KR20220139234A - Compound having thermotropic liquid crystalline structure and polyethylene glycol polymer thereof - Google Patents
Compound having thermotropic liquid crystalline structure and polyethylene glycol polymer thereof Download PDFInfo
- Publication number
- KR20220139234A KR20220139234A KR1020220041487A KR20220041487A KR20220139234A KR 20220139234 A KR20220139234 A KR 20220139234A KR 1020220041487 A KR1020220041487 A KR 1020220041487A KR 20220041487 A KR20220041487 A KR 20220041487A KR 20220139234 A KR20220139234 A KR 20220139234A
- Authority
- KR
- South Korea
- Prior art keywords
- polyethylene glycol
- compound
- polymer
- nmr
- epcnn
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 37
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 title abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- -1 bulk Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000005267 main chain polymer Substances 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 40
- 239000012071 phase Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000004973 liquid crystal related substance Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229920000106 Liquid crystal polymer Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 150000002924 oxiranes Chemical group 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical group C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- LAUFPZPAKULAGB-UHFFFAOYSA-N 4-butoxybenzoic acid Chemical compound CCCCOC1=CC=C(C(O)=O)C=C1 LAUFPZPAKULAGB-UHFFFAOYSA-N 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- YIWBRSAYFRNTMR-UHFFFAOYSA-N (4-hydroxyphenyl) 4-butoxybenzoate Chemical compound C1=CC(OCCCC)=CC=C1C(=O)OC1=CC=C(O)C=C1 YIWBRSAYFRNTMR-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YUVYQNWFSWWBCC-UHFFFAOYSA-N 1-hydroxy-4-phenylcyclohexa-2,4-diene-1-carbonitrile Chemical compound C1=CC(O)(C#N)CC=C1C1=CC=CC=C1 YUVYQNWFSWWBCC-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TWQLLXNQLKTMIT-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr.BrCCCCBr TWQLLXNQLKTMIT-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- LVWSZGCVEZRFBT-UHFFFAOYSA-N 1,7-dibromoheptane Chemical compound BrCCCCCCCBr LVWSZGCVEZRFBT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- WGAXVZXBFBHLMC-UHFFFAOYSA-N 1,9-dibromononane Chemical compound BrCCCCCCCCCBr WGAXVZXBFBHLMC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IALWCYFULVHLEC-UHFFFAOYSA-N 4-(octyloxy)benzoic acid Chemical compound CCCCCCCCOC1=CC=C(C(O)=O)C=C1 IALWCYFULVHLEC-UHFFFAOYSA-N 0.000 description 1
- NZNICZRIRMGOFG-UHFFFAOYSA-N 4-decoxybenzoic acid Chemical compound CCCCCCCCCCOC1=CC=C(C(O)=O)C=C1 NZNICZRIRMGOFG-UHFFFAOYSA-N 0.000 description 1
- HBQUXMZZODHFMJ-UHFFFAOYSA-N 4-hexoxybenzoic acid Chemical compound CCCCCCOC1=CC=C(C(O)=O)C=C1 HBQUXMZZODHFMJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WQYCMMCJHPUYJP-UHFFFAOYSA-L benzyl(trimethyl)azanium dibromide Chemical compound [Br-].C(C1=CC=CC=C1)[N+](C)(C)C.[Br-].C(C1=CC=CC=C1)[N+](C)(C)C WQYCMMCJHPUYJP-UHFFFAOYSA-L 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3411—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a three-membered ring
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3876—Polyoxyalkylene polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/122—Ph-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K2019/2035—Ph-COO-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3411—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a three-membered ring
- C09K2019/3413—Three-membered member ring with oxygen(s), e.g. oxirane in fused, bridged or spiro ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 열방성 액정 분자에 에폭사이드 작용기를 수식하여 수득된 열방성 액정 구조를 갖는 화합물 및 이를 개환 중합하여 얻어지는 폴리에틸렌글리콜 중합체에 관한 것으로서, 보다 구체적으로 박막, 벌크, 섬유 상으로 성형이 용이하고, 열전도도가 높아 방열 고분자로 단독 활용 또는 복합재료의 형태로 사용가능한 폴리에틸렌글리콜 주쇄의 중합체에 관한 것이다.The present invention relates to a compound having a thermotropic liquid crystal structure obtained by modifying an epoxide functional group in a thermotropic liquid crystal molecule, and a polyethylene glycol polymer obtained by ring-opening polymerization thereof, and more specifically, to a thin film, bulk, or fiber form. , It relates to a polymer of a polyethylene glycol main chain that can be used alone or in the form of a composite material because of its high thermal conductivity.
액정고분자(Liquid crystalline polymer, LCP)는 용융 또는 용액 상태에서 액정상을 나타내는 고분자로 일반적으로 메소겐 단위(mesogenic unit)를 포함하는 구조를 가지고 있다. 열방성 액정고분자(Thermotropic liquid crystalline polymer, TLCP)의 경우, 온도의 변화에 따른 액정거동이 나타나며 메소겐 단위의 위치, 형태, 구조에 따라 그 특성이 크게 달라진다. 높은 내열성과 내화학성 외에 뛰어난 기계적 물성을 나타내므로 고성능 복합체나 엔지니어링 플라스틱과 같은 분야에 응용이 가능하며 학문적, 산업적으로 많은 연구가 이루어져 왔다.Liquid crystalline polymer (LCP) is a polymer that exhibits a liquid crystal phase in a molten or solution state, and generally has a structure including a mesogenic unit. In the case of a thermotropic liquid crystalline polymer (TLCP), a liquid crystal behavior according to a change in temperature appears, and its properties vary greatly depending on the position, shape, and structure of the mesogenic unit. Because it exhibits excellent mechanical properties in addition to high heat resistance and chemical resistance, it can be applied to fields such as high-performance composites and engineering plastics, and many studies have been made academically and industrially.
하지만, 기존에 보고된 열방성 액정고분자의 경우, 높은 용융 온도와 내화학성 때문에 높은 온도 또는 강산 및 유기 용매의 용액 상태에서 합성, 가공하여야 한다는 단점이 존재한다. 대부분의 액정고분자들의 경우 용매를 사용하여 합성하며, 대표적으로 미국 등록특허 제04954606호, 미국 등록특허 제05109100호 및 미국 등록특허 제04912193호에 자세하게 나타나 있는데, 이 경우 액정고분자를 제조한 후 용매를 제거하는 공정을 거쳐야 한다는 단점이 존재함과 동시에 용융상태에서의 가공이 어렵다는 단점이 있다. 중합 및 가공 온도를 낮추기 위해 측쇄(side chain)에 부피가 큰 분자를 배치하거나 주쇄 내 긴 유연쇄를 도입하는 등의 방식을 사용하고 있으며, 이러한 종래 기술로는 Journal of Polymer Science Part A: Polymer Chemistry, Vol. 19, (8), 1901 (1981); Macromolecular Chemistry and Physics, Vol. 192, (2), 201 (1991); Polymer Journal, Vol. 17, (1), 105 (1985); Polymer, Vol. 32, (9), 1703 (1991); Polymer Preprint (American Chemical Society), Vol. 27, (1), 369 (1986) : Polymer Journal, Vol. 17, (1), 277 (1985); Journal of Polymer Science Part A: Polymer Chemistry, Vol. 21, (11), 3313 (1983) 등이 있다. 하지만, 어느 이러한 구조의 중합 및 가공온도에서는 어느 정도 성능 저하가 일어나고 새로운 공정이나 반응물의 투입은 원가 상승을 가져오며, 제조한 액정고분자를 가공하기 위해서 추가 공정을 거쳐야 한다는 한계점이 있다.However, in the case of the previously reported thermotropic liquid crystal polymer, there is a disadvantage that it must be synthesized and processed at a high temperature or in a solution state of a strong acid and an organic solvent because of its high melting temperature and chemical resistance. Most liquid crystal polymers are synthesized using a solvent, and are typically shown in detail in U.S. Patent No. 04954606, U.S. Patent No. 05109100, and U.S. Patent No. 04912193. In this case, after preparing the liquid crystal polymer, the solvent is There is a disadvantage that it has to go through a removal process, and at the same time, there is a disadvantage that it is difficult to process in a molten state. In order to lower the polymerization and processing temperature, a method such as placing bulky molecules in the side chain or introducing a long flexible chain in the main chain is used. As such prior art, Journal of Polymer Science Part A: Polymer Chemistry , Vol. 19, (8), 1901 (1981); Macromolecular Chemistry and Physics, Vol. 192, (2), 201 (1991); Polymer Journal, Vol. 17, (1), 105 (1985); Polymer, Vol. 32, (9), 1703 (1991); Polymer Preprint (American Chemical Society), Vol. 27, (1), 369 (1986): Polymer Journal, Vol. 17, (1), 277 (1985); Journal of Polymer Science Part A: Polymer Chemistry, Vol. 21, (11), and 3313 (1983). However, at the polymerization and processing temperature of any of these structures, performance degradation occurs to some extent, and the introduction of a new process or reactant increases the cost, and there is a limitation in that an additional process is required to process the prepared liquid crystal polymer.
따라서, 전술한 문제점을 보완하기 위해 본 발명가는 성형이 용이한 열가소성 액정고분자 개발을 위하여 열방성 액정 구조를 갖는 화합물 및 이의 폴리에틸렌글리콜 중합체의 개발이 시급하다 인식하여, 본 발명을 완성하였다.Therefore, in order to supplement the above-mentioned problems, the present inventor recognized that it is urgent to develop a compound having a thermotropic liquid crystal structure and a polyethylene glycol polymer thereof for the development of a thermoplastic liquid crystal polymer that can be easily molded, and completed the present invention.
본 발명의 목적은 열방성 액정 분자에 에폭사이드 작용기를 수식하여 수득된 열방성 액정 구조를 갖는 화합물 및 이를 개환 중합하여 얻어지는 폴리에틸렌글리콜 중합체를 제공하는 것이다.An object of the present invention is to provide a compound having a thermotropic liquid crystal structure obtained by modifying an epoxide functional group in a thermotropic liquid crystal molecule, and a polyethylene glycol polymer obtained by ring-opening polymerization thereof.
본 발명의 다른 목적은 박막, 벌크, 섬유 상으로 성형이 용이하고, 열전도도가 높아 방열 고분자 및 복합재료로서 사용가능한 폴리에틸렌글리콜 중합체를 제공하는 것이다.Another object of the present invention is to provide a polyethylene glycol polymer that can be easily formed into a thin film, bulk, or fiber form, and has high thermal conductivity, which can be used as a heat dissipating polymer and a composite material.
발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 본 발명의 기재로부터 당해 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있다.The technical problems to be achieved by the invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art from the description of the present invention.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 (I)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 제공한다.In order to achieve the above object, the present invention provides a compound having a thermotropic liquid crystal structure in the side chain represented by the following formula (I).
[화학식 (I)][Formula (I)]
[식 중, n은 1 내지 30 범위의 정수임].[wherein n is an integer ranging from 1 to 30].
본 발명은 하기 화학식 (Ⅱ)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 제공한다.The present invention provides a compound having a thermotropic liquid crystal structure in the side chain represented by the following formula (II).
[화학식 (Ⅱ)][Formula (II)]
[식 중, n은 1 내지 30 범위의 정수임].[wherein n is an integer ranging from 1 to 30].
본 발명은 상기 화학식 (I)로 표시되는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.The present invention provides a polyethylene glycol polymer obtained by ring-opening polymerization of the compound represented by the formula (I).
본 발명은 상기 화학식 (Ⅱ)로 표시되는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.The present invention provides a polyethylene glycol polymer obtained by ring-opening polymerization of a compound represented by the above formula (II).
또한, 본 발명은 하기 화학식 (Ⅲ)으로 표시되며, 상기 화학식 (I) 또는 화학식 (Ⅱ)로 표시되는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.In addition, the present invention provides a polyethylene glycol polymer represented by the following formula (III) and obtained by ring-opening polymerization of a compound represented by the formula (I) or (II).
[화학식 (Ⅲ)][Formula (III)]
[식 중, X1, X2는 동일하거나 다를 수 있고, 제 1 항에 따른 화합물 또는 제 2 항에 따른 화합물에서 선택됨].[wherein, X1 and X2 may be the same or different, and are selected from the compound according to
상기 폴리에틸렌글리콜 중합체는 기판, 컴파운드, 접착제, 패드, 히트스프레드 및 히트싱크 등 각종 전자부품류를 주축으로 한 범용물질로 사용할 수 있다.The polyethylene glycol polymer may be used as a general-purpose material based on various electronic components such as a substrate, a compound, an adhesive, a pad, a heat spread, and a heat sink.
상기 열방성 액정 구조를 갖는 화합물 및 이의 폴리에틸렌글리콜 중합체에 언급된 모든 사항은 모순되지 않는 한 동일하게 적용된다.All matters mentioned for the compound having the thermotropic liquid crystal structure and its polyethylene glycol polymer apply equally unless contradictory.
본 발명에 따라 제조된 신규한 폴리에틸렌글리콜 중합체는 박막, 벌크, 섬유 상으로 성형이 용이하고 열전도도가 향상되어, 다양한 전자부품류에 활용될 수 있다.The novel polyethylene glycol polymer prepared according to the present invention can be easily formed into a thin film, bulk, or fiber form and has improved thermal conductivity, and thus can be used in various electronic components.
본 발명의 효과들은 이상에서 언급한 효과들로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 청구범위의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.
도 1은 본 발명의 일 실시예에 따라 합성된 EPCNn (4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile)의 1H-NMR 스펙트럼으로, (a)는 EPCN4, (b)는 EPCN5, (c)는 EPCN6, (d)는 EPCN7, (e)는 EPCN8, 및 (f)는 EPCN9의 스펙트럼이다.
도 2는 상기 EPCNn의 13C-NMR 스펙트럼으로, (a)는 EPCN4, (b)는 EPCN5, (c)는 EPCN6, (d)는 EPCN7, (e)는 EPCN8, 및 (f)는 EPCN9의 스펙트럼이다.
