JP4383810B2 - 含フッ素重合性環状オレフィン化合物 - Google Patents
含フッ素重合性環状オレフィン化合物 Download PDFInfo
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- JP4383810B2 JP4383810B2 JP2003318803A JP2003318803A JP4383810B2 JP 4383810 B2 JP4383810 B2 JP 4383810B2 JP 2003318803 A JP2003318803 A JP 2003318803A JP 2003318803 A JP2003318803 A JP 2003318803A JP 4383810 B2 JP4383810 B2 JP 4383810B2
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- fluorine
- branched
- substituted
- carbon atoms
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- -1 cyclic olefin compound Chemical class 0.000 title claims description 72
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052731 fluorine Inorganic materials 0.000 title claims description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 35
- 239000011737 fluorine Substances 0.000 title claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000004442 acylamino group Chemical group 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910010082 LiAlH Inorganic materials 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 34
- 238000003786 synthesis reaction Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 0 C[C@@]1C(*C*C(C(F)(F)F)=O)CC(C)(C)[C@](C)CC1 Chemical compound C[C@@]1C(*C*C(C(F)(F)F)=O)CC(C)(C)[C@](C)CC1 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
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- FZOBJNFHPOCQOJ-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-2,2,4,4,4-pentafluorobutane-1,3,3-triol Chemical compound C1C2C(C(O)C(F)(F)C(O)(O)C(F)(F)F)CC1C=C2 FZOBJNFHPOCQOJ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
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- PCTLJZFZEQAELO-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-2,2,4,4,4-pentafluorobutane-1,3-diol Chemical compound C1C2C(C(O)C(F)(F)C(O)C(F)(F)F)CC1C=C2 PCTLJZFZEQAELO-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- AJIBZRIAUXVGQJ-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbaldehyde Chemical compound C1C2C(C=O)CC1C=C2 AJIBZRIAUXVGQJ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002373 hemiacetals Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GMUBKAWEAAZWJM-UHFFFAOYSA-N 1,1,1,3,3-pentafluoro-3-(5-hydroxy-5-bicyclo[2.2.1]hept-2-enyl)propane-2,2-diol Chemical compound C1C2C(C(F)(F)C(O)(C(F)(F)F)O)(O)CC1C=C2 GMUBKAWEAAZWJM-UHFFFAOYSA-N 0.000 description 2
- QYNSUXMCSNIZJN-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-2,2,4,4,4-pentafluoro-3-methoxybutane-1,3-diol Chemical compound C1C2C(C(O)C(F)(F)C(O)(C(F)(F)F)OC)CC1C=C2 QYNSUXMCSNIZJN-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- VDYYBJSLWIJEBB-UHFFFAOYSA-N 2,2,4,4,4-pentafluoro-1-(4-tetracyclo[6.2.1.13,6.02,7]dodec-9-enyl)butane-1,3-diol Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(O)C(F)(F)C(O)C(F)(F)F VDYYBJSLWIJEBB-UHFFFAOYSA-N 0.000 description 2
- DOLHUCKVSMLPMG-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)-1,1,1,3,3-pentafluoro-4-hydroxybutan-2-one Chemical compound C1C2C(C(O)C(F)(F)C(=O)C(F)(F)F)CC1C=C2 DOLHUCKVSMLPMG-UHFFFAOYSA-N 0.000 description 2
- DXZCJKWHPPNRBE-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)-1,1,1,3,3-pentafluoropentane-2,4-diol Chemical compound C1C2C(C(O)(C)C(F)(F)C(O)C(F)(F)F)CC1C=C2 DXZCJKWHPPNRBE-UHFFFAOYSA-N 0.000 description 2
