KR20040090403A - Monomers, Copolyacrylates & Their Synthetic Methods for Photonic Devices - Google Patents
Monomers, Copolyacrylates & Their Synthetic Methods for Photonic Devices Download PDFInfo
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- KR20040090403A KR20040090403A KR1020040008113A KR20040008113A KR20040090403A KR 20040090403 A KR20040090403 A KR 20040090403A KR 1020040008113 A KR1020040008113 A KR 1020040008113A KR 20040008113 A KR20040008113 A KR 20040008113A KR 20040090403 A KR20040090403 A KR 20040090403A
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- South Korea
- Prior art keywords
- nmr
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- synthesis
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- 239000000178 monomer Substances 0.000 title abstract description 30
- 238000010189 synthetic method Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 12
- -1 acrylate compound Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 49
- 230000015572 biosynthetic process Effects 0.000 description 44
- 238000003786 synthesis reaction Methods 0.000 description 44
- 238000005481 NMR spectroscopy Methods 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 230000003287 optical effect Effects 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 3
- NHEKBXPLFJSSBZ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)CO NHEKBXPLFJSSBZ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- DQUIGLNWFFUKSE-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) acetate Chemical compound CC(=O)OCC(O)COC1=CC=CC=C1 DQUIGLNWFFUKSE-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- ZOUZMRQINDFFOK-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)sulfanylbenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1SC1=C(F)C(F)=C(F)C(F)=C1F ZOUZMRQINDFFOK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZSDAMBJDFDRLSS-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diol Chemical compound OC1=C(F)C(F)=C(O)C(F)=C1F ZSDAMBJDFDRLSS-UHFFFAOYSA-N 0.000 description 1
- XOTUAMWIFRDGMZ-UHFFFAOYSA-N 2-chloroprop-2-enoyl chloride Chemical compound ClC(=C)C(Cl)=O XOTUAMWIFRDGMZ-UHFFFAOYSA-N 0.000 description 1
- GUDPJHONHNSJBI-PMMFOGROSA-N C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] Chemical compound C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] GUDPJHONHNSJBI-PMMFOGROSA-N 0.000 description 1
- LYBGFVJTCCAACK-UHFFFAOYSA-N CN(C)C(=O)C1=NC=C2C(=N1)N=CN2 Chemical compound CN(C)C(=O)C1=NC=C2C(=N1)N=CN2 LYBGFVJTCCAACK-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- LLHICPSCVFRWDT-UHFFFAOYSA-N S-(5-acetamido-2-hydroxyphenyl)cysteine Chemical compound CC(=O)NC1=CC=C(O)C(SCC(N)C(O)=O)=C1 LLHICPSCVFRWDT-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WWQLXRAKBJVNCC-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)methanone Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)C1=C(F)C(F)=C(F)C(F)=C1F WWQLXRAKBJVNCC-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 자외선으로 경화가 가능한 정보·전자 소재용 불소가 치환된 새로운 폴리아크릴레이트 화합물을 개발하기 위한 단량체, 중합체 및 그의 제조방법에 관한 것으로서, 고분자 주 사슬에 불소를 치환함으로써 1.3㎛와 1.5㎛ 광통신영역에서의 광 진행 손실을 줄이고, 미세한 굴절률의 조절에 의한 낮은 복굴절률과 열 안정성을 갖는 새로운 아크릴레이트 단량체, 중합체 및 그의 제조 방법을 제공한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monomer, a polymer, and a method for producing the polyacrylate compound substituted with fluorine for information and electronic materials that can be cured by ultraviolet rays. Provided are a new acrylate monomer, a polymer, and a method of manufacturing the same, which reduce light propagation loss in an optical communication area and have low birefringence and thermal stability by controlling fine refractive index.
다가오는 21세기 고도 정보·통신 사회에 대응하여 대용량의 광통신 및 정보기록과 정보처리의 초 고속화를 실현하기 위해서는 전자 기술만으로는 한계에 도달하여 광전자 기술 도입이 필연적이다. 광의 전달자의 속도(～1015Hz)는 전자의 전달자 속도(～109Hz)보다 훨씬 빠르므로 이러한 광의 초 고속성을 사용하여 통신 시스템에 적용하면 현재의 정보 처리 능력의 한계를 극복할 것으로 예측되어 광통신 연구가 시작되었다. 수동 광소자용 고분자 물질 개발은 최근 네덜란드의 Akzo에서 자체 개발한 고분자를 이용하여 광도파로 소자를 BeamBOX란 상품명으로 시판하면서 일본 및 미국 기업들을 중심으로 개발 경쟁이 가열되고 있다. 선형 광도파로 소자용 고분자 물질로 초기 연구진은 주로 기존의 PMMA를 사용하여 제작하였다. 그러나 PMMA는 근적외선 영역에서의 광손실이 크기 때문에 이를 개선하기 위해 일본의 NTT에서는 중수소로 치환된 공중합체를 제조하여 굴절률이 잘 조절된 물질을 클래딩 및 코아로 이용하여 광손실이 1.3㎛에서 0.08dB/cm로 아주 우수한 저 광손실 광소자를 구현하였다. 그러나 PMMA계는 Tg가 100℃ 정도로 열 안정성이 떨어진다. 이를 개선하기 위해 일본의 NTT에서는 중수소화 된 폴리실록산(Electron. Lett., 30, 958 (1994)), 불소화된 폴리이미드를 개발하여 발표하였다. 미국의 Amoco Chemical 사에서 광소자용으로 개발, 상용화한 Ultradel 9000D 이라는 상품명의 불소화된 폴리이미드는 광손실이 비교적 크고 복굴절이 큰 단점은 있으나 광가교(photo-crosslinking)되도록 설계되어 포토리소그래피(photolithography)를 통해 쉽게 광소자를 제작할 수 있어 많은 연구가 이루어졌다. 최근 미국의 Allied Signal사에서는 UV 경화형 불소치환아크릴레이트를 이용한 광소자 개발을 발표하였다(US 6,306,563). 이와 같이 많은 광 도파로 소자용 고분자 물질들이 연구되어져 오고있지만 아직 그 실용화는 미진한 상태에 있는 것이 현실이다.In order to realize the high speed of large capacity optical communication, information recording and information processing in response to the upcoming 21st century high information and communication society, electronic technology alone has reached its limit and optoelectronic technology is inevitable. Since the speed of light carriers (~ 10 15 Hz) is much faster than the speed of electron carriers (~ 10 9 Hz), it is expected that the use of these ultra-high speeds in optical systems will overcome the limitations of current information processing capabilities. The research of optical communication began. The development of polymer materials for passive optical devices recently used BeamBOX to fabricate optical waveguide devices using polymers developed by Akzo in the Netherlands. As the brand is marketed, development competition is heating up around Japanese and US companies. As a polymer material for linear optical waveguide devices, the researchers initially produced them using conventional PMMA. However, PMMA has a large optical loss in the near-infrared region, so in order to improve this, Japan's NTT manufactured a deuterium-substituted copolymer and used a material with a well-adjusted refractive index as cladding and core. A very good low light loss optical device is realized at / cm. However, PMMA is inferior in thermal stability based around 100 ℃ the T g. To improve this, Japan's NTT developed and announced deuterated polysiloxanes (Electron. Lett., 30, 958 (1994)), fluorinated polyimides. Fluorinated polyimide, Ultradel 9000D, developed and commercialized for optical devices by Amoco Chemical of the United States, has the disadvantage of relatively high light loss and high birefringence, but is designed to be photo-crosslinked to provide photolithography. Through the research can be easily manufactured by the optical device. Recently, Allied Signal of the United States announced the development of an optical device using a UV-curable fluorine-substituted acrylate (US 6,306,563). As described above, many polymer materials for optical waveguide devices have been studied, but the practical use is still in a slack state.
현재의 광통신용 광원이 1.34㎛를 사용하고 있으나 조만간 1.55㎛의 레이저를 사용하게 될 것을 고려하면 고분자 내에 1.1 ∼ 1.6㎛사이에서 흡수가 거의 없는 새로운 고분자의 개발이 필요하다. 일반적인 고분자들은 탄화수소 (C, H)로 이루어져 있기 때문에 C-H결합 stretching의 2차 또는 3차 조화 흡수 band에 대한 고려가 필요하다. 다시 말하면 이러한 흡수 영역을 가지지 않으면서도 우수한 dn/dT값을 나타내는 새로운 고분자를 개발하여야 한다. 실제로 광도파로 물질 연구 분야에서는 도파로 내외 광 진행 손실을 줄일 수 있는 방안으로 고분자 내의 C-H결합을 C-D 또는 C-F결합으로 치환하여 사용한다(Makromol. Chem., 189, 2861 (1988)). 예를 들면 중수소 화 또는 불소 화 된 PMMA, 또는 Polyimide등에 관한 연구 결과들이 발표되고 있다(Macromolecules, 27, 6665 (1994)). 이들 광 흡수 특성 이외에도 신뢰성 있는 열광 소자를 제작하기 위해서는 다층 박막 형성이 가능하여야 하기 때문에 내약품 성, 내열성이 우수하고, 화학 구조 자체에 의한 흡수 또는 산란 등이 없는 비정형 고분자이면서도 기계적 강도, 전기적 특성(dielectric properties)이 낮은 고분자의 개발이 필요하다.Although the current optical communication light source uses 1.34 μm, considering that the laser of 1.55 μm will be used in the near future, it is necessary to develop a new polymer with little absorption between 1.1 and 1.6 μm in the polymer. Since general polymers are composed of hydrocarbons (C, H), it is necessary to consider the second or third harmonic absorption band of C-H bond stretching. In other words, it is necessary to develop a new polymer that does not have such an absorption region and exhibits excellent dn / dT value. In fact, in the field of optical waveguide materials research, C-H bonds in polymers are substituted with C-D or C-F bonds to reduce the light propagation loss inside and outside the waveguides (Makromol. Chem., 189, 2861 (1988)). For example, studies on deuterated or fluorinated PMMA or polyimide have been published (Macromolecules, 27, 6665 (1994)). In addition to these light absorption characteristics, in order to fabricate a reliable thermoelectric device, a multilayer thin film must be formed, and thus it is an amorphous polymer having excellent chemical resistance and heat resistance, and no absorption or scattering due to the chemical structure itself, but also mechanical strength and electrical properties ( The development of polymers with low dielectric properties is needed.
광경화(Photocuring) 기술의 사용은 지난 10년 동안 급속도로 성장하였다. 광경화는 단량체들의 가교에 의한 중합 또는 방사에 의한 중합 반응을 포함한다. 중합 반응 메카니즘은 라디칼 또는 양이온에 의한 중합으로 설명될 수 있으며 대게의 경우 라디칼 개시에 의한 중합 반응이 가장 일반적이다. 대부분의 상업적인 광경화 시스템은 다기능성 아크릴레이트(multifunctional acrylate) 단량체들과 자유라디칼 광개시제로 이루어져 있다. 광경화는 자외선을 이용한 경화로 제작 공정의 단순화, 경비 절감 등의 많은 장점들을 가지고 있다. 전기 통신학 산업 극적인 성장으로 인하여 광도파로와 interconnect applications을 위해 광경화가능한 물질의 개발이 절실히 요구되고 있다. 최근에, 많이 알려진 광학 특성을 보유한 고분자 화합물들 가운데 폴리아크릴레이트계 화합물들을 살펴보면 광학적인 특성 즉 광범위한 단량체들의 낮은 복굴절률과 광손실에 의해 광도파로 재료로서 연구되어 왔다. 특히 Halofluorinated 아크릴레이트는 광학적 특성을 갖는 광도파로 재료로서 유용한 투명한 단량체로 광개시제에 의해서 광가교 할 수 있다. 그러나 현재까지 직접 조사에 의해서 공정을 단순화시키며 물질의 열적 안정성을 향상시키는 것이 과제로 남아 있다.The use of photocuring technology has grown rapidly over the last decade. Photocuring includes polymerization by crosslinking of monomers or polymerization by radiation. The polymerization reaction mechanism can be described as polymerization by radicals or cations, and in most cases, polymerization by radical initiation is most common. Most commercial photocuring systems consist of multifunctional acrylate monomers and free radical photoinitiators. Photocuring has many advantages such as simplification of manufacturing process and cost reduction by curing with ultraviolet rays. The dramatic growth of the telecommunications industry is urgently needed to develop photocurable materials for optical waveguides and interconnect applications. Recently, when looking at polyacrylate-based compounds among polymer compounds having many known optical properties, they have been studied as optical waveguide materials due to optical properties, that is, low birefringence and light loss of a wide range of monomers. In particular, halofluorinated acrylate is a transparent monomer useful as an optical waveguide material having optical properties and can be photocrosslinked by a photoinitiator. To date, however, the challenge remains to simplify the process and improve the thermal stability of the material by direct irradiation.