도 3은 본 발명의 다른 실시예에 따라 합성된 P-EPCNn의 1H-NMR 스펙트럼으로, (a)는 P-EPCN4, (b)는 P-EPCN5, (c)는 P-EPCN6, (d)는 P-EPCN7, (e)는 P-EPCN8, 및 (f)는 P-EPCN9의 스펙트럼이다.
도 4는 상기 P-EPCNn의 FT-IR 스펙트럼이다.
도 5는 상기 P-EPCNn의 겔 투과 크로마토그래피(GPC) 분석 결과이다.
도 6은 시차주사열량계(DSC)에 의해 분석된 상 전이도이다.
도 7은 2℃/분의 가열 및 냉각속도로 분석된 상기 EPCNn의 DSC 분석 그래프로, (a)는 EPCN4, (b)는 EPCN5, (c)는 EPCN6, (d)는 EPCN7, (e)는 EPCN8, 및 (f)는 EPCN9의 그래프이다.
도 8은 상기 EPCNn의 편광 광학 현미경 (POM) 이미지이다 (scale bar = 50μm).
도 9는 5℃/분의 가열 및 냉각속도로 분석된 상기 P-EPCNn의 DSC 분석 그래프이다.
도 10은 상기 P-EPCNn의 POM 이미지이다 (scale bar = 50μm).
도 11은 열 전도도 평가를 위해 제조된 P-EPCNn의 벌크 시편이다.
도 12는 실온에서 P-EPCNn의 X-선 회절 분석한(XRD) 그래프이다.
도 13은 B3LYP/6-31G 수준에서 밀도범함수이론(density functional theory, DFT)에 의해 계산된 P-EPCNn 모델 화합물의 최적화된 분자 구조를 나타낸 것이다.
도 14는 본 발명의 다른 실시예에 따라 합성된 OMPBn (4-(oxiran-2-ylmethoxy)phenyl 4-alkoxybenzoate)의 1H-NMR 스펙트럼으로, (a)는 OMPB4, (b)는 OMPB6, (c)는 OMPB8, 및 (d)는 OMPB10의 스펙트럼이다.
도 15는 상기 OMPBn의 13C-NMR 스펙트럼으로, (a)는 OMPB4, (b)는 OMPB6, (c)는 OMPB8, 및 (d)는 OMPB10의 스펙트럼이다.
도 16은 본 발명의 다른 실시예에 따라 합성된 P-OMPBn의 1H-NMR 스펙트럼으로, (a)는 P-OMPB4, (b)는 P-OMPB6, (c)는 P-OMPB8, 및 (d)는 P-OMPB10의 스펙트럼이다.1 is a 1 H-NMR spectrum of EPCNn (4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile) synthesized according to an embodiment of the present invention, (a) is EPCN4, (b ) is the spectrum of EPCN5, (c) is EPCN6, (d) is EPCN7, (e) is EPCN8, and (f) is EPCN9.
2 is a 13 C-NMR spectrum of the EPCNn, (a) is EPCN4, (b) is EPCN5, (c) is EPCN6, (d) is EPCN7, (e) is EPCN8, and (f) is EPCN9 is the spectrum.
3 is a 1 H-NMR spectrum of P-EPCNn synthesized according to another embodiment of the present invention, (a) is P-EPCN4, (b) is P-EPCN5, (c) is P-EPCN6, (d) ) is the spectrum of P-EPCN7, (e) is P-EPCN8, and (f) is P-EPCN9.
4 is an FT-IR spectrum of the P-EPCNn.
5 is a gel permeation chromatography (GPC) analysis result of the P-EPCNn.
6 is a phase transition diagram analyzed by differential scanning calorimetry (DSC).
7 is a DSC analysis graph of the EPCNn analyzed at a heating and cooling rate of 2° C./min. (a) is EPCN4, (b) is EPCN5, (c) is EPCN6, (d) is EPCN7, (e) is a graph of EPCN8, and (f) is a graph of EPCN9.
8 is a polarization optical microscope (POM) image of the EPCNn (scale bar = 50 μm).
9 is a DSC analysis graph of the P-EPCNn analyzed at a heating and cooling rate of 5° C./min.
10 is a POM image of the P-EPCNn (scale bar = 50 μm).
11 is a bulk specimen of P-EPCNn prepared for thermal conductivity evaluation.
12 is an X-ray diffraction analysis (XRD) graph of P-EPCNn at room temperature.
13 shows the optimized molecular structure of the P-EPCNn model compound calculated by density functional theory (DFT) at the B3LYP/6-31G level.
14 is a 1 H-NMR spectrum of OMPBn (4-(oxiran-2-ylmethoxy)phenyl 4-alkoxybenzoate) synthesized according to another embodiment of the present invention, (a) is OMPB4, (b) is OMPB6, ( c) is the spectrum of OMPB8, and (d) is the spectrum of OMPB10.
15 is a 13 C-NMR spectrum of OMPBn, (a) is OMPB4, (b) is OMPB6, (c) is OMPB8, and (d) is OMPB10 spectrum.
16 is a 1 H-NMR spectrum of P-OMPBn synthesized according to another embodiment of the present invention, (a) is P-OMPB4, (b) is P-OMPB6, (c) is P-OMPB8, and ( d) is the spectrum of P-OMPB10.
본 명세서에서 사용되는 용어는 본 발명에서의 기능을 고려하면서 가능한 현재 널리 사용되는 일반적인 용어들을 선택하였으나, 이는 당 분야에 종사하는 기술자의 의도 또는 판례, 새로운 기술의 출현 등에 따라 달라질 수 있다. 또한, 특정한 경우는 출원인이 임의로 선정한 용어도 있으며, 이 경우 해당되는 발명의 설명 부분에서 상세히 그 의미를 기재할 것이다. 따라서 본 발명에서 사용되는 용어는 단순한 용어의 명칭이 아닌, 그 용어가 가지는 의미와 본 발명의 전반에 걸친 내용을 토대로 정의되어야 한다.The terms used in this specification have been selected as currently widely used general terms as possible while considering the functions in the present invention, which may vary depending on the intention or precedent of a person skilled in the art, the emergence of new technology, and the like. In addition, in a specific case, there is a term arbitrarily selected by the applicant, and in this case, the meaning will be described in detail in the description of the corresponding invention. Therefore, the term used in the present invention should be defined based on the meaning of the term and the overall content of the present invention, rather than the name of a simple term.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not
수치 범위는 상기 범위에 정의된 수치를 포함한다. 본 명세서에 걸쳐 주어진 모든 최대의 수치 제한은 낮은 수치 제한이 명확히 쓰여져 있는 것처럼 모든 더 낮은 수치 제한을 포함한다. 본 명세서에 걸쳐 주어진 모든 최소의 수치 제한은 더 높은 수치 제한이 명확히 쓰여져 있는 것처럼 모든 더 높은 수치 제한을 포함한다. 본 명세서에 걸쳐 주어진 모든 수치 제한은 더 좁은 수치 제한이 명확히 쓰여져 있는 것처럼, 더 넓은 수치 범위 내의 더 좋은 모든 수치 범위를 포함할 것이다.Numerical ranges are inclusive of the values defined in that range. Every maximum numerical limitation given throughout this specification includes all lower numerical limitations as if the lower numerical limitation were expressly written. Every minimum numerical limitation given throughout this specification includes all higher numerical limitations as if the higher numerical limitation were expressly written. All numerical limitations given throughout this specification will include all numerical ranges that are better within the broader numerical limits, as if the narrower numerical limitations were expressly written.
이하, 본 발명을 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 (I)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 제공한다.The present invention provides a compound having a thermotropic liquid crystal structure in the side chain represented by the following formula (I).
[화학식 (I)][Formula (I)]
[식 중, n은 1 내지 30 범위의 정수임].[wherein n is an integer ranging from 1 to 30].
상기 화학식 (I)의 화합물은 4-하이드록시-4-바이페닐카르보니트릴(4-hydroxy-4-biphenylcarbonitrile)을 출발물질로 하여 디브로모알칸(dibromoalkane)과의 반응을 통해 4-(4-브로모알콕시)-4-바이페닐카르보니트릴 (4-(4-bromoalkoxy)-4-biphenylcarbonitrile, BRCNn)을 합성할 수 있고, 이후 4-(4-브로모알콕시)-4-바이페닐카르보니트릴을 다시 개시물질로 하여 글리시돌(glycidol)과 의 반응을 통해 상기 화합물을 합성할 수 있다.The compound of formula (I) is 4-(4-) through the reaction with dibromoalkane using 4-hydroxy-4-biphenylcarbonitrile as a starting material Bromoalkoxy)-4-biphenylcarbonitrile (4-(4-bromoalkoxy)-4-biphenylcarbonitrile, BRCNn) can be synthesized, and then 4-(4-bromoalkoxy)-4-biphenylcarbonitrile Again, the compound can be synthesized through a reaction with glycidol as a starting material.
상기 화합물은 4-(n-(옥시란-2-일메톡시)알킬옥시)-4-바이페닐카르보니트릴 (4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile) 일 수 있다.The compound may be 4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile (4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile) .
상기 화학식 (I)의 화합물의 제조는 염기성 조건 하에서, 예컨대 수산화나트륨의 존재 하에서 수행될 수 있다.The preparation of the compound of formula (I) can be carried out under basic conditions, for example in the presence of sodium hydroxide.
상기 화학식 (I)의 화합물의 제조에서 디메틸포름아미드(DMF), N-메틸피릴리돈(NMP), N,N'-디메틸아세트아미드(DMAc), 디메틸설퍼옥사이드(DMSO), 테트라하이드로퓨란(THF), 메타크레졸(m-cresol) 또는 이들의 혼합물 등을 용매로서 사용할 수 있다.In the preparation of the compound of formula (I), dimethylformamide (DMF), N-methylpyrilidone (NMP), N,N'-dimethylacetamide (DMAc), dimethylsulfuroxide (DMSO), tetrahydrofuran ( THF), methacresol (m-cresol), or a mixture thereof may be used as the solvent.
상기 화학식 (I)의 화합물의 제조 반응은 20 내지 45℃ 범위의 온도에서 수행될 수 있고, 바람직하게는 30 내지 45℃ 범위의 온도에서 수행될 수 있다.The reaction for preparing the compound of formula (I) may be carried out at a temperature in the range of 20 to 45 °C, preferably at a temperature in the range of 30 to 45 °C.
상기 화학식 (I)의 화합물의 제조 시간은 36시간 내지 48시간 범위일 수 있고, 바람직하게는 36시간 내지 42시간 범위일 수 있다.The preparation time of the compound of formula (I) may range from 36 hours to 48 hours, preferably from 36 hours to 42 hours.
본 발명은 하기 화학식 (Ⅱ)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 제공한다.The present invention provides a compound having a thermotropic liquid crystal structure in the side chain represented by the following formula (II).
[화학식 (Ⅱ)][Formula (II)]
[식 중, n은 1 내지 30 범위의 정수임].[wherein n is an integer ranging from 1 to 30].
상기 화학식 (Ⅱ)의 화합물은 4-(알콕시)벤조산(4-(alkoxy)benzoic acid)을 출발물질로 하여, 하이드로퀴논(hydroquinone)과의 반응을 통해 4-하이드록시페닐 4-알콕시벤조에이트 (4-hydroxyphenyl 4-alkoxybenzoate, HPBn)를 합성하고, 이후 4-하이드록시페닐 4-알콕시벤조에이트를 개시물질로 하여 에피클로로히드린과의 반응을 통해 상기 화합물을 합성할 수 있다.The compound of formula (II) is 4-(alkoxy)benzoic acid as a starting material, and 4-hydroxyphenyl 4-alkoxybenzoate ( After synthesizing 4-hydroxyphenyl 4-alkoxybenzoate (HPBn), the compound may be synthesized through reaction with epichlorohydrin using 4-hydroxyphenyl 4-alkoxybenzoate as a starting material.
상기 화합물은 4-(옥시란-2-일메톡시)페닐 4-부톡시벤조에이트 (4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate) 일 수 있다.The compound may be 4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate (4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate).
상기 화학식 (Ⅱ)의 화합물의 제조는 염기성 조건 하에서, 예컨대 수산화나트륨의 존재 하에서 수행될 수 있다.The preparation of the compound of formula (II) can be carried out under basic conditions, for example in the presence of sodium hydroxide.
상기 화학식 (Ⅱ)의 화합물의 제조 반응은 65 내지 95℃ 범위의 온도에서 수행될 수 있고, 바람직하게는 70 내지 85℃ 범위의 온도에서 수행될 수 있다.The reaction for preparing the compound of formula (II) may be carried out at a temperature in the range of 65 to 95 °C, preferably at a temperature in the range of 70 to 85 °C.
상기 화학식 (Ⅱ)의 화합물의 제조 시간은 0.5시간 내지 4시간 범위일 수 있고, 바람직하게는 0.5시간 내지 2시간 범위일 수 있다.The preparation time of the compound of formula (II) may be in the range of 0.5 hours to 4 hours, and preferably in the range of 0.5 hours to 2 hours.
본 발명은 상기 화학식 (I)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.The present invention provides a polyethylene glycol polymer obtained by ring-opening polymerization of a compound having a thermotropic liquid crystal structure in the side chain represented by the formula (I).
본 발명은 상기 화학식 (Ⅱ)로 표시되는 측쇄에 열방성 액정 구조를 갖는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.The present invention provides a polyethylene glycol polymer obtained by ring-opening polymerization of a compound having a thermotropic liquid crystal structure in the side chain represented by the formula (II).
또한, 본 발명은 하기 화학식 (Ⅲ)로 표시되며, 상기 화학식 (I) 또는 (Ⅱ)에 따라 열방성 액정 구조를 갖는 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체를 제공한다.In addition, the present invention provides a polyethylene glycol polymer represented by the following formula (III), obtained by ring-opening polymerization of a compound having a thermotropic liquid crystal structure according to the formula (I) or (II).
상기 개환 중합은 음이온성 개환 중합, 양이온성 개환 중합 및 라디칼 개환 중합 중 선택된 어느 하나일 수 있지만, 이에 제한되지는 않는다.The ring-opening polymerization may be any one selected from anionic ring-opening polymerization, cationic ring-opening polymerization, and radical ring-opening polymerization, but is not limited thereto.
