CYCLIC OLEFIN POLYMER HAVING EPOXY FUNCTIONAL GROUP PREPARED BY RING-OPENING METATHESIS POLYMERIZATION

Abstract

The present disclosure relates to a cyclic olefin polymer having an epoxy functional group prepared by ring-opening metathesis polymerization and method of preparing the same.

Claims

1. A cyclic olefin polymer that is produced by ring-opening metathesis polymerization of at least one monomer(s) selected from dicyclopentadiene having an epoxy group represented by the following Chemical Formula 1 and tricyclopentadiene having an epoxy group represented by the following Chemical Formula 2; or by ring-opening metathesis polymerization of at least one monomer(s) selected from the dicyclopentadiene having an epoxy group and the tricyclopentadiene having an epoxy group, and a norbornene monomer represented by the following Chemical Formula 3; and wherein the cyclic olefin polymer includes repeating units represented by the following Chemical Formula 4, Chemical Formula 5, Chemical Formula 6, Chemical Formula 7, Chemical Formula 8, or Chemical Formula 9: ##STR00015## ##STR00016## wherein, in the above Chemical Formula 3, Chemical Formula 4, Chemical Formula 5, Chemical Formula 6, Chemical Formula 7, Chemical Formula 8, and Chemical Formula 9, n is an integer of 5 to 5,000, m is an integer of 5 to 5,000, l is an integer of 5 to 5,000, each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

2. The cyclic olefin polymer of claim 1, wherein a polydispersity index of the cyclic olefin polymer is 1 to 1.3.

3. A hydrogenated cyclic olefin polymer that is produced by hydrogenation of a cyclic olefin polymer of claim 1, and wherein the hydrogenated cyclic polymer includes repeating units represented by the following Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, or Chemical Formula 15: ##STR00017## wherein, in the above Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, and Chemical Formula 15, n is an integer of 5 to 5,000, m is an integer of 5 to 5,000, l is an integer of 5 to 5,000, each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

4. The hydrogenated cyclic olefin polymer of claim 3, wherein the hydrogenated cyclic olefin polymer is used in preparing an optically-isotropic film.

5. The hydrogenated cyclic olefin polymer of claim 4, wherein the film has a glass transition temperature of at least 150° C.

6. The hydrogenated cyclic olefin polymer of claim 4, wherein the film has a transmittance of at least 80% in a visible light region.

7. A method of preparing a hydrogenated cyclic olefin polymer, comprising: (a) polymerizing at least one monomer(s) selected from dicyclopentadiene having an epoxy group represented by the following Chemical Formula 1 and tricyclopentadiene having an epoxy group represented by the following Chemical Formula 2; or at least one monomer(s) selected from the dicyclopentadiene having an epoxy group and the tricyclopentadiene having an epoxy group, and a norbornene monomer represented by the following Chemical Formula 3; in the presence of a first-generation Grubbs catalyst to obtain a cyclic olefin polymer; and (b) hydrogenating the cyclic olefin polymer to obtain a hydrogenated cyclic olefin polymer that includes repeating units represented by the following Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, or Chemical Formula 15: ##STR00018## ##STR00019## wherein, in the above Chemical Formula 3, Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, and Chemical Formula 15, n is an integer of 5 to 5,000, m is an integer of 5 to 5,000, l is an integer of 5 to 5,000, each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

8. The method of claim 7, wherein the step of (b) is performed in the presence of a Pd/C catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG. 1A is a .sup.1H NMR spectrum of epoxidized dicyclopentadiene which is a monomer compound 1 prepared according to an example of the present disclosure, and FIG. 1B is a .sup.13C NMR spectrum of the compound.

[0043] FIG. 2A is a .sup.1H NMR spectrum of a polymer represented by poly(1) in a Reaction Formula 2 according to an example of the present disclosure, and FIG. 2B is a .sup.13C NMR spectrum of the poly(1).

[0044] FIG. 3A is a .sup.1H NMR spectrum of a polymer represented by H-poly(1) in a Reaction Formula 3 according to an example of the present disclosure, and FIG. 3B is a .sup.13C NMR spectrum of the H-poly(1).

[0045] FIG. 4 is a .sup.1H-.sup.13C HSQC NMR spectrum of a polymer represented by H-poly(1) in a Reaction Formula 3 according to an example of the present disclosure.