본 발명의 목적은 자외선 경화를 이용한 불소화 된 폴리아크릴레이트를 개발하기 위해서 낮은 복굴절률과 열적 성질이 우수하고, 광전송 손실이 아주 낮은 광도파로 소재용 불소가 치환된 새로운 아크릴레이트 단량체, 중합체 및 그의 제조방법을 제공하는 것이다.An object of the present invention is to develop a new acrylate monomer, polymer and fluorine-substituted fluorine for optical waveguide material having excellent low birefringence and thermal properties and very low optical transmission loss in order to develop fluorinated polyacrylate using ultraviolet curing. To provide a way.
도 1은 KBr 펠렛을 사용한 (T4F8A/B4F8FA 70 :30) 코폴리머의 IR 스펙트럼.1 is an IR spectrum of a (T4F8A / B4F8FA 70:30) copolymer using KBr pellets.
도 2는 광가교 된 퍼플루오리네이티드 코폴리아크릴레이트의 근적외선 영역의 흡수 스펙트럼.2 is an absorption spectrum of the near infrared region of photocrosslinked perfluorinated copolyacrylate.
상기 목적을 달성하기 위하여 하기 화학 반응식 1 내지 13에서는 광도파로 소재용 불소를 함유하는 새로운 아크릴레이트 단량체, 중합체 및 그의 제조 방법을 화학 메커니즘으로 기재한 것으로 이들에 대한 자세한 구조 및 제조방법은 실시예를 통하여 구체적으로 설명하며, 본 발명이 하기의 실시예에 의하여 한정되는 것이아님은 자명하다.In order to achieve the above object, in Chemical Schemes 1 to 13, a new acrylate monomer, a polymer containing fluorine for an optical waveguide material, and a method for preparing the same are described as chemical mechanisms. It will be described in detail through, it is obvious that the present invention is not limited by the following examples.
위 화학식에서,In the above formula,
Rf는에서 선택되는 어느 하나이고, k는 2 내지 10의 정수 중에서 선택되며, 4가 아니다.)R f is It is any one selected from, k is selected from an integer of 2 to 10, not 4).
여기서, R1, R2, R3및 R4는 서로 독립적으로 하기의 치환기 중에서 선택되는 어느 하나이고,Here, R 1 , R 2 , R 3 and R 4 are any one selected from the following substituents independently of each other,
a, b, c, 및 d는 각각 0 내지 4의 정수에서 서로 독립적으로 선택되는 어느하나이며, a+b+c+d=4이며,a, b, c, and d are each one independently selected from an integer of 0 to 4, and a + b + c + d = 4,
또한 k는 2 내지 10의 정수에서 선택되며, 4가 아니다.K is also selected from integers from 2 to 10, not 4.
(여기서, R1, R2, R3및 R4와 a, b, c, d의 각각은 상기에서 정의한 바와 같고, R11, R22, R33및 R44는 서로 독립적으로 하기의 치환기 중에서 선택되는 어느 하나이며,(Wherein R 1 , R 2 , R 3 and R 4 and each of a, b, c, d are as defined above, and R 11 , R 22 , R 33 and R 44 are each independently of the following substituents: Which one is chosen,
k는 2 내지 10의 정수에서 서로 독립적으로 선택되는 어느 하나이며, 4가 아니다.)k is any one independently selected from an integer of 2 to 10, and is not 4.)
(여기서, 각 치환체 및 반복단위의 정의는 상기에서 정의한 것과 같다.)(Here, the definition of each substituent and repeating unit is as defined above.)
(여기서, Y는 H, F, CF3, Cl에서 선택되는 어느 하나이고, 나머지 치환체 및 반복단위는 상기에서 정의한 바와 같다.)(Wherein Y is any one selected from H, F, CF 3 and Cl, and the remaining substituents and repeating units are as defined above.)
(위 화학식에서, R은 하기의 치환기 중에서 독립적으로 선택되는 어느 하나이다.(In the above formula, R is any one independently selected from the following substituents.
또한, k는 2 내지 10의 정수에서 서로 독립적으로 선택되는 어느 하나이며, 4가 아니다.)K is any one independently selected from an integer of 2 to 10, and not 4).
위 화학식에서 R, k 및 Y는 상기에서 정의한 바와 같다.In the above formula, R, k and Y are as defined above.
위 화학식에서 Rf는R f in the above formula
에서 선택되는 어느 하나이고, Is any one selected from
여기서 k는 2 내지 10의 정수에서 선택되는 어느 하나이다.K is any one chosen from the integer of 2-10 here.
여기서, Rf는 상기에서 정의한 바와 같다.Where R f is as defined above.
여기서, Rf는 상기에서 정의한 바와 같다.Where R f is as defined above.
(위 화학식에서 Rf는 상기에서 정의한 바와 같으며,(Wherein R f is as defined above,
Rh는에서 선택되는 어느 하나이다.)R h is It is either one selected from.)
(위 화학식에서 Rf및 Rh는 상기에서 정의 한 바와 같다.)(In the above formula, R f and R h are as defined above.)
(위 화학식에서 Rf및 Rh는 상기에서 정의 한 바와 같다.)(In the above formula, R f and R h are as defined above.)
본원발명에 사용하는 시약은 하기의 것을 사용하였으며, 이는 편리에 의해 사용한 것일 뿐 본원발명의 실시예는 이 기술 분야에 속하는 통상의 지식을 가진 자가 그 실시를 하기 위해 용이하게 채택할 수 있는 정도라면 어느 것이라도 좋다.Reagents used in the present invention used the following, which is used for convenience only, the embodiment of the present invention as long as it can be easily adopted by those of ordinary skill in the art for the implementation Any may be sufficient.
펜타에리쓰리톨, 헥사플루오로벤젠, 데카플루오로비페닐, 데카플루오로벤조페논, 술포닐클로리드, 펜타플루오로페닐설피드(pentafluorophenyl sulfide), 2-클로로-아크릴로일클로라이드, 2-트리풀루오로메틸아크릴로클로라이드, 2-플루오로아크릴로일클로라이드, 3,4-디히드로-2H-피란, 2,2,3,3,4,4,5,5-옥타플루오로-1,6-헥산디올, NaH(60% dispersion in mineral oil), 아크릴로일클로라이드, 2,3,5,6-테트라플루오로벤젠-1,4-디올, 2,2-비스(4-히드록시페닐)헥사플루오로프로판, 2-히드록시-3-페녹시프로필 아세테이트, 아조비스이소부티로니트릴, 에세톤-d6, 클로로포름-d6는 Aldrich사 제품을 구입하여 사용하였고, 1-메톡시-2-프로판올아세테이트(1-Methoxy-2-propanol acetate)는 Dow chemical 사 제품을 사용하였다. 탄산칼륨은 건조시킨 후 사용하였다. N,N-디메틸푸름아미드, 테트라하이드로퓨란, 메틸렌클로리드, 벤젠은 삼전 화학사 제품으로 정제 후 사용하였고 클로로벤젠, p-톨루엔술폰산, n-헥산, 에틸아세테이트 이상의 시약들은 별다른 정제 과정 없이 사용하였다. 제조한 중간체 또는 단량체는1H-NMR과13C-NMR 그리고 FT-IR로 구조를 확인하였다. H-NMR은 Varian 300 분광기를 사용하여 기록하였고, 모든 화학적 이동도는 내부 표준물질인 테트라메틸 실란에 대해 ppm단위로 기록하였다. IR 스펙트럼은 Perkin-Elmer Spectrometer를 사용하여 KBr 펠렛과 실리콘 웨이퍼에서 그대로 측정하였다. 열중량 분석(Thermogravimetric Analyzer: TGA)및 시차주사열량은 각각 951 TGA 및 910S DSC모듈이 부착된 Dupont 990열분석기를 이용하여 가열속도는 10℃/min로 질소 및 대기 기류하에서 열안정성을 측정하였다. 박막의 굴절률(Refractive Index)및 복굴절율(Birefringence)을 PCA-2000 프리즘 커플러(PCA-2000 Prism Coupler, 새론사, 국내)를 이용하여 측정하였다.Pentaerythritol, hexafluorobenzene, decafluorobiphenyl, decafluorobenzophenone, sulfonyl chloride, pentafluorophenyl sulfide, 2-chloro-acryloyl chloride, 2-triful Fluoromethylacrylochloride, 2-fluoroacryloylchloride, 3,4-dihydro-2H-pyran, 2,2,3,3,4,4,5,5-octafluoro-1,6 Hexanediol, 60% dispersion in mineral oil (NaH), acryloyl chloride, 2,3,5,6-tetrafluorobenzene-1,4-diol, 2,2-bis (4-hydroxyphenyl) Hexafluoropropane, 2-hydroxy-3-phenoxypropyl acetate, azobisisobutyronitrile, ecetone-d6 and chloroform-d6 were purchased from Aldrich and used 1-methoxy-2-propanol Acetate (1-Methoxy-2-propanol acetate) was used by Dow Chemical. Potassium carbonate was used after drying. N, N-dimethylpuramide, tetrahydrofuran, methylene chloride, and benzene were used after purification by Samjeon Chemical Co., and reagents of chlorobenzene, p-toluenesulfonic acid, n-hexane, and ethyl acetate were used without further purification. The prepared intermediate or monomer was confirmed by 1 H-NMR, 13 C-NMR and FT-IR structure. H-NMR was recorded using a Varian 300 spectrometer and all chemical mobility was reported in ppm relative to the internal standard tetramethyl silane. IR spectra were measured intact on KBr pellets and silicon wafers using a Perkin-Elmer Spectrometer. Thermogravimetric Analyzer (TGA) and differential scanning calorimetry were measured using a Dupont 990 thermal analyzer equipped with 951 TGA and 910S DSC modules, respectively, and the thermal stability was measured under nitrogen and atmospheric airflow at a heating rate of 10 ° C / min. The refractive index and birefringence of the thin film were measured using a PCA-2000 Prism Coupler (PCA-2000 Prism Coupler, Salon, Korea).
실시예 1 :Example 1:
2,2,3,3,4,4,5,5-옥타플루오로-(6-테트라히드로-피란-2-일옥시)-헥산-1-올의 합성디클로로메탄에 (300 ml) 2,2,3,3,4,4,5,5-옥타플루오로-1,6-헥산디올 (15g, 57.2mmol)과 p-톨루엔술폰산 (150mg)을 녹인 용액에 3,4-디히드로-2H-피란(2.6ml, 28.5mmol)를 천천히 적가 하고 실온에서 3시간 교반 하였다. TLC로 반응의 완결을 확인한 후 반응 용액을 탄산수소나트륨 포화 수용액 (100ml)으로 1회 씻어준 후 유기층을 증류수(50ml×2)로 씻어 준 후 무수 MgSO4로 탈수 시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그라피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 표재화합물을 8.9g(90%) 얻었다.Synthesis of 2,2,3,3,4,4,5,5-octafluoro- (6-tetrahydro-pyran-2-yloxy) -hexan-1-ol (300 ml) 2, 3,4-dihydro-2H in a solution of 2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (15 g, 57.2 mmol) and p-toluenesulfonic acid (150 mg) Piran (2.6 ml, 28.5 mmol) was slowly added dropwise and stirred at room temperature for 3 hours. After confirming the completion of the reaction by TLC, the reaction solution was washed once with a saturated aqueous solution of sodium bicarbonate (100 ml), and then the organic layer was washed with distilled water (50 ml × 2) and filtered by dehydration with anhydrous MgSO 4 . The filtrate was distilled under reduced pressure and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 8.9 g (90%) of a colorless superficial compound.