[화학식 (Ⅲ)][Formula (III)]
[식 중, X1, X2는 동일하거나 다를 수 있고, 제 1 항에 따른 화합물 또는 제 2 항에 따른 화합물에서 선택됨].[wherein, X1 and X2 may be the same or different, and are selected from the compound according to
상기 화학식 (Ⅲ)은 단독 중합체 또는 공중합체일 수 있다.The formula (III) may be a homopolymer or a copolymer.
상기 개환 중합은 개시제의 존재 하에서 수행될 수 있으며, 상기 개시제는 포타슘 tert-부톡사이드, 리튬 tert-부톡사이드, 소듐 tert-부톡사이드, 포타슘 에톡사이드, 알루미늄 부톡사이드, 알루미늄 이소프로폭사이드와 같은 금속 알콕사이드일 수 있으며, 당업자에게 통상 알려진 개시제가 사용될 수 있다.The ring-opening polymerization may be carried out in the presence of an initiator, wherein the initiator is a metal such as potassium tert-butoxide, lithium tert-butoxide, sodium tert-butoxide, potassium ethoxide, aluminum butoxide, or aluminum isopropoxide. It may be an alkoxide, and initiators commonly known to those skilled in the art may be used.
상기 개환 중합은 촉매의 존재 하에서 수행될 수 있으며, 상기 촉매는 18-크라운-6 에테르, 15-크라운-5 에테르, 디벤조-18-크라운-6, 디시클로헥실-18-크라운-6 및 테트라메틸 암모늄 클로라이드(TMAC)과 같은 촉매일 수 있으며, 당업자에게 통상 알려진 촉매가 사용될 수 있다.The ring-opening polymerization may be carried out in the presence of a catalyst, wherein the catalyst is 18-crown-6 ether, 15-crown-5 ether, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and tetra It may be a catalyst such as methyl ammonium chloride (TMAC), and a catalyst commonly known to those skilled in the art may be used.
상기 개환 중합은 용매의 존재 하에서 수행될 수 있으며, 상기 용매는 톨루엔, 시클로헥산, 헥산, 헵탄, 자일렌, 에틸벤젠과 같은 용매일 수 있으며, 당업자에게 통상 알려진 용매가 사용될 수 있다.The ring-opening polymerization may be performed in the presence of a solvent, and the solvent may be a solvent such as toluene, cyclohexane, hexane, heptane, xylene, or ethylbenzene, and a solvent commonly known to those skilled in the art may be used.
상기 개환 중합에서, 전체 단량체 100 중량부에 대하여, 개시제는 1 내지 45 중량부로 포함될 수 있고, 바람직하게는 5 내지 45 중량부로 포함될 수 있고, 보다 바람직하게는 10 내지 45 중량부로 포함될 수 있다.In the ring-opening polymerization, based on 100 parts by weight of the total monomer, the initiator may be included in an amount of 1 to 45 parts by weight, preferably 5 to 45 parts by weight, and more preferably 10 to 45 parts by weight.
상기 개시제가 1 중량부 미만으로 첨가되는 경우에는 미중합 문제가 있을 수 있고, 상기 개시제가 45 중량부 초과로 첨가되는 경우에는 저분자량 고분자의 생성 문제가 있을 수 있다.When the initiator is added in an amount of less than 1 part by weight, there may be a problem of non-polymerization, and when the initiator is added in an amount of more than 45 parts by weight, there may be a problem of generating a low molecular weight polymer.
상기 개환 중합에서, 전체 단량체 100 중량부에 대하여, 촉매는 0.1 내지 15 중량부로 포함될 수 있고, 바람직하게는 0.5 내지 15 중량부로 포함될 수 있고, 보다 바람직하게는 1 내지 15 중량부로 포함될 수 있다.In the ring-opening polymerization, based on 100 parts by weight of the total monomer, the catalyst may be included in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 15 parts by weight.
상기 촉매가 0.1 중량부 미만으로 첨가되는 경우에는 미중합 또는 반응 속도 저하 문제가 일어날 수 있고, 상기 촉매가 15 중량부 초과로 첨가되는 경우에는 저분자량 고분자 생성 문제가 있을 수 있다.When the catalyst is added in an amount of less than 0.1 parts by weight, a problem of non-polymerization or a decrease in reaction rate may occur, and when the catalyst is added in an amount of more than 15 parts by weight, there may be a problem of generating a low molecular weight polymer.
상기 개환 중합은 50 내지 70℃ 범위의 온도에서 수행될 수 있고, 바람직하게는 55 내지 65℃ 범위의 온도에서 수행될 수 있다.The ring-opening polymerization may be carried out at a temperature in the range of 50 to 70 ℃, preferably at a temperature in the range of 55 to 65 ℃.
상기 개환 중합은 72시간 내지 84시간 동안 수행될 수 있고, 바람직하게는 72시간 내지 80시간 동안 수행될 수 있다.The ring-opening polymerization may be carried out for 72 hours to 84 hours, preferably for 72 hours to 80 hours.
상기 개환 중합은 비반응성 기체 조건으로 치환하여 수행될 수 있으며, 상기 비반응성 기체는 헬륨, 아르곤 또는 질소일 수 있으며, 바람직하게는 아르곤 또는 질소일 수 있고, 가장 바람직하게는 아르곤일 수 있다.The ring-opening polymerization may be performed by substituting a non-reactive gas condition, and the non-reactive gas may be helium, argon or nitrogen, preferably argon or nitrogen, and most preferably argon.
상기 개환 중합 후, 중합 용액을 알코올에 침전시킬 수 있다.After the ring-opening polymerization, the polymerization solution may be precipitated in alcohol.
상기 알코올은 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 펜탄올, 헥산올 및 헵탄올과 같은 알코올일 수 있으며, 당업자에게 통상 알려진 알코올이 사용될 수 있다.The alcohol may be an alcohol such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol and heptanol, and alcohols commonly known to those skilled in the art may be used.
상기 침전은 2회 내지 5회 수행될 수 있고, 바람직하게는 2회 내지 4회 수행될 수 있다.The precipitation may be performed 2 to 5 times, preferably 2 to 4 times.
상기 화학식 (Ⅲ)의 폴리에틸렌글리콜 중합체는 열 전도도가 0.30 (W/m·K) 이상일 수 있고, 예를 들어 0.30 내지 0.45 (W/m·K) 범위일 수 있다.The polyethylene glycol polymer of Formula (III) may have a thermal conductivity of 0.30 (W/m·K) or more, for example, in the range of 0.30 to 0.45 (W/m·K).
상기 화학식 (Ⅲ)의 폴리에틸렌글리콜 중합체는 유리전이온도가 10℃ 이상일 수 있고, 예를 들어 10 내지 60℃ 범위의 유리전이온도를 가질 수 있고, 바람직하게는 10 내지 55℃ 범위의 유리전이온도를 가질 수 있다.The polyethylene glycol polymer of Formula (III) may have a glass transition temperature of 10° C. or higher, for example, may have a glass transition temperature in the range of 10 to 60° C., preferably having a glass transition temperature in the range of 10 to 55° C. can have
상기 화학식 (Ⅲ)의 폴리에틸렌글리콜 중합체는 용융점이 85℃ 이상일 수 있고, 예를 들어 85 내지 200℃ 범위의 용융점을 가질 수 있고, 바람직하게는 88 내지 200℃ 범위의 용융점을 가질 수 있다.The polyethylene glycol polymer of Formula (III) may have a melting point of 85°C or higher, for example, may have a melting point in the range of 85 to 200°C, and preferably may have a melting point in the range of 88 to 200°C.
본 발명의 폴리에틸렌글리콜 중합체는 전자산업계에서, 예컨대 기판, 컴파운드, 접착제, 패드, 히트스프레드 및 히트싱크로 사용될 수 있다.The polyethylene glycol polymer of the present invention can be used in the electronics industry, for example, as a substrate, a compound, an adhesive, a pad, a heat spread, and a heat sink.
이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 다만 하기의 실시예는 본 발명의 내용을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, to help the understanding of the present invention, examples will be described in detail. However, the following examples are merely illustrative of the content of the present invention, and the scope of the present invention is not limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
<사용물질 및 분석방법><Substances used and analysis method>
1. 사용물질1. Substances used
4-하이드록시-4-바이페닐카르보니트릴(4-hydroxy-4-biphenylcarbonitrile) 및 6 종류의 디브로모알칸(dibromoalkanes)은 TCI (Japan)로 부터 구입하였다. 탄산칼륨(potassium carbonate), 무수 톨루엔(anhydrous toluene), 18-크라운-6(18-crown-6), 및 포타슘-터트-부톡사이드(potassium tert-butoxide)는 Alfa Aesar (USA)로 부터 입수하였다. 황산마그네슘 및 수산화나트륨과 같은 일반 화학물질 및 일반 유기용제는 Duksan 및 Daejung Chemicals (Korea)로부터 구입하였다. 무수 톨루엔, 무수 아세톤(anhydrous acetone), 무수 DMF, 및 실리카 겔은 Wako Pure Chemical (Japan)에서 구입하였다. 모든 화학물질은 추가 정제없이 사용하였으며, 모든 반응은 아르곤(Ar) 분위기에서 진행되었다.4-hydroxy-4-biphenylcarbonitrile (4-hydroxy-4-biphenylcarbonitrile) and 6 kinds of dibromoalkanes were purchased from TCI (Japan). Potassium carbonate, anhydrous toluene, 18-crown-6, and potassium tert-butoxide were obtained from Alfa Aesar (USA). . General chemicals and general organic solvents such as magnesium sulfate and sodium hydroxide were purchased from Duksan and Daejung Chemicals (Korea). Anhydrous toluene, anhydrous acetone, anhydrous DMF, and silica gel were purchased from Wako Pure Chemical (Japan). All chemicals were used without further purification, and all reactions were carried out in an argon (Ar) atmosphere.
2. 분석방법2. Analysis method
합성된 물질의 화학 구조는 경북대학교 기기분석센터에서 핵 자기 공명 분광기 (NMR, AVANCE III 500, Bruker)로 CDCl3 또는 DMSO-d6를 용매로 하여 1H NMR (500 MHz) 및 13C NMR (125 MHz)로 결정하였으며, 테트라메틸실란(tetramethylsilane, TMS)을 내부 표준물질로 사용하였다.The chemical structure of the synthesized material was analyzed by nuclear magnetic resonance spectroscopy (NMR, AVANCE III 500, Bruker) at Kyungpook National University's Instrumentation Analysis Center using CDCl 3 or DMSO-d 6 as a solvent 1 H NMR (500 MHz) and 13 C NMR ( 125 MHz), and tetramethylsilane (TMS) was used as an internal standard.
합성된 고분자의 기능기를 조사하기 위하여 푸리에-변환 적외선 분광법 (FT-IR, FT/IR-4100, Jasco)을 수행하였고, 고해상도 질량 스펙트럼 (HRMS)은 한국기초과학연구원 대구센터에서 입수하였다. To investigate the functional groups of the synthesized polymer, Fourier-transform infrared spectroscopy (FT-IR, FT/IR-4100, Jasco) was performed, and high-resolution mass spectra (HRMS) were obtained from the Daegu Center of the Korea Institute of Basic Science.
상전이 거동을 포함한 열적 특성은 N2 분위기 하에서 시차 주사 열량계 (DSC, Q2000, TA Instruments and DSC4000, PerkinElmer)로 조사되었다. 약 5.0 mg의 샘플이 DSC 측정에 사용되었으며, 빈 알루미늄 팬이 기준으로 사용되었다. DSC 측정의 가열 및 냉각 속도는 분당 2℃ 또는 5℃로, 적어도 2회의 반복 사이클 측정을 통해 임계적 차이가 없음을 확인하였다.Thermal properties including phase transition behavior were investigated with a differential scanning calorimeter (DSC, Q2000, TA Instruments and DSC4000, PerkinElmer) under N 2 atmosphere. A sample of about 5.0 mg was used for the DSC measurement, and an empty aluminum pan was used as a reference. The heating and cooling rates of the DSC measurement were 2° C. or 5° C. per minute, and it was confirmed that there was no critical difference through at least two repeated cycle measurements.
중간상 특성(mesomorphic property)은 Linkam stage (LTS420)를 가진 편광 광학 현미경 (POM, BX53M, Olympus)을 사용하여 분석되었다. POM 관찰을 위해, 20μm 두께의 LC(liquid crystals) 셀을 사용하였으며, 하기와 같이 제작하였다: The mesomorphic properties were analyzed using a polarized light microscope (POM, BX53M, Olympus) with a Linkam stage (LTS420). For POM observation, 20 μm thick LC (liquid crystals) cells were used and fabricated as follows:
유리판 (2.5 × 2.5 cm2) 및 세척된 유리판 (7.0 × 5.0 cm2)을 물, 증류수, 및 2-프로판올에 1.0 중량%의 중성 세제를 사용하여 연속 3단계로 초음파 세척하였다. 상기 판 표면을 120℃에서 1시간 동안 건조시킨 후, 스페이서(spacer) 및 에폭시 접착제로 한 쌍의 유리판을 조립하여 20μm의 셀 간격을 가지는 LC 셀을 구성하였다. LC 물질은 LC 상태에서 모세관력에 의해 셀에 주입되었다. The glass plate (2.5 × 2.5 cm 2 ) and the washed glass plate (7.0 × 5.0 cm 2 ) were ultrasonically cleaned in water, distilled water, and 2-propanol using 1.0 wt % of a neutral detergent in three successive steps. After drying the surface of the plate at 120° C. for 1 hour, a pair of glass plates were assembled with a spacer and an epoxy adhesive to construct an LC cell having a cell spacing of 20 μm. The LC material was injected into the cell by capillary force in the LC state.
