polymerization flask at 25 ℃, and mixed for 10min with stirring to obtain a mixture; adding 15.9mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring for polymerization reaction for 15 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.42g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 3 of the present invention was 97.5%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.12g of a cycloolefin copolymer. The method of hydrogenation provided in example 3 of the present invention gave a cycloolefin copolymer in a yield of 82.3%.
According to the method of the technical scheme, nuclear magnetic resonance hydrogen spectrum detection is performed on the polymerization reaction product and the cyclic olefin copolymer obtained in the embodiment 3 of the invention, the molar content of the compound with the structure shown in the formula II in the cyclic olefin copolymer obtained in the embodiment 3 of the invention is 90.8%, the double bond peak of the polymerization reaction product obtained in the embodiment 3 of the invention completely disappears after hydrogenation reaction, and the hydrogenation effect is good.
As can be seen from the gel permeation chromatography detection, the cycloolefin copolymer obtained in example 3 of the present invention had a molecular weight distribution of 1.42 and a number average molecular weight of 5.3X 104g/mol。
The cyclic olefin copolymer obtained in example 3 of the present invention was subjected to the static water contact angle test according to the method described in the above technical solution, and the contact angle between the cyclic olefin copolymer obtained in example 3 of the present invention and water was 103.0 °.
According to the technical scheme, the cyclic olefin copolymer obtained in the embodiment 3 is tested by a differential thermal analysis method, and the cyclic olefin copolymer obtained in the embodiment 3 has the decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 3 of the present invention were tested according to the method described in the above technical solution, and the test results show that the cycloolefin copolymer obtained in example 3 of the present invention has an elongation at break of 2.5%, a tensile strength of 24.8MPa, and a tensile modulus of 1198 MPa.
The transparency of the cycloolefin copolymer obtained in example 3 according to the invention was tested by the method described in the above-mentioned technical solution, and the light transmittance of the cycloolefin copolymer obtained in example 3 according to the invention was > 82%.
Example 4
Adding 1.31g of the compound having the structure shown in the formula II prepared in the example 1, 0.19g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 16.7mg of the compound with the structure shown in the formula V prepared in the example 2 into a small ampoule, adding 5mL of dichloromethane into the small ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into the dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.48g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 4 of the present invention was 98.6%.
1.3g of the above-mentioned polymerization reaction product, 5.37g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.29g of a cycloolefin copolymer. The method of hydrogenation provided in example 4 of the present invention gave a cycloolefin copolymer in a yield of 97.1%.
When the cycloolefin copolymer obtained in example 4 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 81.8%.
The cycloolefin copolymer obtained in example 4 of the present invention was subjected to gel permeation chromatography according to the method described in the above technical solution, and the result of the gel permeation chromatography test was that the cycloolefin copolymer obtained in example 4 of the present invention had a molecular weight distribution of 1.49 and a number average molecular weight of 9.9X 104g/mol。
The cyclic olefin copolymer obtained in example 4 of the present invention was subjected to the static water contact angle test according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 4 of the present invention has a contact angle with water of 100.3 °.
The cycloolefin copolymer obtained in example 4 according to the invention was subjected to a differential thermal analysis test as described in the above-mentioned protocol, the result being that the cycloolefin copolymer obtained in example 4 according to the invention had a glass transition temperature of 188.3 ℃. According to the technical scheme, the thermal weight loss method test is carried out on the cycloolefin copolymer obtained in the embodiment 4 of the invention, and the test result shows that the cycloolefin copolymer obtained in the embodiment 4 of the invention has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 4 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 4 of the present invention had an elongation at break of 3.8%, a tensile strength of 22.6MPa, and a tensile modulus of 1160 MPa.
The transparency of the cycloolefin copolymer obtained in example 4 of the present invention was tested according to the method described in the above technical solution, and the test result showed that the transmittance of the cycloolefin copolymer obtained in example 4 of the present invention was > 82%.