1H-NMR(300MHz, CDCl3): 1.59∼1.85 (m, 6H), 3.12 (s, OH), 3.8∼4.1 (m, 6H), 41.75 (s, 1H):19F-NMR: -120.5 (d, 2F), -123.07 (t, 2F), -124.44 (m, 4F). 1 H-NMR (300 MHz, CDCl 3 ): 1.59 to 1.85 (m, 6H), 3.12 (s, OH), 3.8 to 4.1 (m, 6H), 41.75 (s, 1H): 19 F-NMR: -120.5 (d, 2F), -123.07 (t, 2F), -124.44 (m, 4F).
실시예 2 :테트라키스-(2,3,5,6-펜타플루오로페녹시)메틸메탄의 합성Example 2 Synthesis of Tetrakis- (2,3,5,6-pentafluorophenoxy) methylmethane
질소 기류하에서 둥근 플라스크에 펜타에리쓰리톨 (2g, 14.7mmol)을 무수 디메틸포름아미드(50ml)에 녹이고 수소화나트륨(60% dispersion in mineral oil)(2.64g, 66.1mmol)를 첨가하고 실온에서 2시간 교반시켰다. 또 다른 플라스크에 헥사플루오로벤젠(7.6ml, 66.1mmol)을 무수 디메틸포름아미드(100ml)에 녹인 후 앞서 준비한 반응 용액을 영하 10℃에서 천천히 적가 했다. 적가 후 상온에서 20시간 교반하고 TLC로 반응의 완결을 확인한 후 용매를 감압증류하고 생성물을 관 크로마토그래피(헥산)로 정제하여 흰색의 고체로 표재화합물을 9.4g(80%)얻었다.In a round flask under nitrogen stream, pentaerythritol (2 g, 14.7 mmol) was dissolved in anhydrous dimethylformamide (50 ml), sodium hydride (60% dispersion in mineral oil) (2.64 g, 66.1 mmol) was added and 2 hours at room temperature. Stirred. In another flask, hexafluorobenzene (7.6 ml, 66.1 mmol) was dissolved in anhydrous dimethylformamide (100 ml), and the reaction solution prepared above was slowly added dropwise at -10 ° C. After the addition, the mixture was stirred at room temperature for 20 hours, the reaction was confirmed by TLC, and then the solvent was distilled under reduced pressure, and the product was purified by column chromatography (hexane) to obtain 9.4 g (80%) of the surface compound as a white solid.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2);19F-NMR: -157.15(d, 2F), -162.26(t, 1F), -162.86(t, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2); 19 F-NMR: -157.15 (d, 2F), -162.26 (t, 1F), -162.86 (t, 2F)
실시예 3 :Example 3:
테트라키스-{4'-[6-(2-테트라히드로피란일옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로페녹시메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydropyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2, Synthesis of 3,5,6-tetrafluorophenoxymethyl} methane
질소 기류하에서 둥근 플라스크에 테트라키스-(2,3,5,6-펜타플루오로페녹시)메틸메탄 (1g, 1.25mmol)을 무수 테트라히드로푸란(30ml)에 녹이고 수소화나트륨(60% dispersion in mineral oil) (0.21g, 5.37mmol)를 첨가하고 실온에서 30분간 교반시켰다. 또 다른 플라스크에 2,2,3,3,4,4,5,5-옥타플루오로-(6-테트라히드로-피란-2-일옥시)-헥산-1-올(1.86g, 5.37mmol)을 무수 테트라히드로푸란(10ml)에 녹인 후 앞서 준비한 반응 용액을 상온에서 천천히 적가 했다. 적가 후 상온에서 20 시각 교반하고 TLC로 반응의 완결을 확인한 후 용매를 감압증류하고 생성물을 관크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 표재화합물을 2.5g(95%)얻었다.Dissolve tetrakis- (2,3,5,6-pentafluorophenoxy) methylmethane (1 g, 1.25 mmol) in anhydrous tetrahydrofuran (30 ml) in a round flask under nitrogen stream and sodium hydride (60% dispersion in mineral). oil) (0.21 g, 5.37 mmol) was added and stirred at room temperature for 30 minutes. In another flask, 2,2,3,3,4,4,5,5-octafluoro- (6-tetrahydro-pyran-2-yloxy) -hexane-1-ol (1.86 g, 5.37 mmol) Was dissolved in anhydrous tetrahydrofuran (10ml), and the reaction solution prepared above was slowly added dropwise at room temperature. After dropping, the mixture was stirred at room temperature for 20 hours. After completion of the reaction by TLC, the solvent was distilled under reduced pressure, and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 2.5 g (95%) of a colorless superficial compound. Got it.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H), 3.96 (t, 1H), 4.75 (m, 4H), 4.76(s, 1H);19F-NMR: -120.36 (s, 2F), -121.58 (t, 2F), -123.96 (m, 4F), -155.87 (d, 2F), -157.07 (d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H), 3.96 (t, 1H), 4.75 (m, 4H), 4.76 ( s, 1 H); 19 F-NMR: -120.36 (s, 2F), -121.58 (t, 2F), -123.96 (m, 4F), -155.87 (d, 2F), -157.07 (d, 2F)
테트라키스-{4'-[8-(2-테트라히드로피란일옥시)-2,2,3,3,4,4,5,5,6,6,7,7,8,8-도데카플루오로옥틸옥시]-2,3,5,6-테트라플루오로페녹시메틸}메탄의 합성Tetrakis- {4 '-[8- (2-tetrahydropyranyloxy) -2,2,3,3,4,4,5,5,6,6,7,7,8,8-dodeca Synthesis of fluorooctyloxy] -2,3,5,6-tetrafluorophenoxymethyl} methane
질소 기류하에서 둥근 플라스크에 테트라키스-(2,3,5,6-펜타플루오로페녹시)메틸메탄 (1g, 1.25mmol)을 무수 테트라히드로푸란(30ml)에 녹이고 수소화나트륨(60% dispersion in mineral oil) (0.21g, 5.37mmol)를 첨가하고 실온에서 30분간 교반시켰다. 또 다른 플라스크에 2,2,3,3,4,4,5,5,6,6,7,7-도데카플루오로-8-(테트라히드로-피란-2-일옥시)-옥탄-1-올(3.90g, 8.75mmol)을 무수 테트라히드로푸란(10ml)에 녹인 후 앞서 준비한 반응 용액을 상온에서 천천히 적가 했다. 적가 후 상온에서 20시간 교반하고 TLC로 반응의 완결을 확인한 후 용매를 감압증류하고 생성물을 관 크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 표재화합물을 2.0g(70%)얻었다.Dissolve tetrakis- (2,3,5,6-pentafluorophenoxy) methylmethane (1 g, 1.25 mmol) in anhydrous tetrahydrofuran (30 ml) in a round flask under nitrogen stream and sodium hydride (60% dispersion in mineral). oil) (0.21 g, 5.37 mmol) was added and stirred at room temperature for 30 minutes. In another flask, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-8- (tetrahydro-pyran-2-yloxy) -octane-1 After dissolving -ol (3.90 g, 8.75 mmol) in anhydrous tetrahydrofuran (10 ml), the reaction solution prepared above was slowly added dropwise at room temperature. After dropping, the mixture was stirred at room temperature for 20 hours. After completion of the reaction by TLC, the solvent was distilled under reduced pressure, and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 2.0 g (70%) of a colorless superficial compound. Got it.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 6H), 3.58 (t, 1H), 3.80 (m, 1H), 4.02 (t, 1H), 4.72 (m, 4H), 4.96(s, 1H);19F-NMR: -121.26 (s, 2F), -121.78 (t, 2F), -124.02 (m, 8F), -155.87 (d, 2F), -157.07 (d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 6H), 3.58 (t, 1H), 3.80 (m, 1H), 4.02 (t, 1H), 4.72 (m, 4H), 4.96 ( s, 1 H); 19 F-NMR: -121.26 (s, 2F), -121.78 (t, 2F), -124.02 (m, 8F), -155.87 (d, 2F), -157.07 (d, 2F)
실시예 4 :Example 4:
테트라키스-[4'(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-페녹시)메틸]메탄의 합성Tetrakis- [4 '(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6-tetrafluoro Synthesis of rho-phenoxy) methyl] methane
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로-페녹시메틸}메탄(1.54g, 0.73mmol)을 메탄올(20ml)에 녹인 후 p-톨루엔술폰산 (150mg)을 첨가하고 실온에서 6시간 교반하였다. TLC로 반응의 완결을 확인한 후 트리에틸아민으로 반응을 중단시켰다. 메탄올을 감압증류하고 생성물을 클로로포름(20ml)에 녹여 증류수(50ml×2)로 씻어준 후 무수 MgSO4로 탈수 시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 표재화합물을 1.2g(86%) 얻었다.Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 , 3,5,6-tetrafluoro-phenoxymethyl} methane (1.54 g, 0.73 mmol) was dissolved in methanol (20 ml), then p-toluenesulfonic acid (150 mg) was added and stirred at room temperature for 6 hours. After completion of the reaction by TLC, the reaction was stopped with triethylamine. Methanol was distilled under reduced pressure, and the product was dissolved in chloroform (20 ml), washed with distilled water (50 ml × 2), and dehydrated with anhydrous MgSO 4 and filtered. The filtrate was distilled under reduced pressure and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 1.2 g (86%) of a colorless superficial compound.
1H-NMR(300MHz, Acetone-d6): 3.62 (s, OH), 4,12 (t, 2H), 4.70 (s, 2H), 4.87 (m, 2H);19F-NMR: -121.2 (t, 2F), -121.9 (t, 2F), -122.1 (m, 4F), -157.88(d, 2F), -158.87 (d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 3.62 (s, OH), 4,12 (t, 2H), 4.70 (s, 2H), 4.87 (m, 2H); 19 F-NMR: -121.2 (t, 2F), -121.9 (t, 2F), -122.1 (m, 4F), -157.88 (d, 2F), -158.87 (d, 2F)
실시예 5 :Example 5:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로페녹시메틸]메탄의 합성(T4F8A)Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluorophenoxymethyl ] Synthesis of Methane (T4F8A)
질소 기류하에서 테트라키스-[4'(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-비페녹시)메틸]메탄 (1.24g, 0.70mmol)을 디클로로메탄에 (20 ml)에 녹인 후 트리에틸아민(0.5g, 4.3mmol)을 첨가하고 실온에서 30분 교반한 후 얼음 중탕에서 아크릴로일클로라이드(0.27g, 4.3mmol)를 천천히 적가 하였다. TLC로 반응의 완결을 확인한 후 디클로로메탄을 감압증류하고 생성물을 클로로포름(20ml)에 녹여 증류수(50ml×2)로 씻어 준 후 무수 MgSO4로 탈수시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 표재화합물을 0.97g(70%) 얻었다.Tetrakis- [4 '(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6 under nitrogen stream -Tetrafluoro-biphenoxy) methyl] methane (1.24g, 0.70mmol) was dissolved in dichloromethane (20ml), triethylamine (0.5g, 4.3mmol) was added and stirred at room temperature for 30 minutes. Acryloyl chloride (0.27 g, 4.3 mmol) was slowly added dropwise in an ice bath. After confirming completion of the reaction by TLC, dichloromethane was distilled under reduced pressure, and the product was dissolved in chloroform (20 ml), washed with distilled water (50 ml × 2), and dehydrated with anhydrous MgSO 4 and filtered. The filtrate was distilled under reduced pressure and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to obtain 0.97 g (70%) of a colorless superficial compound.