[0046] FIG. 5 is a photograph of a film prepared using the polymer represented by H-poly(1) in the Reaction Formula 3 according to an example of the present disclosure.

[0047] FIG. 6 is a graph of thermogravimetric analysis in a nitrogen atmosphere. The solid line indicates a graph of the polymer represented by poly(1) in the Reaction Formula 2 according to an example of the present disclosure, and the dotted line indicates a graph of the polymer represented by H-poly(1) in the Reaction Formula 3 according to an example of the present disclosure.

[0048] FIG. 7 is a graph of differential scanning calorimetry in a nitrogen atmosphere. Herein, the solid line indicates a graph of the polymer represented by poly(1) in the Reaction Formula 2 according to an example of the present disclosure, and the dotted line indicates a graph of the polymer represented by H-poly(1) in the Reaction Formula 3 according to an example of the present disclosure.

[0049] FIG. 8 is an infrared spectroscopy graph of the polymer represented by H-poly(1) in the Reaction Formula 3 according to an example of the present disclosure.

[0050] FIG. 9 is a graph of transmittance in the UV-visible region of the polymer represented by H-poly(1) in the Reaction Formula 3 according to an example of the present disclosure.

BEST MODE FOR CARRYING OUT THE INVENTION

[0051] Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that the present disclosure may be readily implemented by those skilled in the art. However, it is to be noted that the present disclosure is not limited to the examples but can be embodied in various other ways. In drawings, parts irrelevant to the description are omitted for the simplicity of explanation, and like reference numerals denote like parts through the whole document.

[0052] Through the whole document, the term “connected to” or “coupled to” that is used to designate a connection or coupling of one element to another element includes both a case that an element is “directly connected or coupled to” another element and a case that an element is “electronically connected or coupled to” another element via still another element.

[0053] Through the whole document, the term “on” that is used to designate a position of one element with respect to another element includes both a case that the one element is adjacent to the other element and a case that any other element exists between these two elements.

[0054] Through the whole document, the term “comprises or includes” and/or “comprising or including” used in the document means that one or more other components, steps, operation and/or existence or addition of elements are not excluded in addition to the described components, steps, operation and/or elements unless context dictates otherwise.

[0055] Through the whole document, the term “about or approximately” or “substantially” is intended to have meanings close to numerical values or ranges specified with an allowable error and intended to prevent accurate or absolute numerical values disclosed for understanding of the present disclosure from being illegally or unfairly used by any unconscionable third party.

[0056] Through the whole document, the term “step of” does not mean “step for”.

[0057] Through the whole document, the term “combination of” included in Markush type description means mixture or combination of one or more components, steps, operations and/or elements selected from a group consisting of components, steps, operation and/or elements described in Markush type and thereby means that the disclosure includes one or more components, steps, operations and/or elements selected from the Markush group.

[0058] Through this whole specification, a phrase in the form “A and/or B” means “A or B, or A and B”.

[0059] Hereinafter, embodiments of the present disclosure have been described in detail, but the present disclosure may not be limited thereto.

[0060] A first aspect of the present disclosure provides a cyclic olefin polymer that is produced by ring-opening metathesis polymerization of at least one monomer(s) selected from dicyclopentadiene having an epoxy group represented by the following Chemical Formula 1 and tricyclopentadiene having an epoxy group represented by the following Chemical Formula 2; or by ring-opening metathesis polymerization of at least one monomer(s) selected from the dicyclopentadiene having an epoxy group and the tricyclopentadiene having an epoxy group, and a norbornene monomer represented by the following Chemical Formula 3; and the cyclic olefin polymer includes repeating units represented by the following Chemical Formula 4, Chemical Formula 5, Chemical Formula 6, Chemical Formula 7, Chemical Formula 8, or Chemical Formula 9:

##STR00006## ##STR00007##

[0061] in the above Chemical Formula 3, Chemical Formula 4, Chemical Formula 5, Chemical Formula 6, Chemical Formula 7, Chemical Formula 8, and Chemical Formula 9,

[0062] n is an integer of 5 to 5,000,

[0063] m is an integer of 5 to 5,000,

[0064] l is an integer of 5 to 5,000

[0065] each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and

[0066] R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

[0067] In an embodiment of the present disclosure, the cyclic olefin polymer may include a cyclic olefin polymer produced by ring-opening metathesis polymerization of at least one monomer(s) selected from the dicyclopentadiene having an epoxy group represented by Chemical Formula 1 and the tricyclopentadiene having an epoxy group represented by the Chemical Formula 2; or a cyclic olefin copolymer produced by ring-opening metathesis polymerization of at least one monomer(s) selected from the dicyclopentadiene having an epoxy group represented by Chemical Formula 1 and the tricyclopentadiene having an epoxy group represented by Chemical Formula 2, and a norbornene monomer represented by the following Chemical Formula 3.