Example 5
Adding 1.20g of the compound having the structure shown in the formula II prepared in the example 1, 0.296g of the compound having the structure shown in the formula III and 20mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 17.6mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.49g of a polymerization product. The polymerization reaction product obtained by the polymerization method provided in example 5 of the present invention had a yield of 99.6%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.05g of a cycloolefin copolymer. The method of hydrogenation provided in example 5 of the present invention gave a cycloolefin copolymer in a yield of 80.7%.
When the cycloolefin copolymer obtained in example 5 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 72.5%.
The cycloolefin copolymer obtained in example 5 of the present invention was subjected to the gel permeation chromatography test according to the method described in the above technical solution, and the test result showed that the cycloolefin copolymer obtained in example 5 of the present invention had a molecular weight distribution of 1.43 and a number average molecular weight of 5.2X 104g/mol。
The cyclic olefin copolymer obtained in example 5 of the present invention was subjected to the static water contact angle test according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 5 of the present invention has a contact angle with water of 96.9 °.
The cycloolefin copolymer obtained in example 5 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned technical solution, and the test result showed that the cycloolefin copolymer obtained in example 5 according to the invention had a glass transition temperature of 171.6 ℃. According to the technical scheme, the cyclic olefin copolymer obtained in the embodiment 5 of the invention is subjected to a thermogravimetric test, and the test result shows that the cyclic olefin copolymer obtained in the embodiment 5 of the invention has a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 5 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 5 of the present invention had an elongation at break of 4.5%, a tensile strength of 23.6MPa, and a tensile modulus of 1120 MPa.
The cyclic olefin copolymer obtained in example 5 of the present invention was tested for transparency according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 5 of the present invention has a light transmittance of > 83%.
Example 6
Adding 1.08g of the compound having the structure shown in the formula II prepared in the example 1, 0.415g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 18.3mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.08g of a polymerization product. The polymerization process provided in example 6 of the present invention gave a polymerization product yield of 72.2%.
1.3g of the above-mentioned polymerization reaction product, 2.69g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.19g of a cycloolefin copolymer. The method of hydrogenation provided in example 6 of the present invention gave a cycloolefin copolymer in a yield of 91.5%.
When the cycloolefin copolymer obtained in example 6 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 62.5%.
The gel permeation chromatography test of the cycloolefin copolymer obtained in example 6 of the present invention was carried out according to the method described in the above technical solution, and the test resultsThe cycloolefin copolymer obtained in example 6 according to the invention had a molecular weight distribution of 1.29 and a number-average molecular weight of 9.7X 104g/mol。
The cyclic olefin copolymer obtained in example 6 according to the present invention was subjected to the static water contact angle test according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 6 according to the present invention had a contact angle with water of 94.4 °.
The cycloolefin copolymer obtained in example 6 according to the invention was subjected to a differential thermal analysis test as described in the above-mentioned protocol, and the test result showed that the cycloolefin copolymer obtained in example 6 according to the invention had a glass transition temperature of 150.5 ℃. According to the technical scheme, the thermal weight loss method test is carried out on the cycloolefin copolymer obtained in the embodiment 6 of the invention, and the test result shows that the cycloolefin copolymer obtained in the embodiment 6 of the invention has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 6 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 6 of the present invention had an elongation at break of 7.1%, a tensile strength of 21.7MPa, and a tensile modulus of 1042 MPa.
The transparency of the cycloolefin copolymer obtained in example 6 according to the present invention was measured by the method described in the above technical solution, and the result of the measurement was that the transmittance of the cycloolefin copolymer obtained in example 6 according to the present invention was > 82%.
Example 7
0.80g of the compound having the structure represented by the formula II prepared in example 1, 0.694g of the compound having the structure represented by the formula III and 25mL of methylene chloride were added to a dry polymerization flask at 25 ℃ and mixed with stirring for 10min to obtain a mixture; adding 20.7mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.45g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 7 of the present invention was 97.0%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.26g of a cycloolefin copolymer. The method of hydrogenation provided in example 7 of the present invention gave a cycloolefin copolymer in a yield of 96.9%.