1H-NMR(300MHz, CDCl3): 4.64-4.79 (m, 6H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H);19F-NMR: -120.11(t, 2F), -121.54 (t, 2F), -124.13(m, 4F), -155.84 (d, 2F), -157.58 (d, 2F). 1 H-NMR (300 MHz, CDCl 3 ): 4.64-4.79 (m, 6H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -120.11 (t, 2F), -121.54 (t, 2F), -124.13 (m, 4F), -155.84 (d, 2F), -157.58 (d, 2F).
실시예 6 :Example 6:
테트라키스-(2,3,5,6,2',3',4',5',6'-노나플루오로비페닐-4-옥시)메틸메탄의 합성Synthesis of Tetrakis- (2,3,5,6,2 ', 3', 4 ', 5', 6'-nonafluorobiphenyl-4-oxy) methylmethane
실시예 2와 동일한 방법으로 표재화합물을 58%의 수득률로 제조하였다.In the same manner as in Example 2, the superposed compound was prepared at a yield of 58%.
1H-NMR(300MHz, CDCl3): 4.86 (s, 2H, CH2):19F-NMR: -137.86(d, 2F), -138.90(t, 2F), -150.24(t, 1F), 156.22(d, 2F), -160.85(t, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.86 (s, 2H, CH 2): 19 F-NMR: -137.86 (d, 2F), -138.90 (t, 2F), -150.24 (t, 1F), 156.22 (d, 2F), -160.85 (t, 2F)
실시예 7 :Example 7:
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6,2',3',5',6'-옥타플루오로-(4-비페녹시)메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 Synthesis of, 3,5,6,2 ', 3', 5 ', 6'-octafluoro- (4-biphenoxy) methyl} methane
실시예 3과 동일한 방법으로 표재화합물을 92%의 수득률로 제조하였다.In the same manner as in Example 3, the superposed compound was prepared at a yield of 92%.
1H-NMR(300MHz, Acetone-d6) 2.98 (s, OH), 4.17 (t, 2H), 5.02-5.15 (m, 4H);19F-NMR (300 MHz, Acetone-d6): -122.02 (t, 2F), -122.93 (t, 2F), -124.51(m, 4F), -141.20 (m, 4F), -157.10 (d, 2F), -157.78(d, 2F). 1 H-NMR (300 MHz, Acetone-d 6 ) 2.98 (s, OH), 4.17 (t, 2H), 5.02-5.15 (m, 4H); 19 F-NMR (300 MHz, Acetone-d 6 ): -122.02 (t, 2F), -122.93 (t, 2F), -124.51 (m, 4F), -141.20 (m, 4F), -157.10 (d , 2F), -157.78 (d, 2F).
실시예 8 :Example 8:
테트라키스-[4'-(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6,2',3',5',6'-옥타플루오로-(4-비페녹시)메틸]메탄의 합성Tetrakis- [4 '-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6,2', 3 ' Synthesis of, 5 ', 6'-octafluoro- (4-biphenoxy) methyl] methane
실시예 4와 동일한 방법으로 표재화합물을 92%의 수득률로 제조하였다.In the same manner as in Example 4, the superposed compound was prepared at a yield of 92%.
1H-NMR(300MHz, Acetone-d6): 2.9 (s, OH), 4.08∼4.19(d, 2H), 5.02∼5.16(m, 4H):19F-NMR: -122.02(t, 2F), -122.93(t, 2F), -124.51(d, 4F), -141.25(d, 2F), -141.4(d, 2F), -157.03(d, 2F), -157.8(d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 2.9 (s, OH), 4.08 to 4.19 (d, 2H), 5.02 to 5.16 (m, 4H): 19 F-NMR: -122.02 (t, 2F) , -122.93 (t, 2F), -124.51 (d, 4F), -141.25 (d, 2F), -141.4 (d, 2F), -157.03 (d, 2F), -157.8 (d, 2F)
실시예 9 :Example 9:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6,2',3',5',6'-옥타프루오로-(4-비페녹시)메틸]메탄의 합성(T8F8A)Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6,2', 3 ', Synthesis of 5 ', 6'-octafluoro- (4-biphenoxy) methyl] methane (T8F8A)
실시예 5와 동일한 방법으로 표재화합물을 50%의 수득률로 제조하였다.A superficial compound was prepared in a yield of 50% in the same manner as in Example 5.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H);19F-NMR: -120.24(t, 2F), -121.56(t, 2F), -124.22(m, 4F), -138.96(t, 2F), -139.38(t, 2F), -156.08(d, 2F), -156.79(d, 2F). 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -120.24 (t, 2F), -121.56 (t, 2F), -124.22 (m, 4F), -138.96 (t, 2F), -139.38 (t, 2F), -156.08 (d, 2F), -156.79 (d, 2F).
실시예 10 :Example 10
테트라키스-[2,3,5,6-테트라플루오로-(4-펜타플루오로페닐옥시)-페녹시]메틸메탄의 합성Synthesis of Tetrakis- [2,3,5,6-tetrafluoro- (4-pentafluorophenyloxy) -phenoxy] methylmethane
실시예 2와 동일한 방법으로 표재화합물을 50%의 수득률로 제조하였다.A superficial compound was prepared in a yield of 50% in the same manner as in Example 2.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2);19F-NMR: -158.8(d, 2F), -159.3(d, 4F), -162.26(t, 1F), -162.86(t, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2 ); 19 F-NMR: -158.8 (d, 2F), -159.3 (d, 4F), -162.26 (t, 1F), -162.86 (t, 2F)
실시예 11 :Example 11:
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐옥시)-페녹시메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 Synthesis of 3,5,6-tetrafluoro- (4-tetrafluorophenyloxy) -phenoxymethyl} methane
실시예 3과 동일한 방법으로 표재화합물을 90%의 수득률로 제조하였다.In the same manner as in Example 3, the superposed compound was prepared at a yield of 90%.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H), 3.96 (t, 1H), 4.75(m, 4H), 4.76(d, 1H);19F-NMR: -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H), 3.96 (t, 1H), 4.75 (m, 4H), 4.76 ( d, 1H); 19 F-NMR: -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 12 :Example 12:
테트라키스-[4'-(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐옥시)-페녹시메틸]메탄의 합성Tetrakis- [4 '-(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6-tetra Synthesis of Fluoro- (4-tetrafluorophenyloxy) -phenoxymethyl] methane
실시예 4와 동일한 방법으로 표재화합물을 92%의 수득률로 제조하였다.In the same manner as in Example 4, the superposed compound was prepared at a yield of 92%.
1H-NMR(300MHz, Acetone-d6): 4.05∼4.12(m, 2H), 4,67∼4.84(m, 3H), 5.12(t, 1H);19F-NMR: -122.1(d, 2F), -123.07(d, 2F), -124.74(d, 4F), -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 4.05-4.12 (m, 2H), 4,67-4.84 (m, 3H), 5.12 (t, 1H); 19 F-NMR: -122.1 (d, 2F), -123.07 (d, 2F), -124.74 (d, 4F), -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 13 :Example 13:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐옥시)-페녹시메틸]메탄의 합성Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenyloxy) -phenoxymethyl] methane
실시예 5와 동일한 방법으로 표재화합물을 70%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 70%.
1H-NMR(300MHz, CDCl3): 4.64∼4.79(m, 6H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H);19F-NMR: -119.8(t, 2F), -121.9(t, 2F), -123.92(d, 4F), -138.5(d, 2F), -138,87(d, 2F), -155.69(d, 2F), -156.38(d, 2F), -157.17(d, 2F), -157.65(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.64-4.79 (m, 6H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -119.8 (t, 2F), -121.9 (t, 2F), -123.92 (d, 4F), -138.5 (d, 2F), -138,87 (d, 2F), -155.69 ( d, 2F), -156.38 (d, 2F), -157.17 (d, 2F), -157.65 (d, 2F)
실시예 14 :Example 14
테트라키스-[2,3,5,6-테트라플루오로-(4-펜타플루오로페닐설파닐)-페녹시]메틸메탄의 합성Synthesis of Tetrakis- [2,3,5,6-tetrafluoro- (4-pentafluorophenylsulfanyl) -phenoxy] methylmethane
실시예 2와 동일한 방법으로 표재화합물을 40%의 수득률로 제조하였다.A superficial compound was prepared in a yield of 40% in the same manner as in Example 2.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2):19F-NMR: -158.8(d, 2F), -159.3(d, 4F), -162.26(t, 1F), -162.86(t, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2 ): 19 F-NMR: -158.8 (d, 2F), -159.3 (d, 4F), -162.26 (t, 1F), -162.86 (t, 2F)
실시예 15 :Example 15:
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐설파닐)-페녹시메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 Synthesis of, 3,5,6-tetrafluoro- (4-tetrafluorophenylsulfanyl) -phenoxymethyl} methane
실시예 3과 동일한 방법으로 표재화합물을 97%의 수득률로 제조하였다.In the same manner as in Example 3, the superposed compound was prepared at a yield of 97%.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 6H), 3.57 (t, 1H), 3 79 (m, 1H), 3.96 (t, 1H), 4.75(m, 4H), 4.76(d, 1H);19F-NMR: -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 6H), 3.57 (t, 1H), 3 79 (m, 1H), 3.96 (t, 1H), 4.75 (m, 4H), 4.76 (d, 1H); 19 F-NMR: -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 16 :Example 16:
테트라키스-[4'-(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐설파닐)-페녹시메틸]메탄의 합성Tetrakis- [4 '-(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6-tetra Synthesis of Fluoro- (4-tetrafluorophenylsulfanyl) -phenoxymethyl] methane
실시예 4와 동일한 방법으로 표재화합물을 92%의 수득률로 제조하였다.In the same manner as in Example 4, the superposed compound was prepared at a yield of 92%.
1H-NMR(300MHz, Acetone-d6): 4.05∼4.12(m, 2H), 4.67∼4.84(m, 3H), 5.12(t, 1H);19F-NMR: -122.1(d, 2F), -123.07(d, 2F), -124.74(d, 4F), -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d,2F), -159.3(d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 4.05-4.12 (m, 2H), 4.67-4.84 (m, 3H), 5.12 (t, 1H); 19 F-NMR: -122.1 (d, 2F), -123.07 (d, 2F), -124.74 (d, 4F), -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 17 :Example 17:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐설파닐)-페녹시메틸]메탄의 합성Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenylsulfanyl) -phenoxymethyl] methane
실시예 5와 동일한 방법으로 표재화합물을 70%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 70%.
1H-NMR(300MHz, CDCl3): 4.55∼4.71(m, 6H), 5.97-6.00 (d, J=10 Hz, 1H), 6.14-6.24 (dd, J=17, 10 Hz, 1H), 6.50-6.56 (d, J=17 Hz, 1H);19F-NMR: -119.8(t, 2F), -121.9(t, 2F), -123.92(d, 4F), -138.5(d, 2F), -138.87(d, 2F), -155.69(d, 2F), -156.38(d, 2F), -157.17(d, 2F), -157.65(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.55 to 4.71 (m, 6H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -119.8 (t, 2F), -121.9 (t, 2F), -123.92 (d, 4F), -138.5 (d, 2F), -138.87 (d, 2F), -155.69 (d, 2F), -156.38 (d, 2F), -157.17 (d, 2F), -157.65 (d, 2F)
실시예 18 :Example 18:
테트라키스-[2,3,5,6-테트라플루오로-(4-펜타플루오로벤젠술폰일)-페녹시]메틸메탄의 합성Synthesis of Tetrakis- [2,3,5,6-tetrafluoro- (4-pentafluorobenzenesulfonyl) -phenoxy] methylmethane
실시예 2와 동일한 방법으로 표재화합물을 40%의 수득률로 제조하였다.A superficial compound was prepared in a yield of 40% in the same manner as in Example 2.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2);19F-NMR: -158.8(d, 2F), -159.3(d, 4F), -162.26(t, 1F), -162.86(t, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2); 19 F-NMR: -158.8 (d, 2F), -159.3 (d, 4F), -162.26 (t, 1F), -162.86 (t, 2F)
실시예 19 :Example 19:
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로-(4-테트라플루오로벤젠술폰일)-페녹시메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 Synthesis of, 3,5,6-tetrafluoro- (4-tetrafluorobenzenesulfonyl) -phenoxymethyl} methane
실시예 3과 동일한 방법으로 표재화합물을 97%의 수득률로 제조하였다.In the same manner as in Example 3, the superposed compound was prepared at a yield of 97%.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H, 3.96 (t, 1H), 4.75(m, 4H), 4.76(d, 1H);19F-NMR: -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158,8(d, 2F), -159,3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 6H), 3.57 (t, 1H), 3.79 (m, 1H, 3.96 (t, 1H), 4.75 (m, 4H), 4.76 (d 19 F-NMR: -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F),- 158,8 (d, 2F), -159,3 (d, 2F)
실시예 20 :Example 20:
테트라키스-[4'-(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로벤젠술폰일)-페녹시메틸]메탄의 합성Tetrakis- [4 '-(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6-tetra Synthesis of Fluoro- (4-tetrafluorobenzenesulfonyl) -phenoxymethyl] methane
실시예 4와 동일한 방법으로 표재화합물을 92%의 수득률로 제조하였다.In the same manner as in Example 4, the superposed compound was prepared at a yield of 92%.