[0068] In an embodiment of the present disclosure, the linear or branched alkyl group having 1 to 20 carbon atoms includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms and all possible isomers thereof. For example, the alkyl or alkyl groups may be methyl group(Me), ethyl group(Et), n-propyl group(.sup.nPr), iso-propyl group(.sup.iPr), n-butyl group(.sup.nBu), iso-butyl group(.sup.iBu), tert-butyl group(tert-Bu, .sup.tBu), sec-butyl group(sec-Bu, .sup.secBu), n-pentyl group(.sup.nPe), iso-pentyl group(.sup.isoPe), sec-pentyl group(.sup.secPe), tert-pentyl group(.sup.tPe), neo-pentyl group(.sup.neoPe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.

[0069] In an embodiment of the present disclosure, a polydispersity index of the cyclic olefin polymer may be about 1 to about 1.3. In an embodiment of the present disclosure, a polydispersity index of the cyclic olefin polymer may be about 1 to about 1.2, about 1 to about 1.1, about 1.1 to about 1.3, about 1.1 to about 1.2, or about 1.2 to about 1.3.

[0070] A second aspect of the present disclosure provides a hydrogenated cyclic olefin polymer that is produced by hydrogenation of a cyclic olefin polymer of the first aspect, and the hydrogenated cyclic polymer includes repeating units represented by the following Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, or Chemical Formula 15:

##STR00008##

[0071] in the above Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, and Chemical Formula 15,

[0072] n is an integer of 5 to 5,000,

[0073] m is an integer of 5 to 5,000,

[0074] l is an integer of 5 to 5,000,

[0075] each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and

[0076] R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

[0077] Detailed descriptions of the second aspect of the present disclosure, which overlap with those of the first aspect of the present disclosure, are omitted hereinafter, but the descriptions of the first aspect of the present disclosure may be identically applied to the second aspect of the present disclosure, even though they are omitted hereinafter.

[0078] In an embodiment of the present disclosure, the linear or branched alkyl group having 1 to 20 carbon atoms includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms and all possible isomers thereof. For example, the alkyl or alkyl groups may be methyl group(Me), ethyl group(Et), n-propyl group(.sup.nPr), iso-propyl group(.sup.iPr), n-butyl group(.sup.nBu), iso-butyl group(.sup.iBu), tert-butyl group(tert-Bu, .sup.tBu), sec-butyl group(sec-Bu, .sup.secBu), n-pentyl group(.sup.nPe), iso-pentyl group(.sup.isoPe), sec-pentyl group(.sup.secPe), tert-pentyl group(.sup.tPe), neo-pentyl group(.sup.neoPe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.

[0079] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer may be used in preparing an optically-isotropic film, but may not be limited thereto.

[0080] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer is introduced with an epoxy functional group that is a small-sized polar functional group, and thus, a chain-chain interaction may be increased.

[0081] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer may have a glass transition temperature of at least about 150° C., or at least about 160° C.

[0082] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer has a high solubility in chlorinated solvents. Therefore, a polymer film can be easily obtained by a solution casting method.

[0083] In an embodiment of the present disclosure, a film may have a transmittance of about at least 80%, about at least 83%, or about at least 85% in a visible light region, but may not be limited thereto.

[0084] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer may be applied to a broad range of applications including optical devices, packaging, electronics, medical devices, and microfluidic devices, but may not be limited thereto.

[0085] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer may have low birefringence, high transparency, high thermal stability, and high chemical resistance.