중합체의 분자량은 50 mM LiBr 용리액과 디메틸포름아미드(DMF)를 사용한 겔 투과 크로마토그래피 (GPC, AS-4050, Jasco)에 의해 결정되었고, 폴리스티렌 (PS)으로 보정하였다. The molecular weight of the polymer was determined by gel permeation chromatography (GPC, AS-4050, Jasco) using 50 mM LiBr eluent and dimethylformamide (DMF) and calibrated with polystyrene (PS).
열 전도도(thermal conductivity, TC)는 원형 시편 (직경: 10 mm, 두께: 약 3 mm)으로 TC 측정 시스템 (TPS 3500S, Hot Disk)을 통해 기록되었다.Thermal conductivity (TC) was recorded through a TC measuring system (TPS 3500S, Hot Disk) with a round specimen (diameter: 10 mm, thickness: about 3 mm).
벌크 상태의 중합체의 미세구조는 X-선 회절계 (XRD, Empyrean, Malvern Panalytical)를 사용하여 조사되었다.The microstructure of the bulk polymer was investigated using an X-ray diffractometer (XRD, Empyrean, Malvern Panalytical).
<실시예 1> EPCNn : 4-(n-(옥시란-2-일메톡시)알킬옥시)-4-바이페닐카르보니트릴 (4-(<Example 1> EPCNn: 4-(n-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile (4-( nn -(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile) 모노머 합성-(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile) monomer synthesis
하기 반응식 1은 측쇄에 열방성 액정 구조인 시아노바이페닐(cyanobiphenyl)을 가지는 에폭사이드 단량체 EPCNn의 합성 과정을 나타낸 것으로, 4-하이드록시-4-바이페닐카르보니트릴(4-hydroxy-4-biphenylcarbonitrile)을 출발물질로 하여, 디브로모알칸(dibromoalkane)과의 반응을 통해 BRCNn을 합성하였고, 이후 글리시돌(glycidol)과의 반응을 통해 EPCNn을 얻었다.
<반응식 1><
① BRCNn : 4-(4-브로모알콕시)-4-바이페닐카르보니트릴 (4-(4-bromoalkoxy)-4-biphenylcarbonitrile)의 합성① BRCNn: Synthesis of 4-(4-bromoalkoxy)-4-biphenylcarbonitrile (4-(4-bromoalkoxy)-4-biphenylcarbonitrile)
A) n=4 (BRCN4)A) n=4 (BRCN4)
3구 라운드 플라스크에 탄산칼륨 (3.19 g, 23.1 mmol)과 4-하이드록시-4-바이페닐카르보니트릴 (3.00 g, 15.4 mmol)을 넣고, 아르곤 분위기로 치환한 후, 아세톤 45 ml을 추가하여 용질을 용해시켰다. 이후 1,4-디브로모부탄(1,4-dibromobutane) (2.80 ml, 23.1 mmol)을 플라스크에 투입하고 60℃에서 24시간 교반하였다. 얻어진 물질은 디에틸에테르를 이용하여 추출하였고, 유기상은 황산마그네슘으로 건조한 후 헥산:에틸 아세테이트 부피비 8:1 용액을 전개액으로 하는 실리카 컬럼 크로마토그래피를 통해 정제되었다. 수율은 57% 였다. Potassium carbonate (3.19 g, 23.1 mmol) and 4-hydroxy-4-biphenylcarbonitrile (3.00 g, 15.4 mmol) were placed in a three-necked round flask, substituted with an argon atmosphere, and 45 ml of acetone was added to the solute. was dissolved. Then, 1,4-dibromobutane (1,4-dibromobutane) (2.80 ml, 23.1 mmol) was added to the flask and stirred at 60° C. for 24 hours. The obtained material was extracted using diethyl ether, and the organic phase was dried over magnesium sulfate and purified through silica column chromatography using a hexane:ethyl acetate volume ratio 8:1 solution as a developing solution. The yield was 57%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.51 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.07 (t, J = 6.0 Hz, 2H), 3.52 (t, J = 6.5 Hz, 2H), 2.13-2.08 (m, 2H), 2.01-1.96 (m, 2H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.51 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.07 (t, J = 6.0 Hz, 2H), 3.52 (t, J = 6.5 Hz, 2H), 2.13-2.08 (m, 2H), 2.01-1.96 (m, 2H) ppm.
B) n=5 (BRCN5)B) n=5 (BRCN5)
1,5-디브로모펜탄(1,5-dibromopentane)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 42%였다. It was synthesized in the same manner as in A) except that 1,5-dibromopentane was used. The yield was 42%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.04 (t, J = 6.5 Hz, 2H), 3.47 (t, J = 7.0 Hz, 2H), 1.99-1.93 (m, 2H), 1.88-1.83 (m, 2H), 1.69-1.64 (m, 2H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.04 (t, J = 6.5 Hz, 2H), 3.47 (t, J = 7.0 Hz, 2H), 1.99-1.93 (m, 2H), 1.88-1.83 (m, 2H), 1.69-1.64 (m, 2H) ppm.
C) n=6 (BRCN6)C) n=6 (BRCN6)
1,6-디브로모헥산(1,6-dibromohexane)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 53%였다. It was synthesized in the same manner as in A), except that 1,6-dibromohexane was used. The yield was 53%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.03 (t, J = 6.0 Hz, 2H), 3.45 (t, J = 7.0 Hz, 2H), 1.93-1.90 (m, 2H), 1.85-1.82 (m, 2H), 1.53-1.52 (m, 4H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.03 (t, J = 6.0 Hz, 2H), 3.45 (t, J = 7.0 Hz, 2H), 1.93-1.90 (m, 2H), 1.85-1.82 (m, 2H), 1.53-1.52 (m, 4H) ppm.
D) n=7 (BRCN7)D) n=7 (BRCN7)
1,7-디브로모헵탄(1,7-dibromoheptane)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 24%였다. It was synthesized in the same manner as in A), except that 1,7-dibromoheptane was used. The yield was 24%.
1H NMR (500 MHz, CDCl3): δ = 7.63 (d, J = 8.5 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 2H), 6.93 (d, J = 9.0 Hz, 2H), 3.95 (t, J = 6.5 Hz, 2H), 3.37 (t, J = 6.5 Hz, 2H), 1.91-1.79 (m, 4H), 1.51-1.40 (m, 6H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.63 (d, J = 8.5 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 2H), 6.93 (d, J = 9.0 Hz, 2H), 3.95 (t, J = 6.5 Hz, 2H), 3.37 (t, J = 6.5 Hz, 2H), 1.91-1.79 (m, 4H), 1.51-1.40 (m, 6H) ppm.
E) n=8 (BRCN8)E) n=8 (BRCN8)
1,8-디브로모옥탄(1,8-dibromooctane)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 34%였다.It was synthesized in the same manner as in A) except that 1,8-dibromooctane was used. The yield was 34%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 9.0 Hz, 2H), 4.02 (t, J = 6.5 Hz, 2H), 3.43 (t, J = 6.5 Hz, 2H), 1.90-1.79 (m, 4H), 1.53-1.34 (m, 8H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 9.0 Hz, 2H), 4.02 (t, J = 6.5 Hz, 2H), 3.43 (t, J = 6.5 Hz, 2H), 1.90-1.79 (m, 4H), 1.53-1.34 (m, 8H) ppm.
F) n=9 (BRCN9)F) n=9 (BRCN9)
1,9-디브로모노난(1,9-dibromononane)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 51%였다.It was synthesized in the same manner as in A), except that 1,9-dibromononane was used. The yield was 51%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.02 (t, J = 6.5 Hz, 2H), 3.43 (t, J = 6.5 Hz, 2H), 1.89-1.78 (m, 4H), 1.51-1.31 (m, 10H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 4.02 (t, J = 6.5 Hz, 2H), 3.43 (t, J = 6.5 Hz, 2H), 1.89-1.78 (m, 4H), 1.51-1.31 (m, 10H) ppm.
② EPCNn (4-(② EPCNn (4-( nn -(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile)의 합성Synthesis of -(oxiran-2-ylmethoxy)alkyloxy)-4-biphenylcarbonitrile)
G) n=4 (EPCN4)G) n=4 (EPCN4)
상기 BRCN4 (1.94 g, 5.87 mmol)와 수산화나트륨 (0.352 g, 8.81 mmol)을 3구 라운드 플라스크에 넣고 아르곤 분위기로 치환한 후, 글리시돌 (1.00 ml, 11.6 mmol)과 다이메틸포름아마이드 35.0 ml을 추가하였다. 30℃에서 3일간 반응을 진행하였고, 얻어진 물질은 에틸 아세테이트를 이용하여 추출하여 황산마그네슘으로 건조한 후 헥산:에틸아세테이트 부피비 4:1 용액을 전개액으로 하는 실리카 컬럼 크로마토그래피를 통해 정제되었다. 수율은 51%였다. 물질의 확인은 1H NMR, 13C NMR, 고분해능 질량 분석을 통해 이뤄졌으며, 분석 결과는 다음과 같다. The BRCN4 (1.94 g, 5.87 mmol) and sodium hydroxide (0.352 g, 8.81 mmol) were placed in a three-necked round flask, substituted with an argon atmosphere, and glycidol (1.00 ml, 11.6 mmol) and dimethylformamide 35.0 ml was added. The reaction was carried out at 30° C. for 3 days, and the obtained material was extracted using ethyl acetate, dried over magnesium sulfate, and purified by silica column chromatography using a 4:1 solution by volume of hexane:ethyl acetate as a developing solution. The yield was 51%. Identification of the material was made through 1 H NMR, 13 C NMR, and high-resolution mass spectrometry, and the analysis results are as follows.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.04 (t, J = 6.5 Hz, 2H), 3.77 (dd, J = 11.5, 3 Hz, 1H), 3.60 (m, 2H), 3.39 (dd, J = 11.5, 6 Hz, 1H), 3.16 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.90 (m, 2H), 1.81 (m, 2H) ppm. 13C NMR (125 MHz, CDCl3):δ = 159.7, 145.3, 132.6, 131.4, 128.3, 127.1, 119.1, 115.1, 110.1, 71.5, 71.1, 67.8, 50.9, 44.2, 26.3, 26.0 ppm. HRMS (+EI): calcd for [C20H21NO3]+: m/z 323.1521; found: m/z 323.1522 (도 1(a) 및 도 2(a)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.04 (t, J = 6.5 Hz, 2H), 3.77 (dd, J = 11.5, 3 Hz, 1H), 3.60 (m, 2H), 3.39 (dd, J = 11.5, 6 Hz, 1H), 3.16 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.90 (m, 2H), 1.81 (m, 2H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.7, 145.3, 132.6, 131.4, 128.3, 127.1, 119.1, 115.1, 110.1, 71.5, 71.1, 67.8, 50.9, 44.2, 26.3, 26.0 ppm. HRMS (+EI): calcd for [C 20 H 21 NO 3 ] + : m/z 323.1521; found: m/z 323.1522 (FIGS. 1(a) and 2(a)).
H) n=5 (EPCN5)H) n=5 (EPCN5)
상기 BRCN5를 사용한 것을 제외하고, G)와 동일한 절차로 합성되었다. 수율은 35%였다.It was synthesized in the same procedure as G) except that BRCN5 was used. The yield was 35%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.02 (t, J = 6 Hz, 2H), 3.77 (dd, J = 11.5, 3 Hz, 1H), 3.55 (m, 2H), 3.40 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4 Hz, 1H), 2.62 (dd, J = 5, 2.5 Hz, 1H), 1.84 (m, 2H), 1.68 (m, 2H), 1.56 (m, 2H) ppm. 13C NMR (125 MHz, CDCl3): δ = 159.7, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.6, 71.4, 68.0, 50.9, 44.3, 29.5, 29.0, 22.7 ppm. HRMS (+EI): calcd for [C21H23NO3]+: m/z 337.1678; found: m/z 337.1680 (도 1(b) 및 도 2(b)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.02 (t, J = 6 Hz, 2H), 3.77 (dd, J = 11.5, 3 Hz, 1H), 3.55 (m, 2H), 3.40 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4 Hz, 1H), 2.62 (dd, J = 5, 2.5 Hz, 1H), 1.84 (m, 2H), 1.68 (m, 2H), 1.56 (m, 2H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.7, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.6, 71.4, 68.0, 50.9, 44.3, 29.5, 29.0, 22.7 ppm. HRMS (+EI): calcd for [C 21 H 23 NO 3 ] + : m/z 337.1678; found: m/z 337.1680 (FIGS. 1(b) and 2(b)).
I) n=6 (EPCN6)I) n=6 (EPCN6)
상기 BRCN6를 사용한 것을 제외하고, G)와 동일한 절차로 합성되었다. 수율은 47%였다. It was synthesized in the same procedure as G) except that BRCN6 was used. The yield was 47%.
1H NMR (500 MHz, CDCl3):δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.01 (t, J = 6.5 Hz, 2H), 3.74 (dd, J = 11.5, 3 Hz, 1H), 3.52 (m, 2H), 3.38 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.82 (m, 2H), 1.64 (m, 2H), 1.50 (m, 4H) ppm. 13C NMR (125 MHz, CDCl3):δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.5, 71.5, 68.0, 50.9, 44.3, 29.6, 29.7, 25.9 ppm. HRMS (+EI): calcd for [C22H25NO3]+: m/z 351.1834; found: m/z 351.1832 (도 1(c) 및 도 2(c)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.01 (t, J = 6.5 Hz, 2H), 3.74 (dd, J = 11.5, 3 Hz, 1H), 3.52 (m, 2H), 3.38 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.82 (m, 2H), 1.64 (m, 2H), 1.50 (m, 4H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.5, 71.5, 68.0, 50.9, 44.3, 29.6, 29.7, 25.9 ppm. HRMS (+EI): calcd for [C 22 H 25 NO 3 ] + : m/z 351.1834; found: m/z 351.1832 (FIGS. 1(c) and 2(c)).
J) n=7 (EPCN7)J) n=7 (EPCN7)
상기 BRCN7을 사용한 것을 제외하고, G)와 동일한 절차로 합성되었다. 수율은 33%였다. It was synthesized in the same procedure as G) except that BRCN7 was used. The yield was 33%.