1H-NMR(300MHz, Acetone-d6): 4.05∼4.12(m, 2H), 4.67∼4.84(m, 3H), 5.12(t, 1H);19F-NMR: -122.1(d, 2F), -123.07(d, 2F), -124.74(d, 4F), -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 4.05-4.12 (m, 2H), 4.67-4.84 (m, 3H), 5.12 (t, 1H); 19 F-NMR: -122.1 (d, 2F), -123.07 (d, 2F), -124.74 (d, 4F), -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 21 :Example 21:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로벤젠술폰일)-페녹시메틸]메탄의 합성Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 -Tetrafluorobenzenesulfonyl) -phenoxymethyl] methane
실시예 5와 동일한 방법으로 표재화합물을 65%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 65%.
1H-NMR(300MHz, CDCl3): 4.55∼4.71(m, 6H), 5.97-6.00 (d, 1=10 Hz, 1H), 6.14-6.24 (dd, J=17, 10 Hz, 1H), 6.50-6.56 (d, J=17 Hz, 1H);19F-NMR: -119.8(t, 2F), -121.9(t, 2F), -123.92(d, 4F), -138.5(d, 2F), -138.87(d, 2F), -155.69(d, 2F), -156.38(d, 2F), -157.17(d, 2F), -157.65(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.55 to 4.71 (m, 6H), 5.97-6.00 (d, 1 = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -119.8 (t, 2F), -121.9 (t, 2F), -123.92 (d, 4F), -138.5 (d, 2F), -138.87 (d, 2F), -155.69 (d, 2F), -156.38 (d, 2F), -157.17 (d, 2F), -157.65 (d, 2F)
실시예 22 :Example 22:
테트라키스-[2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)-페녹시]메틸메탄의 합성Tetrakis- [2,3,5,6-tetrafluoro-4- (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) -phenoxy] Synthesis of Methylmethane
실시예 2와 동일한 방법으로 표재화합물을 42%의 수득률로 제조하였다.A superficial compound was prepared in a yield of 42% in the same manner as in Example 2.
1H-NMR(300MHz, CDCl3): 4.56 (s, 2H, CH2);19F-NMR: -121.2(s, 2F), -121.9(s, 2F), -122.1(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.56 (s, 2H, CH 2); 19 F-NMR: -121.2 (s, 2F), -121.9 (s, 2F), -122.1 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 23 :Example 23:
테트라키스-{4'-[6-(2-테트라히드로-피라닐옥시)-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시]-2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)-페녹시메틸}메탄의 합성Tetrakis- {4 '-[6- (2-tetrahydro-pyranyloxy) -2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy] -2 Synthesis of, 3,5,6-tetrafluoro-4- (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) -phenoxymethyl} methane
실시예 3과 동일한 방법으로 표재화합물을 97%의 수득률로 제조하였다.In the same manner as in Example 3, the superposed compound was prepared at a yield of 97%.
1H-NMR(300MHz, CDCl3): 1.53∼1.84 (m, 12H), 3.57 (t, 2H), 3.79 (m, 2H),3.96 (t, 2H), 4.75(m, 8H), 4.76(d, 2H);19F-NMR: -121.2(s, 4F), -121.9(s, 4F), -122.1(d, 8F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 1.53 to 1.84 (m, 12H), 3.57 (t, 2H), 3.79 (m, 2H), 3.96 (t, 2H), 4.75 (m, 8H), 4.76 ( d, 2H); 19 F-NMR: -121.2 (s, 4F), -121.9 (s, 4F), -122.1 (d, 8F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 24 :Example 24:
테트라키스-[4'-(6-히드록시-2,2,3,3,4,4,5,5,6,6-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)-페녹시메틸]메탄의 합성Tetrakis- [4 '-(6-hydroxy-2,2,3,3,4,4,5,5,6,6-octafluorohexyloxy) -2,3,5,6-tetra Synthesis of Fluoro-4- (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) -phenoxymethyl] methane
실시예 4와 동일한 방법으로 표재화합물을 90%의 수득률로 제조하였다.In the same manner as in Example 4, the superposed compound was prepared at a yield of 90%.
1H-NMR(300MHz, Acetone-d6): 4.05∼4.12(m, 2H), 4.67∼4.84(m, 6H), 5.12(t, 2H),19F-NMR: -121.2(s, 4F), -121.9(s, 4F), -122.1(d, 8F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, Acetone-d 6 ): 4.05-4.12 (m, 2H), 4.67-44.8 (m, 6H), 5.12 (t, 2H), 19 F-NMR: -121.2 (s, 4F) , -121.9 (s, 4F), -122.1 (d, 8F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 25 :Example 25:
테트라키스[4'-(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)-페녹시메틸]메탄의 합성Tetrakis [4 '-(6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro-4- Synthesis of (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) -phenoxymethyl] methane
실시예 5와 동일한 방법으로 표재화합물을 65%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 65%.
1H-NMR(300MHz, CDCl3): 4.55∼4.71(m, 10H), 5.97-6.00 (d, J=10 Hz, 1H), 6.14-6.24 (dd, J=17, 10 Hz, 1H), 6.50-6.56 (d, J=17 Hz, 1H);19F-NMR: -120.08(t, 4F), -121.9(t, 4F), -124.1(d, 8F), -157.1(d, 2F), -157.6(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.55 to 4.71 (m, 10H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -120.08 (t, 4F), -121.9 (t, 4F), -124.1 (d, 8F), -157.1 (d, 2F), -157.6 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 26 :Example 26:
4-4'-비스(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6,2',3',5',6'-옥타플루오로비페닐의 합성4-4'-bis (6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6,2 ', 3', Synthesis of 5 ', 6'-octafluorobiphenyl
질소 기류하에서 둥근 플라스크에 2,2,3,3,4,4,5,5-옥타플루오로-1,6-헥산디올 (5g, 19.1mmol)과 탄산세슘(13.7g, 41.9mmol)을 무수 디메틸포름아미드(150ml)에 녹이고 데카플루오로비페닐(12.7g, 38.1mmol)를 첨가하고 실온에서 20시간 교반시켰다. TLC로 반응의 완결을 확인한 후 용매를 감압증류하고 증류수(30ml)를 가하고 에틸아세테이트(50ml×2)로 추출하고 무수 MgSO4로 탈수 시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그라피(헥산:에틸아세테이트=3:1)로 정제하여 흰색의 표제화합물을 14.6g(90%) 얻었다.2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (5 g, 19.1 mmol) and cesium carbonate (13.7 g, 41.9 mmol) were dried in a round flask under nitrogen stream. It was dissolved in dimethylformamide (150 ml) and decafluorobiphenyl (12.7 g, 38.1 mmol) was added and stirred at room temperature for 20 hours. After confirming the completion of the reaction by TLC, the solvent was distilled under reduced pressure, distilled water (30 ml) was added, extracted with ethyl acetate (50 ml × 2), dehydrated with anhydrous MgSO 4 , and filtered. The filtrate was distilled under reduced pressure and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to give 14.6 g (90%) of a white title compound.
1H-NMR(300MHz, CDCl3): 3.94 (m, 2H), 4.63 (s, OH), 4.72 (m, 2H);19F-NMR(300 MHz, CDCl3): -121.64 (t, 2F), -122.85 (t, 2F), -124.36 (m, 4F), -141.20(t, 4F), -157.05(d, 4F). 1 H-NMR (300 MHz, CDCl 3 ): 3.94 (m, 2H), 4.63 (s, OH), 4.72 (m, 2H); 19 F-NMR (300 MHz, CDCl 3): -121.64 (t, 2F), -122.85 (t, 2F), -124.36 (m, 4F), -141.20 (t, 4F), -157.05 (d, 4F) .
실시예 27 :Example 27:
4-4'-비스(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6,2',3',5',6'-옥타플루오로비페닐의 합성 (B4F8FA)4-4'-bis (6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6,2 ', 3', Synthesis of 5 ', 6'-octafluorobiphenyl (B4F8FA)
실시예 5와 동일한 방법으로 표재화합물을 80%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 80%.
1H-NMR: H-NMR(300MHz, CDCl3): 4.61-4.79 (m, 4H), 5.94-5.97 (d,J=10 Hz, 1H), 6.13-6.23 (dd,J=17, 10 Hz, 1H), 6.47-6.52 (d,J=17 Hz, 1H);19F-NMR (300 MHz, CDCl3): -120.05 (t, 2F), -121.32 (t, 2F), -123.92-124.15 (m, 4F), -138.57 (t, 4F), -155.67 (d, 4F). 1 H-NMR: H-NMR (300 MHz, CDCl 3 ): 4.61-4.79 (m, 4H), 5.94-5.97 (d, J = 10 Hz, 1H), 6.13-6.23 (dd, J = 17, 10 Hz , 1H), 6.47-6.52 (d, J = 17 Hz, 1H); 19 F-NMR (300 MHz, CDCl 3): -120.05 (t, 2F), -121.32 (t, 2F), -123.92-124.15 (m, 4F), -138.57 (t, 4F), -155.67 (d, 4F).
실시예 28 :Example 28:
4-4'-비스(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐옥시)페닐의 합성4-4'-bis (6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenyloxy) phenyl
실시예 26과 동일한 방법으로 표재화합물을 85%의 수득률로 제조하였다.In the same manner as in Example 26, the superposed compound was prepared at a yield of 85%.
1H-NMR(300MHz, CDCl3): 3.94(m, 2H), 4.63(s, OH), 4.72(m, 2H);19F-NMR: -121.64(d, 2F), -122.85(d, 2F), -124.36(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 3.94 (m, 2H), 4.63 (s, OH), 4.72 (m, 2H); 19 F-NMR: -121.64 (d, 2F), -122.85 (d, 2F), -124.36 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 29 :Example 29:
4-4'-비스(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐옥시)페닐의 합성4-4'-bis (6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenyloxy) phenyl
실시예 5와 동일한 방법으로 표재화합물을 80%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 80%.
1H-NMR: H-NMR(300MHz, CDCl3) : 4.61∼4.79(m, 4H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H);19F-NMR:-120.05(t, 2F), -121.32(t, 2F), -123.92∼124.15(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR: H-NMR (300 MHz, CDCl 3 ): 4.61-4.79 (m, 4H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz , 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -120.05 (t, 2F), -121.32 (t, 2F), -123.92-124.15 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 ( d, 2F), -159.3 (d, 2F)
실시예 30 :Example 30:
4-4'-비스(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐설파닐옥시)페닐의 합성4-4'-bis (6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenylsulfanyloxy) phenyl
실시예 26과 동일한 방법으로 표재화합물을 85%의 수득률로 제조하였다.In the same manner as in Example 26, the superposed compound was prepared at a yield of 85%.