[0086] A third aspect of the present disclosure provides a method of preparing a hydrogenated cyclic olefin polymer including: (a) polymerizing at least one monomer(s) selected from dicyclopentadiene having an epoxy group represented by the following Chemical Formula 1 and tricyclopentadiene having an epoxy group represented by the following Chemical Formula 2; or at least one monomer(s) selected from the dicyclopentadiene having an epoxy group and the tricyclopentadiene having an epoxy group, and a norbornene monomer represented by the following Chemical Formula 3; in the presence of a first-generation Grubbs catalyst to obtain a cyclic olefin polymer; and (b) hydrogenating the cyclic olefin polymer to obtain a hydrogenated cyclic olefin polymer that includes repeating units represented by the following Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, or Chemical Formula 15:

##STR00009## ##STR00010##

[0087] in the above Chemical Formula 3, Chemical Formula 10, Chemical Formula 11, Chemical Formula 12, Chemical Formula 13, Chemical Formula 14, and Chemical Formula 15,

[0088] n is an integer of 5 to 5,000,

[0089] m is an integer of 5 to 5,000,

[0090] l is an integer of 5 to 5,000,

[0091] each of R.sub.1 and R.sub.2 is independently selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an ester group (—COOR.sub.3), or an amide group (—CONHR.sub.3), and

[0092] R.sub.3 is a linear or branched alkyl group having 1 to 20 carbon atoms.

[0093] Detailed descriptions of the third aspect of the present disclosure, which overlap with those of the first aspect and the second aspect of the present disclosure, are omitted hereinafter, but the descriptions of the first aspect and the second aspect of the present disclosure may be identically applied to the third aspect of the present disclosure, even though they are omitted hereinafter.

[0094] In an embodiment of the present disclosure, the linear or branched alkyl group having 1 to 20 carbon atoms includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms and all possible isomers thereof. For example, the alkyl or alkyl groups may be methyl group(Me), ethyl group(Et), n-propyl group(.sup.nPr), iso-propyl group(.sup.iPr), n-butyl group(.sup.nBu), iso-butyl group(.sup.iBu), tert-butyl group(tert-Bu, .sup.tBu), sec-butyl group(sec-Bu, .sup.secBu), n-pentyl group(.sup.nPe), iso-pentyl group(.sup.isoPe), sec-pentyl group(.sup.secPe), tert-pentyl group(.sup.tPe), neo-pentyl group(.sup.neoPe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.

[0095] In an embodiment of the present disclosure, the step of (b) may be performed in the presence of a Pd/C catalyst.

[0096] In an embodiment of the present disclosure, a catalyst used for preparing the hydrogenated cyclic olefin polymer according to embodiments of the present disclosure does not have reactivity with the epoxy functional group. Therefore, a side reaction may not occur in polymerization and hydrogenation.

[0097] In an embodiment of the present disclosure, the hydrogenated cyclic olefin polymer further including a norbornene monomer may have improved properties such as tensile strength, elasticity, or adhesion.

[0098] Hereinafter, the present disclosure will be explained in more detail with reference to Examples. However, the following Examples are illustrative only for better understanding of the present disclosure but do not limit the present disclosure.

MODE FOR CARRYING OUT THE INVENTION

Examples

1. Experiment Design

[0099] The following experiment was conducted to prepare a cyclic olefin-based polymer having a glass transition temperature of at least 150° C., high-temperature durability and high transmittance through synthesis and ring-opening metathesis polymerization of monomers introduced with an epoxy functional group, and a remaining functional group in each polymerization process was identified through NMR.

2. Experiment

2.1 Synthesis of Dicyclopentadiene Introduced with an Epoxy Functional Group

[0100] Dicyclopentadiene introduced with an epoxy functional group was synthesized by a method shown in the following Reaction Formula 1.

##STR00011##

[0101] 6.78 g (51.3 mmol) of dicyclopentadiene (DCPD) was put into a 1 L one-neck round flask and dissolved by the addition of 50 mL of anhydrous dichloromethane (CH.sub.2Cl.sub.2). After 11.4 g (50.9 mmol) of meta-chloroperoxybenzoic acid (C.sub.7H.sub.5ClO.sub.3) was dissolved in 100 mL of anhydrous dichloromethane, which is the same kind of solvent, the resultant solution was slowly put into a round flask by dividing it in three parts. The solution in the round flask was stirred for three hours at room temperature under ambient conditions, and the produced white suspension was filtered through a celite pad. The filtrate was extracted continuously with 10 wt % of a sodium bicarbonate (NaHCO.sub.3) aqueous solution, dried with anhydrous magnesium sulfate (MgSO.sub.4), and then concentrated in a vacuum. The residue was purified by silica gel column chromatography using ethyl acetate-hexane (with a volume ratio of 1:9) as an eluent to obtain 2.35 g of a white solid.