When the cycloolefin copolymer obtained in example 7 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 41.3%.
The gel permeation chromatography test of the cycloolefin copolymer obtained in example 7 of the present invention was carried out according to the method described in the above technical solution, and the test result shows that the cycloolefin copolymer obtained in example 7 of the present invention had a molecular weight distribution of 1.31 and a number average molecular weight of 10.8X 104g/mol。
The cyclic olefin copolymer obtained in example 7 of the present invention was subjected to the static water contact angle test according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 7 of the present invention had a contact angle with water of 84.5 °.
The cycloolefin copolymer obtained in example 7 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned protocol, and the test result showed that the cycloolefin copolymer obtained in example 7 according to the invention had a glass transition temperature of 130.4 ℃. According to the technical scheme, the thermal weight loss method test is carried out on the cycloolefin copolymer obtained in the embodiment 7 of the invention, and the test result shows that the cycloolefin copolymer obtained in the embodiment 7 of the invention has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 7 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 7 of the present invention had an elongation at break of 9.7%, a tensile strength of 17.7MPa, and a tensile modulus of 1190 MPa.
The cyclic olefin copolymer obtained in example 7 of the present invention was tested for transparency according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 7 of the present invention had a light transmittance of > 82%.
Example 8
1.397g of the compound having the structure represented by the formula II prepared in example 1, 0.0698g of the compound having the structure represented by the formula III and 25mL of dichloromethane were added to a dry polymerization flask at 25 ℃ and mixed for 10min with stirring to obtain a mixture; adding 15.3mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.47g of a polymerization product. The polymerization reaction product obtained by the polymerization method provided in example 8 of the present invention had a yield of 99.0%.
1.3g of the above-mentioned polymerization reaction product, 2.69g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.05g of a cycloolefin copolymer. The method of hydrogenation provided in example 8 of the present invention gave a cycloolefin copolymer in a yield of 70.0%.
When the cycloolefin copolymer obtained in example 8 according to the invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure of the formula II in the cycloolefin copolymer was 96.3%.
The cycloolefin copolymer obtained in example 8 of the present invention was subjected to gel permeation chromatography according to the method described in the above technical solution, and the result of the gel permeation chromatography test was that the cycloolefin copolymer obtained in example 8 of the present invention had a molecular weight distribution of 1.41 and a number average molecular weight of 6.6X 104g/mol。
According to the method of the technical scheme, the cyclic olefin copolymer obtained in the embodiment 8 of the invention is subjected to a static water contact angle test, and the contact angle of the cyclic olefin copolymer obtained in the embodiment 8 of the invention with water is 95.4 degrees.
The cycloolefin copolymer obtained in example 8 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned technical solution, and the test result showed that the cycloolefin copolymer obtained in example 8 according to the invention had a glass transition temperature of 205.9 ℃. According to the method of the technical scheme, the cyclic olefin copolymer obtained in the embodiment 8 of the invention is tested by a thermal weight loss method, and the cyclic olefin copolymer obtained in the embodiment 8 of the invention has a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 8 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 8 of the present invention had an elongation at break of 1.7%, a tensile strength of 22.4MPa, and a tensile modulus of 1580 MPa.
The transparency of the cycloolefin copolymer obtained in example 8 according to the present invention was tested by the method described in the above technical solution, and the test result showed that the transmittance of the cycloolefin copolymer obtained in example 8 according to the present invention was > 82%.
Example 9
Adding 1.365g of the compound having the structure shown in the formula II and prepared in the example 1, 0.14g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 14.1mg of the compound with the structure shown in the formula V prepared in the example 2 into a small ampoule, adding 5mL of dichloromethane into the small ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into the dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.5g of a polymerization product. The polymerization process provided in example 9 of the present invention gave a polymerization product with a yield of 100%.