1H-NMR(300MHz, CDCl3): 3.94(m, 2H), 4.63(s, OH), 4.72(m, 2H);19F-NMR: -121.64(d, 2F), -122.85(d, 2F), -124.36(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 3.94 (m, 2H), 4.63 (s, OH), 4.72 (m, 2H); 19 F-NMR: -121.64 (d, 2F), -122.85 (d, 2F), -124.36 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 31 :Example 31:
4-4'-비스(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로페닐설파닐옥시)페닐의 합성4-4'-bis (6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorophenylsulfanyloxy) phenyl
실시예 5와 동일한 방법으로 표재화합물을 80%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 80%.
1H-NMR: H-NMR(300MHz, CDCl3): 4.61∼4.79(m, 4H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6,24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H);19F-NMR: -120.05(t, 2F), -121.32(t, 2F), -123.92∼124.15(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR: H-NMR (300 MHz, CDCl 3 ): 4.61-4.79 (m, 4H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6,24 (dd, J = 17, 10 Hz, 1H), 6.50-6.56 (d, J = 17 Hz, 1H); 19 F-NMR: -120.05 (t, 2F), -121.32 (t, 2F), -123.92-124.15 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 ( d, 2F), -159.3 (d, 2F)
실시예 32 :Example 32:
4-4'-비스(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로벤젠술폰일옥시)페닐의 합성4-4'-bis (6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorobenzenesulfonyloxy) phenyl
실시예 26과 동일한 방법으로 표재화합물을 85%의 수득률로 제조하였다.In the same manner as in Example 26, the superposed compound was prepared at a yield of 85%.
1H-NMR(300MHz, CDCl3): 3.94(m, 2H), 4.63(s, OH), 4.72(m, 2H):19F-NMR: -121.64(d, 2F), -122.85(d, 2F), -124.36(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 3.94 (m, 2H), 4.63 (s, OH), 4.72 (m, 2H): 19 F-NMR: -121.64 (d, 2F), -122.85 (d, 2F), -124.36 (d, 4F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 33 :Example 33:
4-4'-비스(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-(4-테트라플루오로벤젠술폰일옥시)페닐의 합성4-4'-bis (6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro- (4 Synthesis of Tetrafluorobenzenesulfonyloxy) phenyl
실시예 5와 동일한 방법으로 표재화합물을 80%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 80%.
1H-NMR: H-NMR(300MHz, CDCl3): 4.61∼4.79(m, 4H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H),19F-NMR: -120.05(t, 2F), -121.32(t, 2F), -123.92∼124.15(d, 4F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR: H-NMR (300 MHz, CDCl 3 ): 4.61-4.79 (m, 4H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz , 1H), 6.50-6.56 (d, J = 17 Hz, 1H), 19 F-NMR: -120.05 (t, 2F), -121.32 (t, 2F), -123.92-124.15 (d, 4F),- 157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 34 :Example 34:
4-4'-비스(6-히드록시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)페닐의 합성4-4'-bis (6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro-4- Synthesis of (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) phenyl
실시예 26과 동일한 방법으로 표재화합물을 85%의 수득률로 제조하였다.In the same manner as in Example 26, the superposed compound was prepared at a yield of 85%.
1H-NMR(300MHz, CDCl3): 3.94(m, 4H), 4.1(m, 4H), 4.63(s, OH), 4.72(m, 4H);19F-NMR: -121.64(d, 6F), -122.85(d, 6F), -124.36(d, 12F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 3.94 (m, 4H), 4.1 (m, 4H), 4.63 (s, OH), 4.72 (m, 4H); 19 F-NMR: -121.64 (d, 6F), -122.85 (d, 6F), -124.36 (d, 12F), -157.17 (d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 35 :Example 35:
4-4'-비스(6-아크릴옥시-2,2,3,3,4,4,5,5-옥타플루오로헥실옥시)-2,3,5,6-테트라플루오로-4-(2,2,3,3,4,4,5,5,-옥타플루오로-6-헥실옥시)페닐의 합성4-4'-bis (6-acryloxy-2,2,3,3,4,4,5,5-octafluorohexyloxy) -2,3,5,6-tetrafluoro-4- Synthesis of (2,2,3,3,4,4,5,5, -octafluoro-6-hexyloxy) phenyl
실시예 5와 동일한 방법으로 표재화합물을 80%의 수득률로 제조하였다.In the same manner as in Example 5, the superposed compound was prepared at a yield of 80%.
1H-NMR: H-NMR(300MHz, CDCl3): 4.61∼4.79(m, 14H), 5.97-6.00 (d,J=10 Hz, 1H), 6.14-6.24 (dd,J=17, 10 Hz, 1H), 6.50-6.56 (d,J=17 Hz, 1H):19F-NMR: -121.64(d, 6F), -122.85(d, 6F), -124.36(d, 12F), -157.17(d, 2F), -157.65(d, 2F), -158.8(d, 2F), -159.3(d, 2F) 1 H-NMR: H-NMR (300 MHz, CDCl 3 ): 4.61-4.79 (m, 14H), 5.97-6.00 (d, J = 10 Hz, 1H), 6.14-6.24 (dd, J = 17, 10 Hz , 1H), 6.50-6.56 (d, J = 17 Hz, 1H): 19 F-NMR: -121.64 (d, 6F), -122.85 (d, 6F), -124.36 (d, 12F), -157.17 ( d, 2F), -157.65 (d, 2F), -158.8 (d, 2F), -159.3 (d, 2F)
실시예 36 : 광가교와 열경화 의한 공중합체의 합성Example 36 Synthesis of Copolymer by Photocrosslinking and Thermosetting
T4F8A/ B4F8FA와 T8F8A/ B4F8FA의 공중합체는 광 개시재의 존재 하에서 몰비율을 (10 : 90, 20 : 80, 30 : 70, 50 : 50, 70 : 30, 그리고 80 : 20) 변화시키면서 혼합모노머 비율로 합성하였다. 광 개시제는 TA2-107 [2-벤조-(1,3)디옥솔-5-일-4,6-비스-트리클로로메틸-(1,3,5)트리아진]을 1중량% 사용하였고 전체 모노머재료에 대해 80중량%에 해당하는 PGMEA (프로필렌글리콜 모노메틸에테르아세테이트)에 녹인 후, 혼합물을 테플론 얇은 막 필터를 통하여 여과한후, 그 용액을 실리콘 웨이퍼(Silicon Wafer)상에 1,100rpm의 속도로 30초간 스핀 코팅한 다음 박막을 진공 오븐에서 12시간 방치하여 용매를 제거한 후 80℃에서 10분 예열하고 100 W/cm 수은 램프 자외선 경화기에서 1 m/min의 속도로 경화시키고 250℃ 오븐에서 2시간 열 경화 시켰다.The copolymer of T4F8A / B4F8FA and T8F8A / B4F8FA mixed monomer ratio while varying the molar ratio (10: 90, 20: 80, 30: 70, 50: 50, 70: 30, and 80: 20) in the presence of a photoinitiator. Synthesized. Photoinitiator used TA2-107 [2-benzo- (1,3) dioxol-5-yl-4,6-bis-trichloromethyl- (1,3,5) triazine] by weight 1% by weight After dissolving in PGMEA (propylene glycol monomethyl ether acetate) corresponding to 80% by weight of the monomer material, the mixture was filtered through a Teflon thin membrane filter, and the solution was subjected to a speed of 1,100 rpm on a silicon wafer. Spin-coated for 30 seconds and then the film was left for 12 hours in a vacuum oven to remove the solvent, then preheated at 80 ° C for 10 minutes, cured at a rate of 1 m / min in a 100 W / cm mercury lamp UV curing machine and in a 250 ° C oven. Time hardened.
합성된 공중합체는 FT-IR 분광기를 사용하여 광가교 공중합체의 구조를 분석하였다. 도 1에 도시된 바와 같이 T4F8A/B4F8FA 70: 30 몰비의 조성의 공중합체를 예로 들어 혼합된 모노머(a)와 광가교 공중합체(b), 열가교공중합체(c)(도면상에서 아래부터 이로 순차적으로 표시)의 FT-IR 스펙트럼들을 비교하면 자외선 경화와 열 경화 후 단량체들의 에틸렌기의 CH-streching에 의한 1650 cm-1가 현저하게 감소되었다. 그리고 전환율(conversion)은 90%로 나타났다.The synthesized copolymer was analyzed by using FT-IR spectroscopy to analyze the structure of the photocrosslinked copolymer. As shown in FIG. 1, a copolymer having a composition of T 4 F 8 A / B 4 F 8 FA 70: 30 molar ratio is used as an example, a mixed monomer (a), a photocrosslinked copolymer (b), and a thermal crosslinked polymer (c) (from below on the drawing). Comparing the FT-IR spectra of the sequential marks) 1650 cm −1 was significantly reduced by CH-streching of the ethylene groups of the monomers after UV curing and thermal curing. The conversion was 90%.
또한 광 가교 공중합체의 광학적 성질과 열적 성질을 알아보기 위하여 상기 몰 비가 다양한 광 가교된 공중합체 플루오로 폴리아크릴레이트(photocrosslinked perfluorinated copolyacrylates) 박막의 굴절율(Refractive Index) 및 복굴절율(Birefringence)은 PCA-200 프리즘 커플러를 이용하여 1.55 nm 파장에서 측정한 후, 그 결과를 하기 표에 나타내었다. 굴절율은 1.441에서 1.400의 범위 내에 있었고 대표적인 공중합체(T4F8A/B4F8FA= 2 : 8) 의 복굴절율은 0.0002이었다. 상기 폴리아크릴레이트의 복굴절율을 조절하는 데에는 단량체 T4F8A, T8F8A와 단량체 B4F8FA의 몰 비가 중요하며 단량체 T4F8A, T8F8A에 대한 단량체 B4F8FA의 몰비가 높아질수록 최종 폴리아크릴레이트의 복굴절율 값이 감소한다. 또한, 합성된 공중합체들의 열적 안정성은 질소 분위기하에서 열분석기(TGA)에 의하여 분석되었다. 대부분 초기 분해온도 (Td) 는 360℃ 이상으로 측정 되었다. 공중합체의 유리 전이온도 (Tg) 는 측정되지 않았다.In addition, in order to examine the optical and thermal properties of the optical crosslinked copolymer, the refractive index and the birefringence of the photocrosslinked perfluorinated copolyacrylates thin films having various molar ratios are PCA- After measuring at 1.55 nm wavelength using a 200 prism coupler, the results are shown in the table below. The refractive index was in the range of 1.441 to 1.400 and the birefringence of the representative copolymer (T4F8A / B4F8FA = 2: 8) was 0.0002. In controlling the birefringence of the polyacrylate, the molar ratio of the monomers T4F8A, T8F8A and the monomer B4F8FA is important, and as the molar ratio of the monomers B4F8FA to the monomers T4F8A, T8F8A increases, the birefringence value of the final polyacrylate decreases. In addition, the thermal stability of the synthesized copolymers was analyzed by a thermal analyzer (TGA) in a nitrogen atmosphere. Most of the initial decomposition temperature (T d ) was measured above 360 ℃. The glass transition temperature (T g ) of the copolymer was not measured.
[표] UV 경화형 다관능 퍼플루오리네이티드 아크릴 단량체의 광가교 반응[Table] Photocrosslinking Reaction of UV Curable Multifunctional Perfluorinated Acrylic Monomer
aT4F8FA ＆ B4F8FA,bT8F8FA ＆ B4F8FA,cFrom DSC thermograms measured in N2,d5% weight loss, N2 a T4F8FA & B4F8FA, b T8F8FA & B4F8FA, c From DSC thermograms measured in N 2 , d 5% weight loss, N 2
또한, 도 2에 도시된 바와 같이 폴리메틸메타아크릴레이트(PMMA)와 광 가교된 공중합체 플루오로 폴리아크릴레이트의 근적외선 영역의 흡수 스펙트럼 (NIR)을 비교한 결과 1,300과 1,550 nm의 파장에서 흡수가 매우 낮은 것을 알 수 있었다.In addition, as shown in FIG. 2, the absorption spectrum (NIR) of the near infrared region of polymethyl methacrylate (PMMA) and the photo-crosslinked copolymer fluoro polyacrylate was compared. As a result, the absorption was observed at wavelengths of 1,300 and 1,550 nm. It was found to be very low.