1H NMR (500 MHz, CDCl3): δ = 7.70 (d, J = 9 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.73 (dd, J =11.5, 3 Hz, 1H), 3.51 (m, 2H), 3.39 (dd, J =11.5, 5.5 Hz, 1H), 3.14 (m, 1H), 2.80 (dd, J =5, 4 Hz, 1H), 2.61 (dd, J =5, 2.5 Hz, 1H), 1.81 (m, 2H), 1.61 (m, 2H), 1.50 (m, 2H), 1.39 (m, 4H) ppm. 13C NMR (125 MHz, CDCl3): δ= 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.6, 71.5, 68.1, 50.9, 44.3, 29.6, 29.2, 29.1, 26.0, 25.9 ppm. HRMS (+EI): calcd for [C23H27NO3]+: m/z 365.1991; found: m/z 365.1992 (도 1(d) 및 도 2(d)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 9 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.73 (dd, J = 11.5, 3 Hz, 1H), 3.51 (m, 2H), 3.39 (dd, J = 11.5, 5.5 Hz, 1H), 3.14 (m, 1H), 2.80 (dd, J =5, 4 Hz, 1H), 2.61 (dd, J =5, 2.5 Hz, 1H), 1.81 (m, 2H), 1.61 (m, 2H), 1.50 (m, 2H), 1.39 (m, 4H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.6, 71.5, 68.1, 50.9, 44.3, 29.6, 29.2, 29.1, 26.0, 25.9 ppm. HRMS (+EI): calcd for [C 23 H 27 NO 3 ] + : m/z 365.1991; found: m/z 365.1992 (FIGS. 1(d) and 2(d)).
K) n=8 (EPCN8)K) n=8 (EPCN8)
상기 BRCN8을 사용한 것을 제외하고, G)와 동일한 절차로 합성되었다. 수율은 44%였다. It was synthesized in the same procedure as G) except that BRCN8 was used. The yield was 44%.
1H NMR (500 MHz, CDCl3):δ = 7.70 (d, J = 8 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.73 (dd, J = 11.5, 3 Hz, 1H), 3.50 (m, 2H), 3.39 (dd, J = 11.5, 5.5 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.80 (m, 2H), 1.60 (m, 2H), 1.47 (m, 2H), 1.36 (m, 6H) ppm. 13C NMR (125 MHz, CDCl3):δ= 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.7, 71.5, 68.1, 50.9, 44.3, 29.7, 29.4, 29.3, 29.2, 26.0, 25.9 ppm. HRMS (+EI): calcd for [C24H29NO3]+: m/z 379.2147; found: m/z 379.2145 (도 1(e) 및 도 2(e)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 9 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.73 (dd, J = 11.5, 3 Hz, 1H), 3.50 (m, 2H), 3.39 (dd, J = 11.5, 5.5 Hz, 1H), 3.15 (m, 1H), 2.80 (dd, J = 5, 4.5 Hz, 1H), 2.61 (dd, J = 5, 3 Hz, 1H), 1.80 (m, 2H), 1.60 (m, 2H), 1.47 (m, 2H), 1.36 (m, 6H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.7, 71.5, 68.1, 50.9, 44.3, 29.7, 29.4, 29.3, 29.2, 26.0 , 25.9 ppm. HRMS (+EI): calcd for [C 24 H 29 NO 3 ] + : m/z 379.2147; found: m/z 379.2145 (FIGS. 1(e) and 2(e)).
L) n=9 (EPCN9)L) n=9 (EPCN9)
상기 BRCN9를 사용한 것을 제외하고, G)와 동일한 절차로 합성되었다. 수율은 38%였다. It was synthesized in the same procedure as G) except that BRCN9 was used. The yield was 38%.
1H NMR (500 MHz, CDCl3):δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.72 (dd, J = 11.5, 3 Hz, 1H), 3.50 (m, 2H), 3.37 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.79 (dd, J = 5, 4 Hz, 1H), 2.61 (dd, J = 5, 2.5 Hz, 1H), 1.80 (m, 2H), 1.59 (m, 2H), 1.47 (m, 2H), 1.33 (m, 8H) ppm. 13C NMR (125 MHz, CDCl3):δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.7, 71.5, 68.2, 50.9, 44.3, 29.7, 29.5, 29.4, 29.3, 29.2, 26.1, 26.0 ppm. HRMS (+EI): calcd for [C25H31NO3]+: m/z 393.2304; found: m/z 393.2304 (도 1(f) 및 도 2(f)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.70 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 9 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 4.00 (t, J = 6.5 Hz, 2H), 3.72 (dd, J = 11.5, 3 Hz, 1H), 3.50 (m, 2H), 3.37 (dd, J = 11.5, 6 Hz, 1H), 3.15 (m, 1H), 2.79 (dd, J = 5, 4 Hz, 1H), 2.61 (dd, J = 5, 2.5 Hz, 1H), 1.80 (m, 2H), 1.59 (m, 2H), 1.47 (m, 2H), 1.33 (m, 8H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ = 159.8, 145.3, 132.6, 131.3, 128.3, 127.1, 119.1, 115.1, 110.0, 71.7, 71.5, 68.2, 50.9, 44.3, 29.7, 29.5, 29.4, 29.3, 29.2 , 26.1, 26.0 ppm. HRMS (+EI): calcd for [C 25 H 31 NO 3 ] + : m/z 393.2304; found: m/z 393.2304 (FIGS. 1(f) and 2(f)).
<실시예 2> EPCNn 폴리머 (P-EPCNn) 의 합성<Example 2> Synthesis of EPCNn polymer (P-EPCNn)
하기 반응식 2는 측쇄에 액정 구조인 시아노바이페닐을 가지는 폴리에틸렌글리콜 유도체인 P-EPCNn의 합성 과정을 나타낸 것으로, 하기 반응식 2에 나타낸 바와 같이 폴리에틸렌글리콜 주쇄를 형성하기 위한 에폭사이드 단량체 EPCNn의 음이온성 개환 중합을 통해 합성되었다.
<반응식 2><
A) n=4 (P-EPCN4)A) n=4 (P-EPCN4)
EPCN4 (1.34 mmol), 포타슘 tert-부톡사이드(potassium tert-butoxide) (50.5 mg, 500 μmol), 18-크라운-6(18-crown-6) (28.0 mg, 100 μmol)을 Schlenk 튜브에 넣은 후 아르곤 분위기로 치환한 후, 톨루엔 3 ml을 추가하였다. 중합 용액을 60℃에서 3일간 교반한 후 메탄올 50 ml에 부어 침전시킨 후, 침전물을 회수하였다. 침전 과정은 2번 반복되었고, 옅은 노란색의 고체를 61%의 수율로 수득하였다.EPCN4 (1.34 mmol), potassium tert -butoxide (50.5 mg, 500 μmol), and 18-crown-6 (18-crown-6) (28.0 mg, 100 μmol) were added to a Schlenk tube. After replacing with an argon atmosphere, 3 ml of toluene was added. After the polymerization solution was stirred at 60° C. for 3 days, it was poured into 50 ml of methanol for precipitation, and the precipitate was recovered. The precipitation process was repeated twice, and a pale yellow solid was obtained in a yield of 61%.
1H NMR (500 MHz, CDCl3): δ = 7.63-7.45 (m, 6H), 6.93-6.92 (m, 2H), 3.98-3.95 (m, 2H), 3.76-3.39 (m, 7H), 1.83-1.40 (m, 4H), 1.09 (s, terminal-9H) ppm. FT-IR (ATR): 3365, 3184, 2940, 2867, 2225, 1651, 1603, 1495, 1250, 1110, 822, 770 cm-1 (도 3(a)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.63-7.45 (m, 6H), 6.93-6.92 (m, 2H), 3.98-3.95 (m, 2H), 3.76-3.39 (m, 7H), 1.83 -1.40 (m, 4H), 1.09 (s, terminal-9H) ppm. FT-IR (ATR): 3365, 3184, 2940, 2867, 2225, 1651, 1603, 1495, 1250, 1110, 822, 770 cm -1 (Fig. 3(a)).
B) n=5 (P-EPCN5)B) n=5 (P-EPCN5)
상기 EPCN5를 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 72%였다.It was synthesized in the same manner as in A) except that EPCN5 was used. The yield was 72%.
1H NMR (500 MHz, CDCl3): δ = 7.67-7.66 (m, 2H), 7.62-7.61 (m, 2H), 7.50-7.49 (m, 2H), 6.96-6.95 (m, 2H), 3.98-3.97 (m, 2H), 3.80-3.41 (m, 7H), 1.80-1.42 (m, 6H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3360, 3181, 2937, 2865, 2224, 1657, 1602, 1494, 1248, 1110, 821, 771 cm-1 (도 3(b)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.67-7.66 (m, 2H), 7.62-7.61 (m, 2H), 7.50-7.49 (m, 2H), 6.96-6.95 (m, 2H), 3.98 -3.97 (m, 2H), 3.80-3.41 (m, 7H), 1.80-1.42 (m, 6H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3360, 3181, 2937, 2865, 2224, 1657, 1602, 1494, 1248, 1110, 821, 771 cm -1 (Fig. 3(b)).
C) n=6 (P-EPCN6)C) n=6 (P-EPCN6)
상기 EPCN6을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 71%였다.It was synthesized in the same manner as in A) except that EPCN6 was used. The yield was 71%.
1H NMR (500 MHz, CDCl3): δ = 7.66 (s, 2H), 7.62-7.61 (m, 2H), 7.50-7.49 (m, 2H), 6.96-6.95 (m, 2H), 3.98-3.97 (m, 2H), 3.77-3.41 (m, 7H), 1.80-1.42 (m, 8H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3362, 3176, 2935, 2863, 2224, 1656, 1603, 1495, 1250, 1111, 822, 770 cm-1 (도 3(c)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.66 (s, 2H), 7.62-7.61 (m, 2H), 7.50-7.49 (m, 2H), 6.96-6.95 (m, 2H), 3.98-3.97 (m, 2H), 3.77-3.41 (m, 7H), 1.80-1.42 (m, 8H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3362, 3176, 2935, 2863, 2224, 1656, 1603, 1495, 1250, 1111, 822, 770 cm -1 (Fig. 3(c)).
D) n=7 (P-EPCN7)D) n=7 (P-EPCN7)
상기 EPCN7을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 71%였다.It was synthesized in the same manner as in A) except that EPCN7 was used. The yield was 71%.
1H NMR (500 MHz, CDCl3): δ = 7.66 (s, 2H), 7.62 (s, 2H), 7.50 (s, 2H), 6.97 (s, 2H), 3.98-3.97 (m, 2H), 3.78-3.43 (m, 7H), 1.79-1.37 (m, 10H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3364, 3184, 2989, 2990, 2225, 1653, 1603, 1495, 1393, 1249, 1065, 822, 771 cm-1 (도 3(d)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.66 (s, 2H), 7.62 (s, 2H), 7.50 (s, 2H), 6.97 (s, 2H), 3.98-3.97 (m, 2H), 3.78-3.43 (m, 7H), 1.79-1.37 (m, 10H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3364, 3184, 2989, 2990, 2225, 1653, 1603, 1495, 1393, 1249, 1065, 822, 771 cm −1 ( FIG. 3(d) ).
E) n=8 (P-EPCN8)E) n=8 (P-EPCN8)
상기 EPCN8을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 71%였다.It was synthesized in the same procedure as A) except that EPCN8 was used. The yield was 71%.
1H NMR (500 MHz, CDCl3): δ = 7.68-7.67 (m, 2H), 7.63-7.62 (m, 2H), 7.52-7.50 (m, 2H), 6.97-6.96 (m, 2H), 3.98-3.96 (m, 2H), 3.74-3.42 (m, 7H), 1.79-1.34 (m, 12H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3364, 3185, 2930, 2859, 2224, 1652, 1603, 1495, 1250, 1111, 1077, 822, 770 cm-1 (도 3(e)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.68-7.67 (m, 2H), 7.63-7.62 (m, 2H), 7.52-7.50 (m, 2H), 6.97-6.96 (m, 2H), 3.98 -3.96 (m, 2H), 3.74-3.42 (m, 7H), 1.79-1.34 (m, 12H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3364, 3185, 2930, 2859, 2224, 1652, 1603, 1495, 1250, 1111, 1077, 822, 770 cm -1 (Fig. 3(e)).
F) n=9 (P-EPCN9)F) n=9 (P-EPCN9)
상기 EPCN9를 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 71%였다.It was synthesized in the same manner as in A) except that EPCN9 was used. The yield was 71%.
1H NMR (500 MHz, CDCl3): δ = 7.68-7.67 (m, 2H), 7.65-7.62 (m, 2H), 7.53-7.51 (m, 2H), 6.98-6.97 (m, 2H), 4.00-3.94 (m, 2H), 3.73-3.41 (m, 7H), 1.79-1.31 (m, 14H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3380, 3192, 2931, 2854, 2225, 1650, 1603, 1495, 1394, 1251, 1110, 1077, 823, 770 cm-1 (도 3(f)). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.68-7.67 (m, 2H), 7.65-7.62 (m, 2H), 7.53-7.51 (m, 2H), 6.98-6.97 (m, 2H), 4.00 -3.94 (m, 2H), 3.73-3.41 (m, 7H), 1.79-1.31 (m, 14H), 1.11 (s, terminal-9H) ppm. FT-IR (ATR): 3675, 3380, 3192, 2931, 2854, 2225, 1650, 1603, 1495, 1394, 1251, 1110, 1077, 823, 770 cm -1 (Fig. 3(f)).
상기에 따라 수득된 P-EPCNn의 FT-IR (Fourier transform infrared) 스펙트럼인 도 4를 참조하면, 폴리에틸렌글리콜(PEG) 골격 중합체가 남은 에폭사이드 모이어티없이 합성되었음을 확인할 수 있다.Referring to FIG. 4, which is a Fourier transform infrared (FT-IR) spectrum of P-EPCNn obtained as described above, it can be confirmed that the polyethylene glycol (PEG) backbone polymer was synthesized without the remaining epoxide moiety.