1.2g of the above-mentioned polymerization reaction product, 4.13g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.12g of a cycloolefin copolymer. The hydrogenation process of the present invention as provided in example 9 gave a cycloolefin copolymer in a yield of 86.2%.
When the cycloolefin copolymer obtained in example 9 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 90.0%.
The gel permeation chromatography test of the cycloolefin copolymer obtained in example 9 of the present invention was carried out according to the method described in the above technical solution, and the test result shows that the cycloolefin copolymer obtained in example 9 of the present invention had a molecular weight distribution of 1.26 and a number average molecular weight of 10.3X 104g/mol。
The cyclic olefin copolymer obtained in example 9 of the present invention was tested for static water contact angle according to the method described in the above technical solution, and the cyclic olefin copolymer obtained in example 9 of the present invention had a contact angle with water of 94.5 °.
The cycloolefin copolymer obtained in example 9 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned technical scheme, and the test result showed that the cycloolefin copolymer obtained in example 9 according to the invention had a glass transition temperature of 189.7 ℃. According to the method of the technical scheme, the cyclic olefin copolymer obtained in the embodiment 9 of the invention is tested by a thermal weight loss method, so that the cyclic olefin copolymer obtained in the embodiment 9 of the invention has a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 9 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 9 of the present invention had an elongation at break of 1.8%, a tensile strength of 22.0MPa, and a tensile modulus of 1250 MPa.
The transparency of the cycloolefin copolymer obtained in example 9 according to the present invention was tested by the method described in the above technical solution, and as a result, the transmittance of the cycloolefin copolymer obtained in example 9 according to the present invention was > 82%.
Example 10
Adding 1.31g of the compound having the structure shown in the formula II prepared in the example 1, 0.19g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 15.3mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.5g of a polymerization product. The polymerization process provided in example 10 of the present invention gave a polymerization product with a yield of 100%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.12g of a cycloolefin copolymer. The method of hydrogenation provided in example 10 of the present invention gave a cycloolefin copolymer in a yield of 86.2%.
When the cycloolefin copolymer obtained in example 10 of the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 86.5%.
The cycloolefin copolymer obtained in example 10 of the present invention was subjected to the gel permeation chromatography test according to the method described in the above technical solution, and the test result shows that the cycloolefin copolymer obtained in example 10 of the present invention had a molecular weight distribution of 1.28 and a number average molecular weight of 9.7X 104g/mol。
The cyclic olefin copolymer obtained in example 10 of the present invention was tested for the static water contact angle according to the method described in the above technical solution, and the cyclic olefin copolymer obtained in example 10 of the present invention had a contact angle with water of 94.1 °.
According to the method of the technical scheme, the cycloolefin copolymer obtained in the embodiment 10 of the invention is tested by the differential thermal analysis method, the cycloolefin copolymer obtained in the embodiment 10 of the invention has no melting temperature and is amorphous, and the glass transition temperature of the cycloolefin copolymer obtained in the embodiment 10 of the invention is 172.5 ℃. According to the technical scheme, the cyclic olefin copolymer obtained in the embodiment 10 of the invention is subjected to a thermogravimetric test, and the test result shows that the cyclic olefin copolymer obtained in the embodiment 10 of the invention has a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 10 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 10 of the present invention had an elongation at break of 2.0%, a tensile strength of 20.4MPa, and a tensile modulus of 1320 MPa.
The cyclic olefin copolymer obtained in example 10 of the present invention was tested for transparency according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 10 of the present invention has a light transmittance of > 82%.
Example 11
Adding 1.42g of the compound having the structure shown in the formula II prepared in the example 1, 0.084g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 15.3mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.5g of a polymerization product. The polymerization process provided in example 12 of the present invention gave a polymerization product with a yield of 100%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.12g of a cycloolefin copolymer. The method of hydrogenation provided in example 12 of the present invention gave a cycloolefin copolymer in a yield of 86.2%.