실시예 37 : 바인더용 단량체의 합성Example 37 Synthesis of Monomer for Binder
2,2,3,3,4,4,5,5-옥타플루오로-6-(2,3,5,6,2',3',4',5',6'-노나플루오로-비페닐-4-일옥시)-헥산-1-올의 합성2,2,3,3,4,4,5,5-octafluoro-6- (2,3,5,6,2 ', 3', 4 ', 5', 6'-nonafluoro- Synthesis of Biphenyl-4-yloxy) -hexan-1-ol
질소 기류 하에서 둥근 플라스크에 2,2,3,3,4,4,5,5-옥타플루오로-1,6-헥산디올 (6.0g, 22.9mmol)과 포타슘칼륨(1.58g, 11.4mmol)을 무수디메틸포름아미드(60ml)에 녹이고 데카플루오로비페닐(3.82g , 11.4mmol)를 첨가하고 실온에서 24시간 교반시켰다. TLC로 반응의 완결을 확인한 후 용매를 감압증류하고 증류수(30ml)를 가하고 에틸아세테이트(50ml×2)로 추출하고 무수 MgSO4로 탈수 시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 흰색 고체상의 표재화합물을 3.0g(46%) 얻었다.In a round flask under nitrogen stream, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (6.0 g, 22.9 mmol) and potassium potassium (1.58 g, 11.4 mmol) It was dissolved in anhydrous dimethylformamide (60 ml), decafluorobiphenyl (3.82 g, 11.4 mmol) was added, and stirred at room temperature for 24 hours. After confirming the completion of the reaction by TLC, the solvent was distilled under reduced pressure, distilled water (30 ml) was added, extracted with ethyl acetate (50 ml × 2), dehydrated with anhydrous MgSO 4 , and filtered. The filtrate was distilled under reduced pressure, and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to obtain 3.0 g (46%) of the surface compound as a white solid.
1H-NMR(300MHz, CDCl3): 4.0-4.1 (m, 2H), 5.01-5.11(t, 2H):19F-NMR (300 MHz, CDCl3), -122.0 (t, 2F), -123.0 (t, 2F), -124.53-124.73(d, 4F), -140.59(m, 2F), -141.07-141.17(m, 2F), -152.93(t, 1F), -156.89(d, 2F), -163.11-163.30(dt, 2F) 1 H-NMR (300 MHz, CDCl 3 ): 4.0-4.1 (m, 2H), 5.01-5.11 (t, 2H): 19 F-NMR (300 MHz, CDCl 3), -122.0 (t, 2F), -123.0 (t, 2F), -124.53-124.73 (d, 4F), -140.59 (m, 2F), -141.07-141.17 (m, 2F), -152.93 (t, 1F), -156.89 (d, 2F), -163.11-163.30 (dt, 2F)
2,2,3,3,4,4,5,5-옥타플루오로-6-(2,3,5,6,2',3',4',5',6'-노나플르오로-비페닐-4-일옥시)-헥실 아크릴레이트의 합성2,2,3,3,4,4,5,5-octafluoro-6- (2,3,5,6,2 ', 3', 4 ', 5', 6'-nonafluoro- Synthesis of Biphenyl-4-yloxy) -hexyl acrylate
질소 기류하에서 2,2,3,3,4,4,5,5-옥타플루오로-6-(2,3,5,6,2',3',4',5',6'-노나플루오로-비페닐-4-일옥시)-헥산-1-올 (1.0g, 1.69mmol) 을 디클로로메탄에(20 ml)에 녹인 후 트리에틸아민(0.47ml, 3.38mmol)을 첨가하고 실온에서 30분 교반한 후 얼음 중탕에서 아크릴로일클로라이드(0.18ml, 2.19mmol))를 천천히 적가하였다. TLC로 반응의 완결을 확인한 후 디클로로메탄을 감압증류하고 생성물을 클로로포름(20ml)에 녹여 증류수(50ml×2)로 씻어 준 후 무수 황산마그네슘으로 탈수시켜 여과하였다. 여액을 감압증류하고 생성물을 관 크로마토그래피(헥산:에틸아세테이트=3:1)로 정제하여 무색의 오일상으로 표재화합물을 0.74g(70%) 얻었다.2,2,3,3,4,4,5,5-octafluoro-6- (2,3,5,6,2 ', 3', 4 ', 5', 6'-nona under nitrogen stream Dissolve fluoro-biphenyl-4-yloxy) -hexane-1-ol (1.0 g, 1.69 mmol) in dichloromethane (20 ml), then add triethylamine (0.47 ml, 3.38 mmol) and at room temperature After stirring for 30 minutes, acryloyl chloride (0.18 ml, 2.19 mmol) was slowly added dropwise in an ice bath. After confirming the completion of the reaction by TLC, dichloromethane was distilled under reduced pressure, and the product was dissolved in chloroform (20 ml), washed with distilled water (50 ml x 2), and dehydrated with anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure, and the product was purified by column chromatography (hexane: ethyl acetate = 3: 1) to obtain 0.74 g (70%) of the surface compound as a colorless oil.
1H-NMR(300MHz, CDCl3): δ 4.82-4.91 (t, 2H), 5.09-5.18 (t, 2H), 6.05-6.09 (d,J=10 Hz, 1H), 6.21-6,30 (dd,J=17, 10 Hz, 1H), 6.46-6.53 (d,J=17 Hz, 1H);19F-NMR (300 MHz, CDCl3): δ -122.50 (t, 2F), -121.93 (t, 2F), -124.35-124.64(d, 4F), -139.98-140.06(m, 2F), -141.04-141.13(m, 2F). -152.95(t, 1F), -156.89(d, 2F), -163.15-163.28(dt, 2F) 1 H-NMR (300 MHz, CDCl 3 ): δ 4.82-4.91 (t, 2H), 5.09-5.18 (t, 2H), 6.05-6.09 (d, J = 10 Hz, 1H), 6.21-6,30 ( dd, J = 17, 10 Hz, 1H), 6.46-6.53 (d, J = 17 Hz, 1H); 19 F-NMR (300 MHz, CDCl 3): δ -122.50 (t, 2F), -121.93 (t, 2F), -124.35-124.64 (d, 4F), -139.98-140.06 (m, 2F), -141.04 -141.13 (m, 2F). -152.95 (t, 1F), -156.89 (d, 2F), -163.15-163.28 (dt, 2F)
실시예 38 : 바인더 고분자(F9BPH-HPP) Ⅰ의 합성Example 38 Synthesis of Binder Polymer (F9BPH-HPP) I
진공 하에서 건조시킨 플라스크에 질소기류 하에서 2,2,3,3,4,4,5,5-옥타플루오로-6-(2,3,5,6,2',3',4',5',6'-노나플루오로-비페닐-4-일옥시)-헥실 아크릴레이트 (1.0g, 0.79mmol)와 2-히드록시-3-페녹시 프로필 아크릴레이트를 무수 벤젠(3ml)에 녹이고 아조비스이소부티로니트릴(5mg) 첨가한 후 70℃에서 50시간동안 방치하였다. 반응기를 냉각시키고 반응 용액을 과량의 메틸 알콜에 침전시켰다. 생성된 침전물을 여과하여 진공 하에서 건조시킨 후. 무게를 측정하여 중합수율을 측정하였다. 고분자(F9BPH-HPP)를 1.0g(83%)얻었다. 합성된 중합체의 함량비는1H-NMR에 의하여 특정 peak의 면적비율을 측정하여 계산하였다. 고분자는 몰비 1 : 1로 정량적으로 중합이 되었음을 알 수 있었다. 합성된 중합체의 수평균 분자량은 5.7×104(g/mol)로 나타났고 분자량 분포도는 4.0-4.9 이었다.In a flask dried under vacuum, 2,2,3,3,4,4,5,5-octafluoro-6- (2,3,5,6,2 ', 3', 4 ', 5 under nitrogen stream Dissolve ', 6'-nonafluoro-biphenyl-4-yloxy) -hexyl acrylate (1.0 g, 0.79 mmol) and 2-hydroxy-3-phenoxy propyl acrylate in anhydrous benzene (3 ml) and azo Bisisobutyronitrile (5 mg) was added and then left at 70 ° C. for 50 hours. The reactor was cooled down and the reaction solution precipitated in excess methyl alcohol. The resulting precipitate was filtered off and dried under vacuum. The polymerization yield was measured by measuring the weight. 1.0 g (83%) of a polymer (F9BPH-HPP) was obtained. The content ratio of the synthesized polymer was calculated by measuring the area ratio of specific peaks by 1 H-NMR. It was found that the polymer was quantitatively polymerized at a molar ratio of 1: 1. The number average molecular weight of the synthesized polymer was found to be 5.7 × 10 4 (g / mol) and the molecular weight distribution was 4.0-4.9.
1H-NMR(300MHz, CDCl3): 7.18(2H), 6.88(3), 5.06(2H), 4.72(2H), 4.19(3H),3.99(2H), 2.68(2H), 1.67(4H):19F-NMR: -120.53(2F), -121.88(2F), -124.62(4F), -140.01(2F), -141.06(2F), -152.90(1F), -156.93(2F), -163.17(2F) 1 H-NMR (300 MHz, CDCl 3 ): 7.18 (2H), 6.88 (3), 5.06 (2H), 4.72 (2H), 4.19 (3H), 3.99 (2H), 2.68 (2H), 1.67 (4H) : 19 F-NMR: -120.53 (2F), -121.88 (2F), -124.62 (4F), -140.01 (2F), -141.06 (2F), -152.90 (1F), -156.93 (2F), -163.17 (2F)
실시예 39 : 반응성을 가지는 바인더 고분자(F9BPH-HPP) Ⅱ의 합성Example 39 Synthesis of Reactive Binder Polymer (F9BPH-HPP) II
질소 기류하에서 바인더 고분자(F9BPH-HPP) Ⅰ 1.0g을 디클로로메탄 (20ml)과 피리딘 (2ml)이 혼합된 용매에 녹인 후 아크릴로일클로라이드(0.15ml)를 천천히 적가 한 후 실온에서 12시간 교반하였다. 반응물을 과량의 메탄올에 넣고 얼음중탕에서 1시간 교반한 후 메탄올 층을 분리하여 여기에 에틸아세테이트와 헥산 (1:1)혼합용액을 50ml 넣고 실온에서 1시간 교반하였다. 생성된 침전물을 거름종이로 제거하고 여액을 동결 건조하여 반응성을 가지는 바인더 고분자(F9BPH-HPP) Ⅱ를 0.7g(70%)의 수율로 얻었다. 합성된 중합체의 분자량은 7.3×104(g/mol)로 나타났고 분자량 분포도는 3.1-3.4 로 나타났다. 또한, 합성된 공중합체의 열적 안정성은 질소 분위기하에서 열분석기(TGA)에 의하여 분석되었다. 대부분 초기 분해온도 (Td)는 350℃ 이상으로 측정 되어 우수한 열안정성을 보였다.1.0 g of binder polymer (F9BPH-HPP) I was dissolved in a solvent containing dichloromethane (20 ml) and pyridine (2 ml) under a nitrogen stream, and then slowly added dropwise acryloyl chloride (0.15 ml), followed by stirring at room temperature for 12 hours. . The reaction was added to excess methanol, stirred for 1 hour in an ice bath, and the methanol layer was separated. Then, 50 ml of a mixture of ethyl acetate and hexane (1: 1) was added thereto, followed by stirring at room temperature for 1 hour. The resulting precipitate was removed with a filter paper and the filtrate was lyophilized to obtain a reactive binder polymer (F9BPH-HPP) II with a yield of 0.7 g (70%). The molecular weight of the synthesized polymer was found to be 7.3 × 10 4 (g / mol) and the molecular weight distribution was 3.1-3.4. In addition, the thermal stability of the synthesized copolymer was analyzed by a thermal analyzer (TGA) in a nitrogen atmosphere. Most of the initial decomposition temperature (Td) was measured at 350 ℃ or more showed excellent thermal stability.