하기 표 1은 상기에 따라 수득된 P-EPCNn의 분자량을 나타낸 것이고 (도 5), 하기 표 2는 P-EPCNn의 물성을 나타낸 것이다.Table 1 below shows the molecular weight of P-EPCNn obtained as described above (FIG. 5), and Table 2 below shows the physical properties of P-EPCNn.
상기에 따라 합성된 물질의 중간상 및 상전이 거동을 시차주사열량계(DSC) 및 편광광학현미경(POM)을 통해 분석한 결과, 도 6 내지 도 10에 나타난 바와 같이, POM에서 관찰된 상전이 거동이 DSC 결과와 동일한 경향을 보임을 확인할 수 있다.As a result of analyzing the intermediate phase and phase transition behavior of the synthesized material through differential scanning calorimetry (DSC) and polarization optical microscopy (POM), as shown in FIGS. 6 to 10 , the phase transition behavior observed in the POM is the DSC result. It can be seen that the same trend as
단량체 상태에서는 대표적인 열방성(thermotropic)의 액정인 시아노바이페닐(cyanobiphenyl, CB) 구조가 투명한 액정상을 형성하나, 알킬 연결 길이에 따라 약간의 다양화가 관찰되었다. 구체적으로 도 7을 참조하면, EPCN5, EPCN6, 및 EPCN8은 거울상 이방성 중간상을 보인 반면, EPCN4, EPCN7, 및 EPCN9는 냉각 동안 단방성 LC를 나타냈다. EPCN5는 실온 이하(below) 비교적 넓은 범위에서 LC 상을 나타내는 반면, EPCN7은 실온 이상(above) 상당히 좁은 영역에서 중간상을 나타내었다. 게다가, POM 관찰에서 모든 단량체의 LC 상은 투명한 네마틱(nematic) 상임을 확인하였다. 전반적으로, EPCN 시리즈는 실온보다 약간 높은, 약 40℃에서 15℃의 범위의 중간상을 갖는 열방성 LC 였다.In the monomeric state, a typical thermotropic liquid crystal, cyanobiphenyl (CB) structure, forms a transparent liquid crystal phase, but a slight diversification was observed depending on the length of the alkyl linkage. Specifically, referring to FIG. 7 , EPCN5, EPCN6, and EPCN8 showed an enantiotropic mesophase, whereas EPCN4, EPCN7, and EPCN9 showed unidirectional LC during cooling. EPCN5 showed an LC phase in a relatively wide range below room temperature, whereas EPCN7 showed an intermediate phase in a fairly narrow range above room temperature. In addition, the POM observation confirmed that the LC phase of all monomers was a transparent nematic phase. Overall, the EPCN series were thermotropic LCs with mesophases ranging from about 40°C to 15°C, slightly above room temperature.
도 9를 참조하면, P-EPCNn은 고분자 상태에서 EPCNn과 독립적인 상전이 거동을 보임을 확인할 수 있다. PEG 주쇄 중합체가 단량체의 구조를 유지하면서 형성되었기 때문에 중합체의 구조는 어느 정도 경향이 있을 것으로 예상하였으나, 결과는 이를 나타내지 않았다. Referring to FIG. 9 , it can be confirmed that P-EPCNn exhibits a phase transition behavior independent of EPCNn in the polymer state. The structure of the polymer was expected to tend to some extent because the PEG backbone polymer was formed while maintaining the structure of the monomer, but the results did not indicate this.
P-EPCN4를 제외한 유리전이온도(Tg)는 실온에서 약간 낮은 15℃와 20℃ 사이에서 관찰된 반면, P-EPCN4의 Tg는 실온에서 약간 높은 32.6℃에서 관찰되었다.The glass transition temperature (T g ), except for P-EPCN4, was observed between 15 and 20°C, which is slightly lower at room temperature, whereas the T g of P-EPCN4 was observed at 32.6°C, which is slightly higher at room temperature.
용융온도(Tm)의 경우, 홀수 개의 사슬 스페이서를 갖는 P-EPCN5, P-EPCN7, 및 P-EPCN9의 흡열 피크가 100℃ 아래에서 관찰된 반면, 짝수 개의 사슬 스페이서를 갖는 P-EPCN4, P-EPCN6, 및 P-EPCN8의 흡열 피크는 100℃ 이상에서 관찰되었다.For the melting temperature (T m ), endothermic peaks of P-EPCN5, P-EPCN7, and P-EPCN9 with an odd number of chain spacers were observed below 100 °C, whereas P-EPCN4, P with an even number of chain spacers The endothermic peaks of -EPCN6 and P-EPCN8 were observed at 100°C or higher.
유리전이 거동과 달리, 용융 거동에서 홀수-짝수 효과와 관련된 어떤 경향성이 관찰되었는데, 이는 알킬 스페이서 결정 구조의 형성과 관련이 있는 것으로 생각된다.In contrast to the glass transition behavior, a certain trend related to odd-even effects was observed in the melting behavior, which is thought to be related to the formation of alkyl spacer crystal structures.
상기 표 1 및 2에 나타난 바와 같이, P-EPCNn은 알킬 스페이서에 따라 뚜렷한 홀수-짝수 효과를 보였다. 이러한 결과는 측쇄의 평균 형태 변화 및 스페이서의 당량 변화에 대한 메소겐기(mesogenic group)의 상대적 방향의 영향으로 생각된다. 홀수 부재의 경우 메소겐 단위는 골격에 직교하는 반면, 짝수의 경우 메소겐 단위는 골격에 대해 특정 각도에 위치하는 것으로 제한되었다. 게다가, 사슬 길이의 영향이 홀수 부재에서는 현저하지만, 짝수 부재에서는 그렇지 않음을 확인할 수 있다. 이러한 결과는 대칭 효과에 의해 제한되는 짝수 링커가 사슬 길이보다 각도 제한이 더 큼을 암시한다.As shown in Tables 1 and 2 above, P-EPCNn showed a distinct odd-even effect according to the alkyl spacer. This result is considered to be the influence of the relative direction of the mesogenic group on the change in the average conformation of the side chain and the change in the equivalent weight of the spacer. For odd members the mesogenic units were orthogonal to the backbone, whereas for even numbers the mesogenic units were limited to being positioned at specific angles to the backbone. Moreover, it can be seen that the influence of chain length is significant in odd-numbered members, but not in even-numbered members. These results suggest that even linkers constrained by symmetry effects have greater angular restrictions than chain lengths.
전반적으로, P-EPCN4의 상 전이 온도는 다른 고분자에 비해 약간 높았고, 다른 고분자의 거동은 유사하였다. 이는 분자량 및 중합도가 유사하게 조절되어 나타난 결과로 생각된다. P-EPCNn은 주쇄형이 아닌 측쇄 액정고분자(side chain LCP, SCLCP) 였기 때문에 상호작용이 가능한 링커 길이가 어느 정도 확보되었을 때 유사한 상전이 거동이 관찰된 것으로 추정된다. 특히, Tm 이상의 온도에서는 고 점도의 반투명 액상이 얻어지고, Tm 이하에서는 불투명한 고상이 유지되었다. Overall, the phase transition temperature of P-EPCN4 was slightly higher than that of other polymers, and the behavior of other polymers was similar. This is considered to be a result of similarly controlled molecular weight and polymerization degree. Since P-EPCNn was not a main chain type, but a side chain liquid crystal polymer (SCLCP), it is presumed that a similar phase transition behavior was observed when a linker length capable of interaction was secured to some extent. In particular, a translucent liquid with high viscosity was obtained at a temperature above T m , and an opaque solid phase was maintained below T m .
열 전도도(TC) 평가를 위해, 용융 공정을 통해 P-EPCNn 벌크 시편을 제조하였다. P-EPCNn은 각각 폴리머의 Tm 이상의 온도에서 용융되어 1 cm 직경의 원형 칩으로 가공되었다. 두께는 샘플의 양에 따라 다양하나, 약 3 mm 정도로 고정되었다 (도 11). 중합 후 샘플 색은 완전히 흰색이었으나, 가공 후 옅은 노란색으로 변했는데, 이는 방향족 성분의 상호작용 때문일 수 있다. TC 값은 상기 표 2를 통해 확인할 수 있다.For thermal conductivity (TC) evaluation, P-EPCNn bulk specimens were prepared through a melting process. P-EPCNn was melted at a temperature above the T m of the polymer, respectively, and processed into circular chips with a diameter of 1 cm. The thickness varies depending on the amount of the sample, but was fixed to about 3 mm ( FIG. 11 ). The sample color after polymerization was completely white, but turned pale yellow after processing, which may be due to the interaction of aromatic components. The TC value can be confirmed through Table 2 above.
액정고분자는 특정 방향에서 그들 분자 배열로 인해 이방성 열 전도도 특성을 나타낸다. 특히, 이 분자 배향은 특정 방향으로 균일한 배열을 통해 포논 산란(phonon scattering)을 감소시켜 열 전도 특성을 개선시키고, 차원에 따라 다른 포논 경로를 유도한다. 그러나, 본 실험에서는 P-EPCNn이 벌크 재료 준비 과정에서 특별한 배열 과정을 거치지 않았기 때문에, 차원에 따른 이방성을 나타내지는 않았다. 미시적 규모에서는 이방성을 나타내나, 거시적 수준에서는 등방성을 나타낼 것으로 예상된다. 그럼에도 불구하고, P-EPCN4를 제외한 모든 P-EPCNn는 0.42-0.46 W m-1K-1 의 상당히 높은 TC를 나타내었다. P-EPCN4는 0.32 W m-1K-1 의 TC를 나타내었고, 이는 PEG 값을 고려할 때 역시 높은 값이다. 주쇄가 P-EPCNn과 유사한 PEG에서 분자량에 따라 약간의 변화가 관찰되었지만, TC는 약 0.2에서 0.3 W m-1K-1 이었다. 따라서, 펜던트 사슬에서 시아노바이페닐 메소겐의 상호 작용으로 인해 P-EPCNn는 2배 높은 TC를 가짐이 명백하였다.Liquid crystal polymers exhibit anisotropic thermal conductivity properties due to their molecular arrangement in a specific direction. In particular, this molecular orientation reduces phonon scattering through a uniform arrangement in a specific direction to improve heat conduction properties, and induces different phonon pathways depending on the dimension. However, in this experiment, since P-EPCNn did not undergo a special arrangement in the bulk material preparation process, it did not show dimensional anisotropy. It is expected to exhibit anisotropy at the microscopic scale, but isotropic at the macroscopic level. Nevertheless, all P-EPCNn except P-EPCN4 showed a significantly high TC of 0.42-0.46 W m -1 K -1 . P-EPCN4 exhibited a TC of 0.32 W m −1 K −1 , which is also a high value considering the PEG value. A slight change with molecular weight was observed in PEG whose main chain was similar to that of P-EPCNn, but the TC ranged from about 0.2 to 0.3 W m −1 K −1 . Therefore, it was evident that P-EPCNn has a 2-fold higher TC due to the interaction of cyanobiphenyl mesogen in the pendant chain.
분자 상호작용을 확인하기 위해, X-선 회절(XRD) 측정을 통해 벌크 시편의 결정 구조를 분석한 결과, 도 12에 나타난 바와 같이, 회절 곡선에서 2θ가 10°미만인 저각 영역의 피크 (옅은 노란색으로 표시), 20°부근의 피크 (옅은 파란색으로 표시) 및 25°이상의 피크 (옅은 녹색으로 표시)의 3가지 유형의 특정 피크가 관찰되었다. 분자량에 따른 차이는 있으나, 고 결정도의 반 결정성 고분자로서 순수 선형 PEG는 20°전 후에서의 뚜렷한 두 피크 및 25°이상에서의 여러 피크를 보여주며, P-EPCNn이 유사한 골격 구조의 SCLCP 임을 시사하였다. P-EPCN6 내지 P-EPCN8의 경우, 2θ = 20°영역 근처에서 PEG 골격으로부터 유래된 피크가 명확하게 식별되었으며, 나머지는 모호하지만 유사한 모양을 나타내었다. As a result of analyzing the crystal structure of the bulk specimen through X-ray diffraction (XRD) measurement to confirm the molecular interaction, as shown in FIG. 12 , the peak in the low-angle region with 2θ less than 10° in the diffraction curve (pale yellow) 3 types of specific peaks were observed: ), a peak near 20° (indicated in light blue), and a peak above 25° (indicated in pale green). Although there is a difference according to the molecular weight, pure linear PEG as a semi-crystalline polymer with high crystallinity shows two distinct peaks before and after 20° and several peaks at 25° or higher, indicating that P-EPCNn is SCLCP with a similar backbone structure. suggested. In the case of P-EPCN6 to P-EPCN8, peaks derived from the PEG backbone were clearly identified in the vicinity of the 2θ = 20° region, and the rest were vague but exhibited similar shapes.
그러나, 피크 선명도(sharpness)는, 랜덤 LC 배열에 따른 메소겐의 면간 거리를 나타내는 것으로 가정된 PEG 샘플에 대해 다르게 나타났다. 이러한 넓은 피크는 전형적인 메소겐 간 거리에 해당하는 대략 4-5 Å 였다. 특히, 메소겐 자가-조립의 명백한 증거는 10°미만의 저각 영역에서 관찰되었다. 사슬 스페이서의 길이에 따라, 약 4°및 7-8°의 피크에서 약간의 차이는 있었다. 약 4°에서의 피크는 20-25 Å에 해당하고, 7-8°에서의 피크는 11-13 Å에 해당하여, 상대적으로 장거리 규칙성을 나타낸다.However, the peak sharpness was different for the PEG samples, which were assumed to represent the interplanar distances of the mesogens according to the random LC arrangement. These broad peaks were approximately 4-5 Å, corresponding to typical inter-mesogen distances. In particular, clear evidence of mesogen self-assembly was observed in the low angle region of less than 10°. Depending on the length of the chain spacer, there was a slight difference in the peaks of about 4° and 7-8°. The peak at about 4° corresponds to 20-25 Å, and the peak at 7-8° corresponds to 11-13 Å, indicating relatively long-range regularity.