When the cycloolefin copolymer obtained in example 11 according to the invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure of the formula II in the cycloolefin copolymer was 94.8%.
The cycloolefin copolymer obtained in example 11 according to the invention was subjected to the gel permeation chromatography test as described in the above-mentioned protocol, and the test result showed that the cycloolefin copolymer obtained in example 11 according to the invention had a molecular weight distribution of 1.39 and a number average molecular weight of 9.9X 104g/mol。
The cyclic olefin copolymer obtained in example 11 of the present invention was tested for the static water contact angle according to the method described in the above technical solution, and the cyclic olefin copolymer obtained in example 11 of the present invention had a contact angle with water of 96.8 °.
The cycloolefin copolymer obtained in example 11 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned protocol, and the test result showed that the cycloolefin copolymer obtained in example 11 according to the invention had a glass transition temperature of 194.7 ℃. According to the technical scheme, the cyclic olefin copolymer obtained in the embodiment 11 of the invention is tested by a thermal weight loss method, and the cyclic olefin copolymer obtained in the embodiment 11 of the invention is tested to have a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 11 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 11 of the present invention had an elongation at break of 2.1%, a tensile strength of 30.8MPa, and a tensile modulus of 1630 MPa.
The cyclic olefin copolymer obtained in example 11 of the present invention was tested for transparency according to the method described in the above technical solution, and the test result shows that the cyclic olefin copolymer obtained in example 11 of the present invention had a light transmittance of > 82%.
Example 12
Adding 1.23g of the compound having the structure shown in the formula II prepared in the example 1, 0.168g of the compound having the structure shown in the formula III and 25mL of dichloromethane into a dry polymerization reaction bottle at 25 ℃, and stirring and mixing for 10min to obtain a mixture; adding 15.3mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 1.48g of a polymerization product. The polymerization reaction product obtained by the polymerization method provided in example 12 of the present invention had a yield of 98.7%.
1.3g of the above-mentioned polymerization reaction product, 4.48g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 40mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 40mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.25g of a cycloolefin copolymer. The method of hydrogenation provided in example 13 of the present invention gave a cycloolefin copolymer in a yield of 96.2%.
When the cycloolefin copolymer obtained in example 12 according to the present invention was examined for its structure in accordance with the method described in example 3, the molar content of the compound having the structure represented by the formula II in the cycloolefin copolymer was 89.5%.
The cycloolefin copolymer obtained in example 12 of the present invention was subjected to the gel permeation chromatography test according to the method described in the above technical solution, and the test result showed that the cycloolefin copolymer obtained in example 12 of the present invention had a molecular weight distribution of 1.31 and a number average molecular weight of 10.1X 104g/mol。
The cyclic olefin copolymer obtained in example 12 of the present invention was tested for static water contact angle according to the method described in the above technical solution, and the cyclic olefin copolymer obtained in example 12 of the present invention had a contact angle with water of 93.9 °.
The cycloolefin copolymer obtained in example 12 according to the invention was subjected to a differential thermal analysis test in accordance with the method described in the above-mentioned protocol, and the test result showed that the cycloolefin copolymer obtained in example 12 according to the invention had a glass transition temperature of 176.4 ℃. According to the technical scheme, the cyclic olefin copolymer obtained in the embodiment 12 of the invention is subjected to a thermogravimetric test, and the test result shows that the cyclic olefin copolymer obtained in the embodiment 12 of the invention has a decomposition rate of 10% at 350 ℃, and has better thermal stability.
The mechanical properties of the cycloolefin copolymer obtained in example 12 of the present invention were tested according to the method described in the above technical solution, and the test results showed that the cycloolefin copolymer obtained in example 12 of the present invention had an elongation at break of 2.8%, a tensile strength of 31MPa, and a tensile modulus of 1780 MPa.