1H-NMR(300MHz, CDCl3): δ 1.67(4H), 2.68(2H), 3.99(2H), 4.19(3H), 4.72(2H), 5.06(2H), 5.55-5.67(1H), 5.82-6.20(1H), 6.31-6.39(1H);19F-NMR: -120.53(2F), -121.88(2F), -124.62(4F), -140.01(2F), -141.06(2F), -152.90(1F), -156.93(2F), -163.17(2F) 1 H-NMR (300 MHz, CDCl 3 ): δ 1.67 (4H), 2.68 (2H), 3.99 (2H), 4.19 (3H), 4.72 (2H), 5.06 (2H), 5.55-5.67 (1H), 5.82 -6.20 (1 H), 6.31-6.39 (1 H); 19 F-NMR: -120.53 (2F), -121.88 (2F), -124.62 (4F), -140.01 (2F), -141.06 (2F), -152.90 (1F), -156.93 (2F), -163.17 ( 2F)
실시예 40 : 바인더 고분자(HBP) Ⅲ의 합성Example 40 Synthesis of Binder Polymer (HBP) III
진공 하에서 건조시킨 플라스크에 질소기류 하에서 2,2,3,3,4,4,5,5-옥타플루오로-6-(2,3,5,6,2',3',4',5',6'-노나플루오로-비페닐-4-일옥시)-헥실 아크릴레이트 (1.0g, 0.79mmol) 무수 벤젠(3ml)에 녹이고 아조비스이소부티로니트릴 (5mg)첨가한 후 70℃에서 50시간동안 방치하였다. 반응기를 냉각시키고 반응 용액을 과량의 메틸 알콜에 침전시켰다. 생성된 침전물을 여과하여 진공 하에서 건조시킨 후. 무게를 측정하여 중합수율을 측정하였다. 바인더 고분자(HBP)를 0.9g(90%)얻었다. 합성된 중합체의 수평균 분자량은 3.3×104(g/mol)로 나타났고 분자량 분포도는 3.1 이었다. 또한 열안정성은 열중량 분석기 (TGA)를 이용하여 조사하였는데. 350℃ 까지 우수한 열안정성을 보였다.In a flask dried under vacuum, 2,2,3,3,4,4,5,5-octafluoro-6- (2,3,5,6,2 ', 3', 4 ', 5 under nitrogen stream Dissolve in ', 6'-nonafluoro-biphenyl-4-yloxy) -hexyl acrylate (1.0 g, 0.79 mmol) anhydrous benzene (3 ml) and add azobisisobutyronitrile (5 mg) at 70 It was left for 50 hours. The reactor was cooled down and the reaction solution precipitated in excess methyl alcohol. The resulting precipitate was filtered off and dried under vacuum. The polymerization yield was measured by measuring the weight. 0.9 g (90%) of binder polymer (HBP) was obtained. The number average molecular weight of the synthesized polymer was found to be 3.3 × 10 4 (g / mol) and the molecular weight distribution was 3.1. Thermal stability was also investigated using a thermogravimetric analyzer (TGA). It showed excellent thermal stability up to 350 ℃.
1H-NMR(300MHz, CDCl3): 5.00-5.09(2H), 4.74-4.82(2H), 4.19(3H), 3.99(2H), 2.68(1H), 1.68(2H):19F-NMR: -120.53(2F), -121.88(2F), -124.62(4F), -140.01(2F), -141.06(2F), -152.90(1F), -156.93(2F), -162.17(2F) 1 H-NMR (300 MHz, CDCl 3 ): 5.00-5.09 (2H), 4.74-4.82 (2H), 4.19 (3H), 3.99 (2H), 2.68 (1H), 1.68 (2H): 19 F-NMR: -120.53 (2F), -121.88 (2F), -124.62 (4F), -140.01 (2F), -141.06 (2F), -152.90 (1F), -156.93 (2F), -162.17 (2F)
실시예 41 : 바인더 고분자(HBP) Ⅲ를 이용한 광가교성 공중합체의 합성Example 41 Synthesis of Photocrosslinkable Copolymers Using Binder Polymer (HBP) III
HBP Ⅲ과 혼합모노머(T8F8A/ B4F8FA)의 공중합체는 광 개시재의 존재 하에서 HBP Ⅲ과 혼합모노머(T8F8A/ B4F8FA)의 중량 비율을 (20 : 80, 30 : 70, 50 : 50, 70 : 30, 그리고 80 : 20) 변화시키면서 합성하였다. 혼합모노머(T8F8A/ B4F8FA)의 몰 비율은 (50: 50)로 사용하였고 광 개시제는 TA2-107 [2--벤조-(1,3)디옥솔-5-일-4,6-비스-트리클로로메틸-(1,3,5)트리아진]을 1중량%사용하였고 전체 모노머재료에 대해 80중량%에 해당하는 클로로벤젠에 녹인 후, 혼합물을 테플론 얇은 막 필터를 통하여 여과한 후. 그 용액을 실리콘 웨이퍼(Silicon Wafer)상에 1,100rpm의 속도로 30초간 스핀 코팅한 다음 박막을 진공 오븐에서 12시간 방치하여 용매를 제거한 후 80℃에서 10분 예열하고 100 W/cm 수은 램프 자외선 경화기에서 1m/min의 속도로 경화시키고 250℃ 오븐에서 2시간 열 경화 시켰다.The copolymer of HBP III and mixed monomers (T8F8A / B4F8FA) was obtained by weight ratio of HBP III and mixed monomers (T8F8A / B4F8FA) (20:80, 30:70, 50:50, 70:30, And 80: 20) was synthesized while changing. The molar ratio of mixed monomers (T8F8A / B4F8FA) was used as (50:50) and the photoinitiator was TA2-107 [2--benzo- (1,3) dioxol-5-yl-4,6-bis-trichloro Rhomethyl- (1,3,5) triazine] was used and dissolved in 80% by weight of chlorobenzene relative to the total monomer material, and then the mixture was filtered through a Teflon thin membrane filter. The solution was spin-coated on a silicon wafer for 30 seconds at a speed of 1,100 rpm, and the thin film was left in a vacuum oven for 12 hours to remove the solvent, preheated at 80 ° C. for 10 minutes, and then 100 W / cm mercury lamp UV curing machine. Cured at a rate of 1m / min and heat-cured for 2 hours at 250 ℃ oven.
광가교 공중합체의 구조를 알아보기 위하여 합성된 공중합체는 FT-IR 분광기를 이용하여 분석한 결과를 자외선 경화와 열 경화 후 단량체들의 에틸렌기의 CH-streching에 의한 1650 cm-1가 현저하게 감소되었다. 그리고 전환율(conversion)은 90%이상으로 나타났다.In order to investigate the structure of the photocrosslinked copolymer, the synthesized copolymer was analyzed by FT-IR spectroscopy to reduce the 1650 cm -1 by CH-streching of ethylene groups of monomers after UV curing and thermal curing. It became. And the conversion was over 90%.
광 가교 공중합체의 광학적 성질과 열적 성질을 알아보기 위하여 상기 몰 비가 다양하게 광 가교된 공중합체 플루오로 폴리아크릴레이트(photocrosslinked perfluorinated copolyacrylates)들 HBP Ⅲ과 혼합모노머(T8F8A/ B4F8FA)의 중량비율로 50 : 50 으로 혼합한 것(이때, 혼합모노머(T8F8A/ B4F8FA)의 몰 비율은 (50: 50))을 이용하여 물성을 측정하였다. 박막의 굴절율(Refractive Index) 및 복굴절율(Birefringence)은 PCA-200 프리즘 커플러를 이용하여 1.55 nm 파장에서 측정하였다. 그 결과 TE모드의 굴절율은 1.4468로 나타났고 TM모드는 1.4563으로 측정되었으며 복굴절율은 0.0005로 나타났다. 이것은 바인더 고분자 (HBP)Ⅲ을 사용하기전의 복굴절율이 0.0017이었던 것에 반해 상기 바인더 고분자 (HBP)Ⅲ을 사용한 후폴리아크릴레이트의 복굴절율은 0.0005로 감소하였다. 또한, 합성된 공중합체들의 열적 안정성은 질소 분위기하에서 열분석기(TGA)에 의하여 분석되었다. 대부분 초기 분해온도 (Td) 는 390℃ 이상으로 측정 되어 높은 열안정성을 나타냈다.In order to examine the optical and thermal properties of the optically crosslinked copolymer, the molar ratio of the photocrosslinked perfluorinated copolyacrylates HBP III and the mixed monomer (T8F8A / B4F8FA) was 50. : The physical property was measured using the thing mixed by 50 (at this time, the molar ratio of mixed monomer (T8F8A / B4F8FA) (50:50)). The refractive index and birefringence of the thin film were measured at a wavelength of 1.55 nm using a PCA-200 prism coupler. As a result, the refractive index of TE mode was 1.4468, TM mode was 1.4563 and birefringence was 0.0005. The birefringence of the polyacrylate after using the binder polymer (HBP) III was reduced to 0.0005, while the birefringence was 0.0017 before using the binder polymer (HBP) III. In addition, the thermal stability of the synthesized copolymers was analyzed by a thermal analyzer (TGA) in a nitrogen atmosphere. In most cases, the initial decomposition temperature (Td) was measured above 390 ° C, indicating high thermal stability.
본 발명은 저손실 광도파로 고분자 소재로 요구되는 특성을 만족시키고, 자외선 경화를 이용한 새로운 폴리아크릴레이트 화합물을 개발하기 위해서 불소를 포함하는 다양한 아크릴레이트 단량체, 중합체 및 그들이 제조방법을 제공하게 되었다.The present invention provides various acrylate monomers, polymers containing fluorine, and methods for preparing them to satisfy the properties required for low loss optical waveguide polymer materials and to develop new polyacrylate compounds using ultraviolet curing.
본 발명에 의해서 합성된 불소 함유 폴리아크릴레이트 화합물은 불소를 함유함으로써 근 적외선 영역에서 광 손실을 최소화하고 미세한 굴절률의 조절로 인한 낮은 복굴절률과 분자 내에 방향족을 도입함으로써 열적 안정성의 증가 및 자외선 경화를 통한 소자 화 공정을 단순화시키는 효과가 있다.The fluorine-containing polyacrylate compound synthesized according to the present invention minimizes light loss in the near-infrared region by containing fluorine, and improves thermal stability and ultraviolet curing by introducing aromatics into molecules with low birefringence due to control of fine refractive index. The effect is to simplify the deviceization process.
또한 바인더 고분자를 합성하여 혼합한 공중합체의 경우 굴절율과 복굴절율이 현저하게 감소하고 열안정성의 증가와 낮은 광손실을 나타냄으로써 합성에 따른 경비절감의 장점이 있다.In addition, in the case of a copolymer mixed with a binder polymer, the refractive index and the birefringence are significantly reduced, the thermal stability is increased, and the low light loss has the advantage of cost reduction due to the synthesis.
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| CN116004123A (en) * | 2022-12-20 | 2023-04-25 | 广州鹿山新材料股份有限公司 | Super-water-resistant OCA, and preparation method and application thereof |
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| CN116004123A (en) * | 2022-12-20 | 2023-04-25 | 广州鹿山新材料股份有限公司 | Super-water-resistant OCA, and preparation method and application thereof |
| CN116004123B (en) * | 2022-12-20 | 2023-08-22 | 广州鹿山新材料股份有限公司 | Super-water-resistant OCA, and preparation method and application thereof |
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