[0102] To increase the synthesis efficiency, as for two monomer compounds 1 and 2 obtained in a synthesis process of a dicyclopentadiene monomer introduced with an epoxy functional group as shown in the Reaction Formula 1, a monomer compound 1 can be polymerized without any pretreatment for isolating each compound. In this case, the ratio of the two monomers in a mixture is identified through an NMR spectrum and polymerization is carried out to obtain the same polymer.

[0103] Referring to FIGS. 1A and 1B, 1H NMR spectrum and .sup.13C NMR spectrum analysis were performed to identify a functional group remaining in dicyclopentadiene introduced with an epoxy functional group.

[0104] .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): δ 6.10 (dd, J=8.7, 2.9 Hz, 2H, C═C—H), 3.33 (t, J=2.5 Hz, .sup.1H, CH), 3.17 (d, J=2.5 Hz, .sup.1H, CH), 2.93 (td, J=3.0, 1.5 Hz, .sup.1H, CH), 2.82 (m, 2H, CH.sub.2), 2.55 (tt, J=8.1, 3.9 Hz, .sup.1H, CH), 1.91 (dd, J=14.9, 9.0 Hz, .sup.1H, CH), 1.51 (dt, J=8.3, 1.9 Hz, .sup.1H, CH), 1.39-1.31 (m, 2H, CH.sub.2). .sup.13C NMR (101 MHz, CDCl.sub.3, ppm): δ 135.19 (s, C═C), 135.04 (s, C═C), 62.03 (s, C—O), 60.92 (s, C—O), 52.15 (s, CH), 51.15 (s, CH), 46.59 (s, CH.sub.2), 44.79 (s, CH), 44.08 (s, CH), 31.22 (s, CH.sub.2). Anal. Calcd. For C.sub.10H.sub.12O: C, 81.04; H, 8.16. Found: C, 81.22; H, 8.20.

2.2 Synthesis of Cyclic Olefin Polymer Introduced with an Epoxy Functional Group

[0105] Cyclic olefin polymer introduced with an epoxy functional group was synthesized by a method shown in the following Reaction Formula 2.

##STR00012##

[0106] A first-generation Grubbs catalyst (G1; [(PCy.sub.3).sub.2(Cl).sub.2Ru═CHPh]) (5.1 mg, 6.0 μmol) was dissolved in 1.0 mL of dichloromethane in a 4 mL vial. After 180 mg (1.2 mmol) of dicyclopentadiene introduced with an epoxy functional group was dissolved in 2.0 mL of dichloromethane, the dissolved solution was rapidly added to the vial with a syringe at room temperature under nitrogen conditions. After 30 minutes, 0.5 mL of ethyl vinyl ether was added to the reaction mixture to terminate the reaction. After the solution was stirred for 15 minutes and settled in methanol, a resultant precipitate was collected and dried to obtain a white solid.

[0107] Referring to FIGS. 2A and 2B, 1H NMR spectrum and .sup.13C NMR spectrum analysis were performed to identify a functional group remaining in cyclic olefin polymer represented by poly(1) in the Reaction Formula 2.

[0108] .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): δ 5.53-5.29 (br, 2H), 3.55-3.42 (br, .sup.1H), 3.40-3.27 (br, .sup.1H), 3.10-2.51 (br, 3H), 2.47-2.30 (br, .sup.1H), 2.02-1.84 (br, .sup.1H), 1.80-1.64 (br, .sup.1H), 1.52-1.21 (br, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3, ppm): δ 131.48, 130.56, 59.70, 59.52, 48.77, 44.83, 44.73, 44.61, 44.47, 43.11, 42.92, 36.44, 29.89. Anal. Calcd. For C.sub.10H.sub.12O: C, 81.04; H, 8.16. Found: C, 79.89; H, 8.21.

2.3 Hydrogenation of Cyclic Olefin Polymer Introduced with an Epoxy Functional Group

[0109] Hydrogenation of cyclic olefin polymer introduced with an epoxy functional group was synthesized by a method shown in the following Reaction Formula 3.