The transparency of the cycloolefin copolymer obtained in example 12 of the present invention was tested by the method described in the above technical solution, and the test result showed that the transmittance of the cycloolefin copolymer obtained in example 12 of the present invention was > 82%
Comparative example 1
The preparation of the cycloolefin copolymer according to the method described in the above example gave a cycloolefin homopolymer having a structure of the formula II:
2.0g of the compound having the structure represented by the formula II prepared in example 1 and 25mL of methylene chloride were added to a dry polymerization reaction flask at 25 ℃ and stirred and mixed for 10min to obtain a mixture; adding 20.32mg of the compound with the structure shown in the formula V prepared in the example 2 into a ampoule, adding 5mL of dichloromethane into the ampoule, and carrying out ultrasonic treatment for 3min to fully dissolve the compound with the structure shown in the formula V into dichloromethane to obtain a compound solution with the structure shown in the formula V; adding the compound solution with the structure shown in the formula V into the polymerization reaction bottle under the condition of stirring to perform polymerization reaction for 120 min;
after the polymerization reaction is finished, adding 300eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; pouring the obtained polymerization reaction solution into anhydrous methanol after 30min to obtain a precipitate product; the precipitated product was filtered, washed 3 times with acetone, and dried in a vacuum oven at 40 ℃ for 12 hours to obtain 2.0g of a polymerization product. The polymerization process provided in comparative example 1 of the present invention gave a polymerization product with a yield of 100%.
2.0g of the above-mentioned polymerization reaction product, 6.8g of p-toluenesulfonylhydrazide, 7eqv of 2, 6-di-t-butyl-4-methylphenol (BHT) and 60mL of toluene were sequentially added to a dry polymerization reaction flask, and the mixture was stirred under reflux at 130 ℃ for 16 hours to conduct hydrogenation reaction, thereby obtaining a hydrogenation reaction product; the hydrogenation reaction product was dropped into 300mL of 98% pure ethanol, the resulting mixture was filtered and drained, and then dissolved again in 60mL of toluene at 120 ℃ for 30min, the dissolved solution was added again to 300mL of 98% pure ethanol, and the resulting mixture was placed in a vacuum oven and dried at 60 ℃ for 12 hours to obtain 1.88g of a cycloolefin copolymer. The method of hydrogenation provided in comparative example 1 of the present invention gave a cycloolefin copolymer in a yield of 94.0%.
The gel permeation chromatography test of the cycloolefin homopolymer obtained in comparative example 1 of the present invention was performed according to the method described in the above technical solution, and the test result shows that the cycloolefin homopolymer obtained in comparative example 1 of the present invention has a molecular weight distribution of 1.34 and a number average molecular weight of 12.7 × 105g/mol。
According to the method of the technical scheme, the cycloolefin homopolymer obtained in the comparative example 1 of the invention is subjected to a static water contact angle test, and the contact angle of the cycloolefin homopolymer obtained in the comparative example 1 of the invention and water is 103.2 degrees.
According to the method of the technical scheme, the cycloolefin homopolymer obtained in the comparative example 1 of the invention is tested by differential thermal analysis, the cycloolefin homopolymer obtained in the comparative example 1 of the invention has no melting temperature and is amorphous, and the glass transition temperature of the cycloolefin homopolymer obtained in the comparative example 1 of the invention is 218.8 ℃.
The cycloolefin homopolymer obtained in comparative example 1 of the present invention had an elongation at break of 1.9%, a tensile strength of 28.8MPa and a tensile modulus of 1910 MPa.
The transparency of the cycloolefin homopolymer obtained in comparative example 1 of the present invention was tested according to the method described in the above technical solution, and the transmittance of the cycloolefin homopolymer obtained in comparative example 1 of the present invention was > 82%.
The structure and properties of the cycloolefin homopolymer obtained in comparative example 1 of the present invention were measured according to the method described in example 3, and it was found that the cycloolefin homopolymer obtained in comparative example 1 of the present invention was inferior in hydrophilicity to those of the above examples, had a higher glass transition temperature than those of the above examples, and had a slightly lower elongation at break.