P-EPCN5 내지 P-EPCN9는 장거리 상호작용이 관찰되었는데, 실온에서 LC 상을 나타내는 P-EPCN4에서는 약한 상호작용이 관찰되었다. 그 결과, P-EPCN4의 배열 품질이 상호작용에 의해 저하되었고, 다른 샘플보다 열 전도도가 더 낮았다. 또한, P-EPCNn의 LC 상은 광학적 관찰을 통해 모든 P-EPCNn이 네마틱 상을 가지고 있음을 확인하였으나, 구조적 분석을 통해 P-EPCN5 내지 P-EPCN9는 스메틱 상(smectic phase)은 아니었지만 상온에서 상대적으로 강한 질서를 가짐을 유추할 수 있다.Long-range interactions were observed between P-EPCN5 and P-EPCN9, whereas weak interactions were observed with P-EPCN4, which exhibited an LC phase at room temperature. As a result, the sequence quality of P-EPCN4 was degraded by the interaction, and the thermal conductivity was lower than that of other samples. In addition, the LC phase of P-EPCNn confirmed that all P-EPCNn had a nematic phase through optical observation, but structural analysis showed that P-EPCN5 to P-EPCN9 were not in a smectic phase, but at room temperature. It can be inferred that there is a relatively strong order in
또한, XRD 결과는 P-EPCN5 내지 P-EPCN9가 유사한 분자 배열 수준을 보였고, 그들이 TC에서도 유사한 경향을 보임을 확인하였다. 한편, XRD에서 분자 배열 수준의 차이를 나타내는 P-EPCN4는 TC에서 큰 차이를 나타내었다. 이러한 결과는 폴리머 네트워크에서 분자 배열 수준이 TC 값에 큰 영향을 미침을 보여준다.In addition, XRD results confirmed that P-EPCN5 to P-EPCN9 showed a similar molecular alignment level, and they showed a similar trend in TC. On the other hand, P-EPCN4, which shows a difference in molecular arrangement level in XRD, showed a large difference in TC. These results show that the level of molecular alignment in the polymer network has a significant effect on the TC value.
B3LYP/6-31G 수준에서 밀도범함수이론(density functional theory, DFT)에 의해 계산된 P-EPCNn 모델 화합물의 최적화된 분자 구조는 도 13에 나타난 바와 같이, P-EPCNn의 CB 분자의 장축 길이가 7-8°영역에서 보이는 피크에 해당하는 약 11 Å로 나타났다. 또한, 측쇄 전체 부분의 장축 길이는 동일한 DFT 계산 결과로부터 P-EPCN4에서 17 Å 및 P-EPCN9에서 23 Å로 획득되어, 펜던트 그룹의 규칙성은 4°근처에서 확인되었다. 피크가 선명하지 않아 P-EPCNn이 높은 결정도를 갖는 것으로 보긴 어려우나, 이들이 고분자 물질임을 감안할 때, P-EPCNn은 메소겐 자가 조립으로부터 유래된 충분히 높은 수준의 결정 구조를 가진다. The optimized molecular structure of the P-EPCNn model compound calculated by density functional theory (DFT) at the B3LYP/6-31G level is as shown in FIG. 13 , the long axis length of the CB molecule of P-EPCNn is It appeared to be about 11 Å corresponding to the peak seen in the 7-8° region. In addition, the long-axis length of the entire part of the side chain was obtained as 17 Å for P-EPCN4 and 23 Å for P-EPCN9 from the same DFT calculation result, confirming the regularity of the pendant group around 4°. Although it is difficult to see that P-EPCNn has high crystallinity because the peak is not clear, considering that they are high molecular materials, P-EPCNn has a sufficiently high level of crystal structure derived from mesogenic self-assembly.
더욱이, 다른 P-EPCNn과는 달리, P-EPCN4에서 낮은 TC가 관찰되는 이유는 결정 구조와 TC 사이의 상관관계로부터 확인할 수 있다. 다른 P-EPCNn과는 달리, P-EPCN4의 저각 영역에서는 피크가 거의 관찰되지 않았고, 이는 메소겐 자가 조립이 충분히 발생하지 않음을 나타내며, 이것이 P-EPCN4의 낮은 TC의 이유이다.Moreover, the reason for the low TC observed in P-EPCN4, unlike other P-EPCNn, can be confirmed from the correlation between the crystal structure and TC. Unlike other P-EPCNn, almost no peak was observed in the low angle region of P-EPCN4, indicating that mesogen self-assembly does not occur sufficiently, which is the reason for the low TC of P-EPCN4.
또한, 주쇄로부터 4개의 탄소 알킬 결합을 통해 위치하는 P-EPCN4의 메소겐은 다른 긴 스페이서 P-EPCNn과 달리, 상호작용을 위한 충분한 거리를 확보하기 어렵게 하였다. 게다가, 실온 유리질 상으로 인해 P-EPCN4를 제외한 P-EPCNn은 실온의 고무질 영역에서 LC 상으로 형성될 수 있다. 이는 P-EPCN4의 낮은 결정도 및 TC를 초래하였다. 반대로, P-EPCNn은 실온에서 LC 상을 나타내어 높은 TC를 가진다.In addition, the mesogen of P-EPCN4 located through a four-carbon alkyl bond from the main chain made it difficult to secure a sufficient distance for interaction, unlike other long spacer P-EPCNn. Moreover, P-EPCNn except for P-EPCN4 due to the room temperature glassy phase can form into the LC phase in the rubbery region at room temperature. This resulted in low crystallinity and TC of P-EPCN4. Conversely, P-EPCNn exhibits an LC phase at room temperature with a high TC.
<실시예 3> OMPBn : 4-(옥시란-2-일메톡시)페닐 4-부톡시벤조에이트 (4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate) 단량체의 합성<Example 3> OMPBn: Synthesis of 4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate (4-(oxiran-2-ylmethoxy)phenyl 4-butoxybenzoate) monomer
하기 반응식 3은 측쇄에 열방성 액정 구조인 페닐 벤조에이트(phenyl benzoate)를 가지는 에폭사이드 단량체 OMPBn의 합성 과정을 나타낸 것으로, 4-(알콕시)벤조산(4-(alkoxy)benzoic acid)을 출발물질로 하여, 하이드로퀴논(hydroquinone)과의 반응을 통해 HPBn을 합성하고, 이후 에피클로로히드린과의 반응을 통해 OMPBn을 얻었다.
<반응식 3><
① HPBn : 4-하이드록시페닐 4-알콕시벤조에이트 (4-hydroxyphenyl 4-alkoxybenzoate)의 합성 ① HPBn: Synthesis of 4-hydroxyphenyl 4-alkoxybenzoate
A) n=4 (HPB4)A) n=4 (HPB4)
3구 라운드 플라스크에 4-부톡시벤조산(4-butoxybenzoic acid) (3.00 g, 15.4 mmol), 하이드로퀴논 (6.80 g, 61.7 mmol)과 BH3O3 (0.0318 g)를 넣고, 아르곤 분위기로 치환하였다. 이후 톨루엔 120 ml과 황산 0.1 ml을 넣고, 130℃에서 12시간 교반하였다. 얻어진 용액은 회전증발농축기를 이용하여 농축된 후 디에틸에테르로 유기물을 추출하였고, 유기상은 황산마그네슘으로 건조한 후 헥산:에틸아세테이트 부피비 7:1 용액을 전개액으로 하는 실리카 컬럼 크로마토그래피를 통해 정제되었다. 수율은 24%였다.In a three-necked round flask, 4-butoxybenzoic acid (3.00 g, 15.4 mmol), hydroquinone (6.80 g, 61.7 mmol) and BH 3 O 3 (0.0318 g) were placed, and the mixture was substituted with an argon atmosphere. . Then, 120 ml of toluene and 0.1 ml of sulfuric acid were added, and the mixture was stirred at 130° C. for 12 hours. The resulting solution was concentrated using a rotary evaporator, and organic matter was extracted with diethyl ether, and the organic phase was dried over magnesium sulfate and purified through silica column chromatography using a hexane:ethyl acetate volume ratio of 7:1 as a developing solution. . The yield was 24%.
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.06 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 9.0 Hz, 2H), 4.87 (s, 1H), 4.06 (t, J = 6.5 Hz, 2H), 1.84-1.78 (m, 2H), 1.54-1.48 (m, 2H), 1.00 (t, J = 7.5 Hz, 3H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.06 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 9.0 Hz, 2H), 4.87 (s, 1H), 4.06 (t, J = 6.5 Hz, 2H), 1.84-1.78 (m, 2H), 1.54-1.48 (m, 2H), 1.00 ( t, J = 7.5 Hz, 3H) ppm.
B) n=6 (HPB6)B) n=6 (HPB6)
4-부톡시벤조산 대신 4-(헥실옥시)벤조산(4-(hexyloxy)benzoic acid)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 58%였다. It was synthesized in the same manner as in A), except that 4-(hexyloxy)benzoic acid was used instead of 4-butoxybenzoic acid. The yield was 58%.
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.87 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.85-1.79 (m, 2H), 1.52-1.45 (m, 2H), 1.37-1.34 (m, 4H), 0.93 (t, J = 7.0 Hz, 3H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.87 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.85-1.79 (m, 2H), 1.52-1.45 (m, 2H), 1.37- 1.34 (m, 4H), 0.93 (t, J = 7.0 Hz, 3H) ppm.
C) n=8 (HPB8)C) n=8 (HPB8)
4-부톡시벤조산 대신 4-(옥틸옥시)벤조산(4-(octyloxy)benzoic acid)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 57%였다. It was synthesized in the same manner as in A), except that 4-(octyloxy)benzoic acid was used instead of 4-butoxybenzoic acid. The yield was 57%.
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9 .0Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.88 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.86-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.38-1.29 (m, 8H), 0.91 (t, J = 7.0 Hz, 3H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.88 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.86-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.38 -1.29 (m, 8H), 0.91 (t, J = 7.0 Hz, 3H) ppm.
D) n=10 (HPB10)D) n=10 (HPB10)
4-부톡시벤조산 대신 4-(데실옥시)벤조산(4-(decyloxy)benzoic acid)을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 59%였다. It was synthesized in the same manner as in A), except that 4-(decyloxy)benzoic acid was used instead of 4-butoxybenzoic acid. The yield was 59%.
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 8.5 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.80 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.85-1.79 (m, 2H), 1.51-1.44 (m, 2H), 1.38-1.27 (m, 10H), 0.90 (t, J = 7.0 Hz, 3H) ppm. 1 H NMR (500 MHz, CDCl 3 ): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.07 (d, J = 8.5 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 4.80 (s, 1H), 4.05 (t, J = 6.5 Hz, 2H), 1.85-1.79 (m, 2H), 1.51-1.44 (m, 2H), 1.38- 1.27 (m, 10H), 0.90 (t, J = 7.0 Hz, 3H) ppm.
② OMPBn (4-(oxiran-2-ylmethoxy)phenyl 4-alkoxybenzoate)의 합성② Synthesis of OMPBn (4-(oxiran-2-ylmethoxy)phenyl 4-alkoxybenzoate)
E) n=4 (OMPB4)E) n=4 (OMPB4)
3구 플라스크에 4-하이드록시페닐 4-부톡시벤조에이트(4-hydroxyphenyl 4-butoxybenzoate, HPB4) (0.50 g, 1.74 mmol), NaOH (0.0701 g, 1.74 mmol) 및 벤질 트리메틸 암모늄 브로마이드(benzyl trimethyl ammonium bromide) (0.401 g, 1.74 mmol)를 넣고 아르곤 분위기로 치환한 후, 에피클로로히드린 10 ml과 물 1 ml을 추가하여 70℃에서 1시간 교반하였다. 얻어진 용액은 용매를 제거한 후 헥산:에틸아세테이트 부피비 5:1 용액을 전개액으로 하는 실리카 컬럼 크로마토그래피를 통해 정제되었다. 수율은 29%였다.In a three-neck flask, 4-hydroxyphenyl 4-butoxybenzoate (HPB4) (0.50 g, 1.74 mmol), NaOH (0.0701 g, 1.74 mmol) and benzyl trimethyl ammonium bromide (benzyl trimethyl ammonium) bromide) (0.401 g, 1.74 mmol) was added, and the mixture was replaced with an argon atmosphere, 10 ml of epichlorohydrin and 1 ml of water were added, followed by stirring at 70° C. for 1 hour. The obtained solution was purified through silica column chromatography using a hexane:ethyl acetate volume ratio 5:1 solution as a developing solution after removing the solvent. The yield was 29%.
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.5 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.05 (t, J = 6.5 Hz, 2H), 3.98 (dd, J = 11, 5.5 Hz, 1H), 3.38-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.84-1.78 (m, 2H), 1.53-1.48 (m, 2H), 0.99 (t, J = 7.0 Hz, 3H) ppm. 13C (125 MHz, CDCl3): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.2, 68.0, 50.1, 44.7, 31.1, 19.2, 13.8 ppm. HRMS (+EI) : calcd for [C20H22O5]+ : 342.1467 ; found : 342.1467 (도 14(a) 및 도 15(a)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.13 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.5 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.05 (t, J = 6.5 Hz, 2H), 3.98 (dd, J = 11, 5.5 Hz, 1H) , 3.38-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.84-1.78 (m, 2H), 1.53-1.48 (m, 2H), 0.99 (t, J = 7.0 Hz, 3H) ppm. 13 C (125 MHz, CDCl 3 ): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.2, 68.0, 50.1, 44.7, 31.1, 19.2, 13.8 ppm. HRMS (+EI): calcd for [C 20 H 22 O 5 ] + : 342.1467; found: 342.1467 (Figs. 14(a) and 15(a)).
F) n=6 (OMPB6)F) n=6 (OMPB6)
상기 HPB6을 사용한 것을 제외하고, E)와 동일한 절차로 합성되었다. 수율은 40%였다.It was synthesized in the same procedure as E) except that the above HPB6 was used. The yield was 40%.