##STR00013##

[0110] 160 mg of the cyclic olefin-based polymer obtained in the process 2.2 was dissolved in 25 mL of anhydrous dichloromethane. The solution was transferred to an autoclave and then, 10 wt % of Pd/C (40.0 mg) was added thereto. The mixture solution was stirred violently at 65° C. for 24 hours under hydrogen pressure of 35 bar and then cooled to room temperature. The mixture was isolated by filtration and concentrated under reduced pressure. The concentrated mixture solution was poured into methanol and then, a resultant precipitate was collected and dried to obtain a white solid.

[0111] Referring to FIGS. 3A, 3B and 4, 1H NMR spectrum, .sup.13C NMR spectrum, and .sup.1H-.sup.13C HSQC NMR spectrum analysis was performed to identify a functional group remaining in cyclic olefin polymer represented by H-poly(1) in the Reaction Formula 3.

[0112] .sup.1H NMR (400 MHz, CDCl.sub.3, ppm): δ 3.54-3.45 (br, .sup.1H), 3.39-3.30 (br, .sup.1H), 2.77-2.66 (br, .sup.1H), 2.35-2.24 (br, .sup.1H), 1.99-1.85 (br, 2H), 1.83-1.71 (br, 2H), 1.50-1.11 (br, 5H), 0.92-0.72 (br, .sup.1H). .sup.13C NMR (101 MHz, CDCl.sub.3, ppm): δ 59.68, 59.14, 47.03, 43.30, 43.15, 42.23, 40.12, 39.89, 37.66, 31.89, 29.94, 29.58, 28.45. Anal. Calcd. For C.sub.10H.sub.14O: C, 79.96; H, 9.39. Found: C, 78.10; H, 9.29.

2.4 Synthesis of Transparent Polymer Film Including Epoxy Functionalization Polymer

[0113] The cyclic olefin-based polymer obtained in the process 2.3 was put into a vial with a screw cap and tetrachloroethane was added thereto. The mixture was heated at 50° C. and dissolved with stirring until it was completely dissolved. After the cyclic olefin-based polymer was completely dissolved, it was cooled to room temperature to obtain a transparent solution. The transparent solution was poured onto a Teflon plate with a syringe filter and then, all the volatile materials were evaporated to prepare a film. The prepared film was further dried in a vacuum oven at 60° C. for 24 hours. The thickness of the obtained film was measured using a Mitutoyo IP65 coolant-proof micrometer.

[0114] Referring to FIG. 5, the transparent polymer film prepared in the process 2.4 can be confirmed.

3. Characteristic Evaluation

3.1 Characteristics of Non-Epoxidized Polymers

[0115] According to the previously published related document entitled “New catalysts for linear polydicyclopentadiene synthesis” (M. J. Abadie, M. Dimonie, Christine Couve, V. Dragutanc), linear polydicyclopentadiene (LPDCPD) has a glass transition temperature of 53° C. The following Table 1 is polymer-related data as a result of ring-opening polymerization of dicyclopentadiene (DCPD), which was performed at 25° C. using a tungsten catalyst:

TABLE-US-00001 TABLE 1 Conversion [catalyst] rate after 4 Gel content Catalyst system (mol/L × 10.sup.3) Si/W hours (%) (%) M.sub.o M.sub.n WCl.sub.6—SiAll.sub.4 0.5 1 52 0 39.000 22.000 WCl.sub.6—SiAll.sub.4 1.12 1 98 53 39.900 19.000 WCl.sub.6—SiAll.sub.4 1.7 1 100 0 — — WOCl.sub.4—SiAll.sub.4 0.8 1 87 0 58.000 28.000 WOCl.sub.4—SiAll.sub.4 3.4 1 100 0 46.000 22.000 WOCl.sub.4—SiAll.sub.4 5 2 100 0 36.000 18.000 WOCl.sub.4—SiMe.sub.2All.sub.2 3.4 2 100 0 57.000 30.000 WOCl.sub.6—H.sub.2O—SiMe.sub.2All.sub.2 3.4 2 100 0 50.100 26.000 H.sub.2O/WCl.sub.6 = 0.7ª WOCl.sub.6—H.sub.2O—SiMe.sub.2All.sub.2 3.4 2 100 0 234 41.400 H.sub.2O/WCl.sub.6 = 0.7.sup.b

[0116] In the above Table 1, All represents an allyl group, superscript “a” means being inactivated immediately after the completion of polymerization, and superscript “b” means being inactivated 20 hours after the completion of polymerization.