From the above examples, it can be seen that the present invention provides a polar cycloolefin copolymer having a structure according to formula I. The side chain of the polar cycloolefin copolymer provided by the invention contains a formyl imine group and a benzene ring structure, so that the polar cycloolefin copolymer has polarity, better heat resistance and good mechanical property. In addition, the polar cycloolefin copolymer provided by the invention also has better transparency. The experimental result shows that the contact angle of the cycloolefin copolymer provided by the invention and the water surface is 84.5-103.0 degrees; the glass transition temperature is 130.4-205.9 ℃; the tensile strength is 17.7MPa to 31MPa, the tensile modulus is 1042MPa to 1780MPa, the elongation at break is 1.7 percent to 9.7 percent, and the light transmittance is more than 82 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A polar cyclic olefin copolymer having the structure of formula I:
Figure FDA0002800820410000011
110≤a≤600；5≤b≤120。
2. the polar cycloolefin copolymer according to claim 1, characterized in that 110. ltoreq. a.ltoreq.450; b is more than or equal to 10 and less than or equal to 110.
3. A method for preparing a polar cycloolefin copolymer according to any one of claims 1 to 2, comprising the steps of:
a) carrying out polymerization reaction on a compound with a structure shown in a formula II and a compound with a structure shown in a formula III in a solvent under a carbene type catalyst to obtain a polymerization product;
b) carrying out hydrogenation reaction on the polymerization product and a hydrogen source to obtain a polar cyclic olefin copolymer with a structure shown in a formula I;
Figure FDA0002800820410000012
4. the preparation method according to claim 3, wherein the molar ratio of the compound with the structure of formula II to the compound with the structure of formula III is 0.5-15: 1;
the molar ratio of the total mole of the compound with the formula II and the compound with the formula III to the carbene-type catalyst is 220-500: 1;
the molar ratio of the polymerization product to the hydrogen source is 1: 3-6.
5. The method according to claim 3, wherein the polymerization reaction temperature is 5 to 60 ℃;
the polymerization reaction time is 60-120 min.
6. The preparation method according to claim 3, wherein the hydrogen source is one or more selected from the group consisting of alcohol compounds, hydrocarbon compounds, hydrazine compounds and formic acid.
7. The method according to claim 3, wherein the temperature of the hydrogenation reaction is 120 to 160 ℃;
the hydrogenation reaction time is 10-20 h.
8. The method according to claim 3, wherein the carbene-based catalyst is selected from ruthenium-based carbene catalysts.
CN202011349360.4A 2020-11-26 2020-11-26 Polar cycloolefin copolymer and preparation method thereof Pending CN112480374A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011349360.4A CN112480374A (en) 2020-11-26 2020-11-26 Polar cycloolefin copolymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011349360.4A CN112480374A (en) 2020-11-26 2020-11-26 Polar cycloolefin copolymer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112480374A true CN112480374A (en) 2021-03-12

Family

ID=74935177

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011349360.4A Pending CN112480374A (en) 2020-11-26 2020-11-26 Polar cycloolefin copolymer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112480374A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115850581A (en) * 2022-12-01 2023-03-28 无锡阿科力科技股份有限公司 Cycloolefin copolymer and preparation method and application thereof
WO2023107787A1 (en) * 2021-12-06 2023-06-15 Exxonmobil Chemical Patents Inc. Functional cyclic olefin polymer, process for obtaining the same and compositions containing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910329A (en) * 2015-06-04 2015-09-16 天津大学 Polar cycloolefin copolymer and preparation method thereof