1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H), 3.38-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.52-1.45 (m, 2H), 1.37-1.34 (m, 4H), 0.91 (t, J = 7.0 Hz, 3H) ppm. 13C (125 MHz, CDCl3): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.3, 68.3, 50.1, 44.7, 31.6, 29.1, 25.7, 22.6, 14.0 ppm. HRMS (+EI) : calcd for [C22H26O5]+ : 370.1780 ; found : 370.1779 (도 14(b) 및 도 15(b)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H) , 3.38-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.52-1.45 (m, 2H), 1.37-1.34 (m, 4H), 0.91 (t, J = 7.0 Hz, 3H) ppm. 13 C (125 MHz, CDCl 3 ): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.3, 68.3, 50.1, 44.7, 31.6, 29.1, 25.7, 22.6, 14.0 ppm. HRMS (+EI): calcd for [C 22 H 26 O 5 ] + : 370.1780 ; found: 370.1779 (FIGS. 14(b) and 15(b)).
G) n=8 (OMPB8)G) n=8 (OMPB8)
상기 HPB8을 사용한 것을 제외하고, E)와 동일한 절차로 합성되었다. 수율은 35%였다.It was synthesized in the same procedure as E) except that the above HPB8 was used. The yield was 35%.
1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.5 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H), 3.38-3.34 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.38-1.29 (m, 8H), 0.89 (t, J = 7.0 Hz, 3H) ppm. 13C (125 MHz, CDCl3): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.3, 68.3, 50.1, 44.7, 31.8, 29.3, 29.2, 29.1, 26.0 25.7, 14.1 ppm. HRMS (+EI) : calcd for [C24H30O5]+ : 398.2093 ; found : 398.2094 (도 14(c) 및 도 15(c)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.5 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H) , 3.38-3.34 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.38-1.29 (m, 8H), 0.89 (t, J = 7.0 Hz, 3H) ppm. 13 C (125 MHz, CDCl 3 ): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.6, 121.6, 115.3, 114.3, 69.3, 68.3, 50.1, 44.7, 31.8, 29.3, 29.2, 29.1, 26.0 25.7, 14.1 ppm. HRMS (+EI) : calcd for [C 24 H 30 O 5 ] + : 398.2093 ; found: 398.2094 (FIGS. 14(c) and 15(c)).
H) n=10 (OMPB10)H) n=10 (OMPB10)
상기 HPB10을 사용한 것을 제외하고, E)와 동일한 절차로 합성되었다. 수율은 36%였다.It was synthesized in the same procedure as E) except that the above HPB10 was used. The yield was 36%.
1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H), 3.39-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.39-1.28 (m, 12H), 0.88 (t, J = 7.0 Hz, 3H) ppm. 13C (125 MHz, CDCl3): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.7, 121.6, 115.4, 114.3, 69.3, 68.3, 50.1, 44.7, 31.9, 29.6, 29.6, 29.4, 29.3, 29.1, 26.0, 25.7, 14.1 ppm. HRMS (+EI) : calcd for [C26H34O5]+ : 426.2406 ; found : 426.2409 (도 14(d) 및 도 15(d)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.11 (d, J = 9.0 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 4.22 (dd, J = 11, 3.0 Hz, 1H), 4.04 (t, J = 6.5 Hz, 2H), 3.97 (dd, J = 11, 5.5 Hz, 1H) , 3.39-3.35 (m, 1H), 2.91 (dd, J = 5.0, 4.5 Hz, 1H), 2.77 (dd, J = 5.0, 2.5 Hz, 1H), 1.85-1.79 (m, 2H), 1.50-1.44 (m, 2H), 1.39-1.28 (m, 12H), 0.88 (t, J = 7.0 Hz, 3H) ppm. 13 C (125 MHz, CDCl 3 ): δ = 165.3, 163.5, 156.1, 145.0, 132.2, 122.7, 121.6, 115.4, 114.3, 69.3, 68.3, 50.1, 44.7, 31.9, 29.6, 29.6, 29.4, 29.3, 29.1, 26.0, 25.7, 14.1 ppm. HRMS (+EI) : calcd for [C 26 H 34 O 5 ] + : 426.2406 ; found: 426.2409 (Figs. 14(d) and 15(d)).
<실시예 4> OMPBn 폴리머 (P-OMPBn)의 합성<Example 4> Synthesis of OMPBn polymer (P-OMPBn)
하기 반응식 4는 측쇄에 액정 구조인 페닐 벤조에이트를 가지는 폴리에틸렌글리콜 유도체인 P-OMPBn의 합성 과정을 나타낸 것으로, 하기 반응식 4에 나타난 바와 같이, 폴리에틸렌글리콜 주쇄를 형성하기 위해 에폭사이드 단량체 OMPBn의 음이온성 개환 중합을 통해 합성되었다.
<반응식 4><
A) n=4 (P-OMPB4)A) n=4 (P-OMPB4)
OMPB4 (0.300 g, 0.876 mmol), 포타슘 tert-부톡사이드 (39.0 mg, 327 μmol), 18-크라운-6 (18.0 mg, 65.0 μmol)을 Schlenk 튜브에 넣은 후 아르곤 분위기로 치환한 후, 톨루엔 3 ml을 추가하고 실온에서 3일간 교반하여 중합을 실시하였다. 이후 중합 용액을 메탄올 50 ml에 침전시킨 후, 침전물을 회수하였다. 침전 과정은 2번 반복되었고, 갈색의 고체가 81%의 수율로 얻어졌다.OMPB4 (0.300 g, 0.876 mmol), potassium tert -butoxide (39.0 mg, 327 μmol), and 18-crown-6 (18.0 mg, 65.0 μmol) were placed in a Schlenk tube, substituted with an argon atmosphere, and then 3 ml of toluene was added and stirred at room temperature for 3 days to carry out polymerization. After the polymerization solution was precipitated in 50 ml of methanol, the precipitate was recovered. The precipitation process was repeated twice, and a brown solid was obtained in a yield of 81%.
1H NMR (500 MHz, CDCl3): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.64 (m, 5H), 1.81-1.26 (m, 4H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (도 16(a)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.64 (m, 5H), 1.81 -1.26 (m, 4H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (Fig. 16(a)).
B) n=6 (P-OMPB6)B) n=6 (P-OMPB6)
상기 OMPB6를 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 82%였다.It was synthesized in the same manner as in A), except that OMPB6 was used. The yield was 82%.
1H NMR (500 MHz, CDCl3): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.63 (m, 5H), 1.82-1.26 (m, 8H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (도 16(b)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.63 (m, 5H), 1.82 -1.26 (m, 8H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (Fig. 16(b)).
C) n=8 (P-OMPB8)C) n=8 (P-OMPB8)
상기 OMPB8을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 82%였다.It was synthesized in the same manner as in A), except that OMPB8 was used. The yield was 82%.
1H NMR (500 MHz, CDCl3): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.63 (m, 5H), 1.82-1.26 (m, 8H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (도 16(c)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.02-7.96 (m, 2H), 6.91-6.82 (m, 6H), 4.29-4.28 (m, 2H), 4.08-3.63 (m, 5H), 1.82 -1.26 (m, 8H), 1.11 (s, 9H), 0.10-0.81 (m, 3H) ppm (Fig. 16(c)).
D) n=10 (P-OMPB10)D) n=10 (P-OMPB10)
상기 OMPB10을 사용한 것을 제외하고, A)와 동일한 절차로 합성되었다. 수율은 92%였다.It was synthesized in the same manner as in A), except that OMPB10 was used. The yield was 92%.
1H NMR (500 MHz, CDCl3): δ = 8.02-7.94 (m, 2H), 7.12-6.86 (m, 6H), 4.37-4.28 (m, 2H), 4.05-3.97 (m, 5H), 1.82-1.26 (m, 16H), 1.11 (s, 9H), 0.89-0.87 (m, 3H) ppm (도 16(d)). 1 H NMR (500 MHz, CDCl 3 ): δ = 8.02-7.94 (m, 2H), 7.12-6.86 (m, 6H), 4.37-4.28 (m, 2H), 4.05-3.97 (m, 5H), 1.82 -1.26 (m, 16H), 1.11 (s, 9H), 0.89-0.87 (m, 3H) ppm (Fig. 16(d)).
하기 표 3은 상기에 따라 수득된 P-OMPBn의 분자량을 나타낸 것이고, 하기 표 4는 P-OMPBn의 물성을 나타낸 것이다.Table 3 below shows the molecular weight of P-OMPBn obtained as described above, and Table 4 below shows the physical properties of P-OMPBn.
이상으로 본 발명의 특정한 부분을 상세히 기술한 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며,이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다. 본 발명의 범위는 후술하는 청구범위에 의하여 나타내어지며, 청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, these specific descriptions are only preferred embodiments, and it is clear that the scope of the present invention is not limited thereto. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents. The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.
Claims (6)
[화학식 (I)]
[식 중, n은 1 내지 30 범위의 정수임].
A compound having a thermotropic liquid crystal structure in a side chain represented by the following formula (I):
[Formula (I)]
[wherein n is an integer ranging from 1 to 30].
[화학식 (Ⅱ)]
[식 중, n은 1 내지 30 범위의 정수임].
A compound having a thermotropic liquid crystal structure in a side chain represented by the following formula (II):
[Formula (II)]
[wherein n is an integer ranging from 1 to 30].
A polyethylene glycol polymer obtained by ring-opening polymerization of the compound according to claim 1.
A polyethylene glycol polymer obtained by ring-opening polymerization of the compound according to claim 2.
제 1 항 또는 제 2 항에 따른 화합물을 개환 중합하여 수득한 폴리에틸렌글리콜 중합체:
[화학식 (Ⅲ)]
[식 중, X1, X2는 동일하거나 다를 수 있고, 제 1 항에 따른 화합물 또는 제 2 항에 따른 화합물에서 선택됨].
It is represented by the following formula (III),
A polyethylene glycol polymer obtained by ring-opening polymerization of the compound according to claim 1 or 2:
[Formula (III)]
[wherein, X1 and X2 may be the same or different, and are selected from the compound according to claim 1 or the compound according to claim 2].
상기 폴리에틸렌글리콜 중합체는,
기판, 컴파운드, 접착제, 패드, 히트스프레드 및 히트싱크에서 사용되는 것을 특징으로 하는, 폴리에틸렌글리콜 중합체.6. The method according to any one of claims 3 to 5,
The polyethylene glycol polymer is
Polyethylene glycol polymer, characterized in that it is used in substrates, compounds, adhesives, pads, heat spreads and heat sinks.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023561313A JP2024514257A (en) | 2021-04-07 | 2022-04-05 | Compounds with thermotropic liquid crystal structure and their polyethylene glycol polymers |
PCT/KR2022/004891 WO2022216015A1 (en) | 2021-04-07 | 2022-04-05 | Compound having thermotropic liquid crystalline structure, and polyethylene glycol polymer thereof |
US18/286,082 US20240209262A1 (en) | 2021-04-07 | 2022-04-05 | Compound having thermotropic liquid crystalline structure, and polyethylene glycol polymer thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20210045178 | 2021-04-07 | ||
KR1020210045178 | 2021-04-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
KR20220139234A true KR20220139234A (en) | 2022-10-14 |
Family
ID=83599624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020220041487A KR20220139234A (en) | 2021-04-07 | 2022-04-04 | Compound having thermotropic liquid crystalline structure and polyethylene glycol polymer thereof |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR20220139234A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100597386B1 (en) | 2003-11-21 | 2006-07-07 | 제일모직주식회사 | Thermotropic Liquid Crystalline Polymer Resin Composition and Molding Product Thereof |
-
2022
- 2022-04-04 KR KR1020220041487A patent/KR20220139234A/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100597386B1 (en) | 2003-11-21 | 2006-07-07 | 제일모직주식회사 | Thermotropic Liquid Crystalline Polymer Resin Composition and Molding Product Thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100786659B1 (en) | Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers | |
Mallon et al. | Synthesis and characterization of novel epoxy monomers and liquid crystal thermosets | |
KR102345562B1 (en) | Epoxy resins, epoxy resin compositions, cured epoxy resins, and composite materials | |
JP2012211322A (en) | Polymerizable liquid crystal composition and polymer thereof | |
TW201815867A (en) | Epoxy resin composition, cured product and composite material | |
Dang et al. | Enhancing intrinsic thermal conductivities of epoxy resins by introducing biphenyl mesogen-containing liquid crystalline co-curing agents | |
Mohammed et al. | New class of liquid crystalline epoxy resins: Synthesis and properties | |
KR20140098706A (en) | Epoxy composition and epoxy resin molded article | |
JPS6251292B2 (en) | ||
JP2012177060A (en) | Resin composition and resin cured material | |
Ku et al. | Phase-controllable topochemical polymerization of liquid crystalline epoxy according to spacer length | |
JP2011016787A (en) | Liquid crystalline benzoxazine compound and liquid crystalline benzoxazine polymerizable composition | |
KR101106528B1 (en) | liquid crystal compound having two mesogenic structures | |
Ku et al. | Correlation of self-assembly and thermal conducting properties of PEG-backbone polyether with a room temperature mesophase | |
Lee et al. | Synthesis and curing of liquid crystalline epoxy resin based on naphthalene mesogen | |
KR20220139234A (en) | Compound having thermotropic liquid crystalline structure and polyethylene glycol polymer thereof | |
JP2011153265A (en) | Resin composition and resin cured product | |
US20240209262A1 (en) | Compound having thermotropic liquid crystalline structure, and polyethylene glycol polymer thereof | |
Lin et al. | Synthesis and characterization of liquid crystalline epoxy resins to study the effect of mesogenic length on the physical properties | |
Trinh et al. | Enhancement of thermal conducting properties in epoxy thermoset systems using an aligned liquid-crystalline mesophase | |
JP2014148577A (en) | Epoxy composition and epoxy resin molded article | |
Mormann et al. | ‘Liquid crystalline’thermosets (LCT) from diaromatic diepoxides and aromatic diamines | |
KR102534225B1 (en) | Multifunctional epoxy compounds having multiple liquid crystalline cores and cured products prepared therefrom | |
JP2019065126A (en) | Epoxy resin composition, epoxy resin cured product and composite material | |
KR100997544B1 (en) | Heat resistant reactive mesogens based on triphenylene core with amide group |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
E902 | Notification of reason for refusal |