[0117] Also, another previously published related document entitled “Preparation and characterization of cycloolefin polymer based on dicyclopentadiene (DCPD) and dimethanooctahydronaphthalene (DMON)” (Vania Tanda Widyaya, Huyen Thanh Vo, Robertus Dhimas Dhewangga Putra, Woon Sung Hwang, Byoung Sung Ahn, Hyunjoo Lee) discloses characteristics of a cycloolefin polymer (COP) prepared as shown in the following Reaction Formula 4.

##STR00014##

[0118] The cycloolefin polymer (COP) has a structure in which cycloolefin and ethylene are regularly repeated, and, thus, the structure of cycloolefin determines a glass transition temperature of the COP. The COP prepared by polymerizing dicyclopentadiene (DCPD) exhibits a low glass transition temperature of 100° C. A double bond in a 5-membered ring of dicyclopentadiene is not active to ring-opening polymerization, but can also be polymerized in a very high temperature environment.

[0119] DMON (1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene) shown in the above Reaction Formula 4 can be easily prepared through a Diels-Alder reaction between cyclopentadiene and norbornene. Hydrogenated cycloolefin polymers (H-p-DCPD, H-p-DCPD.sub.0.75-DMON.sub.0.25, H-p-DCPD.sub.0.5-DMON.sub.0.5, and H-p-DMON) exhibit a polydispersity index (PDI) in the range of 2.4 to 2.8.

3.2 Characteristics of Epoxidized Polymers According to the Present Disclosure

[0120] The following Table 2 shows the results of characteristic evaluation on poly(1) and H-poly(1) in the Reaction Formula 3 according to the present disclosure.

TABLE-US-00002 TABLE 2 Yield PDI transmittance thickness Entry Sample [M].sub.o/[I].sub.o (%) (M.sub.w/M.sub.n) T.sub.g(° C.) T.sub.d5(° C.) (%) (μm) 1 Poly(1) 200 96 1.15 204 360 — — 10 2 H-poly(1) 200 95 — 167 364 82 88 10 (440 nm) (550 nm)

3.3 Polydispersity Index (PDI)

[0121] The PDI of poly(1) in the above Reaction Formula 2 was measured.

3.4 Thermogravimetric Analysis

[0122] To check the thermal stability of the poly(1) and the H-poly(1), the temperature of each was measured by using a thermogravimetric analyzer under nitrogen conditions when the weight of each of the poly(1) and the H-poly(1) decreased by 5% while increasing the temperature at a rate of 5° C./min.

[0123] Referring to FIG. 6, the poly(1) is indicated by a solid line and the H-poly(1) is indicated by a dotted line.

3.5 Differential Scanning Calorimetry Analysis

[0124] To measure the glass transition temperature of the poly(1) and the H-poly(1), differential scanning calorimetry analysis was performed under nitrogen conditions.

[0125] Referring to FIG. 7, the poly(1) has a glass transition temperature of 204° C. as indicated by a solid line, and the H-poly(1) has a glass transition temperature of 167° C. as indicated by a dotted line.

3.6 Infrared Spectroscopy

[0126] Referring to FIG. 8, the H-poly(1) was analyzed by infrared spectroscopy.

3.7 the Transmittance of UV-Vis Region

[0127] The transmittance of the H-poly(1) in a UV-VIS region was analyzed.

[0128] Referring to FIG. 9, the H-poly(1) exhibited a transmittance of 82% at a wavelength of 400 nm and a transmittance of 88% at a wavelength of 550 nm.

4. Conclusion

[0129] The H-poly(1) produced in the above-described experiment exhibited a glass transition temperature of 167° C., a transmittance of 82% at a wavelength of 400 nm and a transmittance of 88% at a wavelength of 550 nm, which confirms that the H-poly(1) can be applied to a film having high-temperature durability and high transmittance.

[0130] The above description of the present disclosure is provided for the purpose of illustration, and it would be understood by a person with ordinary skill in the art that various changes and modifications may be made without changing technical conception and essential features of the present disclosure. Thus, it is clear that the above-described examples are illustrative in all aspects and do not limit the present disclosure. For example, each component described to be of a single type can be implemented in a distributed manner. Likewise, components described to be distributed can be implemented in a combined manner.

[0131] The scope of the present disclosure is defined by the following claims rather than by the detailed description of the embodiment. It shall be understood that all modifications and embodiments conceived from the meaning and scope of the claims and their equivalents are included in the scope of the present disclosure.