CN105348442A (en) * 2015-10-26 2016-02-24 中国科学院长春应用化学研究所 Cycloolefine copolymer and preparation method thereof
CN105367713A (en) * 2015-10-26 2016-03-02 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN107216444A (en) * 2017-07-20 2017-09-29 中国科学院长春应用化学研究所 A kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof
CN107226888A (en) * 2017-07-20 2017-10-03 中国科学院长春应用化学研究所 A kind of cyclic olefine copolymer and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910329A (en) * 2015-06-04 2015-09-16 天津大学 Polar cycloolefin copolymer and preparation method thereof
CN105348442A (en) * 2015-10-26 2016-02-24 中国科学院长春应用化学研究所 Cycloolefine copolymer and preparation method thereof
CN105367713A (en) * 2015-10-26 2016-03-02 中国科学院长春应用化学研究所 Cycloolefin copolymer and preparation method thereof
CN107216444A (en) * 2017-07-20 2017-09-29 中国科学院长春应用化学研究所 A kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof
CN107226888A (en) * 2017-07-20 2017-10-03 中国科学院长春应用化学研究所 A kind of cyclic olefine copolymer and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023107787A1 (en) * 2021-12-06 2023-06-15 Exxonmobil Chemical Patents Inc. Functional cyclic olefin polymer, process for obtaining the same and compositions containing the same
CN115850581A (en) * 2022-12-01 2023-03-28 无锡阿科力科技股份有限公司 Cycloolefin copolymer and preparation method and application thereof
CN115850581B (en) * 2022-12-01 2024-03-19 无锡阿科力科技股份有限公司 Cycloolefin copolymer and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN104910329B (en) A kind of polar cyclic olefin copolymer and preparation method thereof
EP3075764B1 (en) Hydrophilically modified fluorinated membrane
CN112480374A (en) Polar cycloolefin copolymer and preparation method thereof
CN108840994B (en) Synthesis method of random copolymer containing α -D-mannose and β -D-glucose
WO2003085025A1 (en) Norbornene-based ring-opening polymerization polymer, product of hydrogenation of norbornene-based ring-opening polymerization polymer, and processes for producing these
TW200906870A (en) Norbornene monomers with epoxy group and polymer material thereof
CN103951786B (en) A kind of cyclic olefine copolymer and preparation method thereof
Al Samak et al. Dramatic solvent effects on ring-opening metathesis polymerization of cycloalkenes
CN107216444B (en) A kind of transparent, high heat resistance cyclic olefine copolymer and preparation method thereof
CN103965402B (en) A kind of cyclic olefine copolymer and its preparation method
JP3264442B1 (en) Novel regioregular copolymer and method for producing the same
KR20070007037A (en) Process for producing cycloolefin addition polymer
CN111285970B (en) Pyrene fluorescent group and epoxy group grafted hyperbranched polyethylene, preparation method thereof and application thereof in preparation of fluorescent epoxy resin
CN112745431A (en) Cycloolefin copolymer and preparation method thereof
CN105367713A (en) Cycloolefin copolymer and preparation method thereof
CN103951787B (en) A kind of cyclic olefine copolymer and preparation method thereof
CN103951775B (en) A kind of cyclic olefine copolymer and preparation method thereof
Yang et al. Ring‐opening metathesis polymerization as a route to controlled copolymers of ethylene and polar monomers: Synthesis of ethylene–vinyl chloride‐like copolymers
CN112646126B (en) Method for preparing cycloolefin polymer by hydrogenation ring-opening metathesis polymerization method
WO2015176588A1 (en) Cycloolefin copolymer and preparation method therefor
Wang et al. Synthesis of polymethylene-b-poly (vinyl acetate) block copolymer via visible light induced radical polymerization and its application
CN113307963B (en) Method for synthesizing glycidyl linear polymer
CN107226888A (en) A kind of cyclic olefine copolymer and preparation method thereof
Chang et al. Palladium catalyzed vinyl addition poly (norbornenes): silane chain transfer agents, hydroxyl group activators and their impact on optical density at 193 nm
US9724686B2 (en) Sulfonated polyethylene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210312