- SSGSXXUUWUKQJL-UHFFFAOYSA-N 5-(1,1,3,3,3-pentafluoro-2-hydroxypropyl)bicyclo[2.2.1]hept-2-en-5-ol Chemical compound C1C2C(C(F)(F)C(C(F)(F)F)O)(O)CC1C=C2 SSGSXXUUWUKQJL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
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- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- MLKNGZVLRYHYOW-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-2,2,4,4,4-pentafluoro-3-methylbutane-1,3-diol Chemical compound C1C2C(C(O)C(F)(F)C(O)(C(F)(F)F)C)CC1C=C2 MLKNGZVLRYHYOW-UHFFFAOYSA-N 0.000 description 1
- LDCMILBYFZTWHV-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-2,2,4,4,4-pentafluoro-3-methylsulfanylbutane-1,3-diol Chemical compound C1C2C(C(O)C(F)(F)C(O)(C(F)(F)F)SC)CC1C=C2 LDCMILBYFZTWHV-UHFFFAOYSA-N 0.000 description 1
- NIMLCWCLVJRPFY-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)ethanone Chemical compound C1C2C(C(=O)C)CC1C=C2 NIMLCWCLVJRPFY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
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- ZHFNIAVMAWRCJH-UHFFFAOYSA-N 2,2,4,4,4-pentafluoro-1-(4-tetracyclo[6.2.1.13,6.02,7]dodec-9-enyl)butane-1,3,3-triol Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(O)C(F)(F)C(O)(O)C(F)(F)F ZHFNIAVMAWRCJH-UHFFFAOYSA-N 0.000 description 1
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XUUPABFIIHGVAB-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)-1,1,1,3,3-pentafluoropentane-2,2,4-triol Chemical compound C1C2C(C(O)(C)C(F)(F)C(O)(O)C(F)(F)F)CC1C=C2 XUUPABFIIHGVAB-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
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- HTYWITOIIFBYSY-UHFFFAOYSA-N CC(O)(F)C(F)(F)C(O)(F)F Chemical compound CC(O)(F)C(F)(F)C(O)(F)F HTYWITOIIFBYSY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- HUQXEIFQYCVOPD-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-5-one Chemical compound C1C2C(=O)CC1C=C2 HUQXEIFQYCVOPD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
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- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
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- 125000000468 ketone group Chemical group 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- WSSJBTPBMIBNDC-UHFFFAOYSA-N n-[4-(5-bicyclo[2.2.1]hept-2-enyl)-1,1,1,3,3-pentafluoro-2,4-dihydroxybutan-2-yl]acetamide Chemical compound C1C2C(C(O)C(F)(F)C(O)(C(F)(F)F)NC(=O)C)CC1C=C2 WSSJBTPBMIBNDC-UHFFFAOYSA-N 0.000 description 1
- KKUVGFMBCBAHAC-UHFFFAOYSA-N n-[4-(5-bicyclo[2.2.1]hept-2-enyl)-1,1,1,3,3-pentafluoro-2,4-dihydroxybutan-2-yl]methanesulfonamide Chemical compound C1C2C(C(O)C(F)(F)C(O)(C(F)(F)F)NS(=O)(=O)C)CC1C=C2 KKUVGFMBCBAHAC-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
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Description
発明者らは、高透明性および高エッチング耐性を有することに加え、疎水性が抑制されて良好な現像特性を有する重合体を得るための原料となる未知の含フッ素重合性環状オレフィン化合物について鋭意検討を重ねた結果、一般式(1)、(2)で示される部分構造を有する含フッ素重合性環状オレフィン化合物が高収率且つ簡便に得られ、更に、この含フッ素重合性環状オレフィン化合物を重合して得られる重合体をベース樹脂として用いれば、波長160nm以下での透明性と、ドライエッチングに対するエッチング耐性に優れ、かつ現像特性に優れたフォトレジスト材料が得られることを見出し、本発明を完成させたものである。
ただし、R1が水酸基である化合物(2)を原料とする重合体は、フォトレジスト材料のベース樹脂として用いた場合に、現像液溶解性が必要以上に高く、未露光部の膜べりが顕著になり、フォトレジストとして使いずらいので、R1が水酸基である場合は除かれる。
尚、化合物(10)〜(13)もまた重合体製造用の単量体として用いることが可能であるが、化合物(10)〜(13)を単量体として用いて製造した重合体は、その現像液溶解性が必要以上に高く、本発明の単量体を用いて製造した重合体と比べると、未露光部の膜べりが顕著であり、フォトレジストとして使用しづらいという欠点を有する。
以上説明した製造法により、本発明の含フッ素重合性環状オレフィン化合物は、高収率且つ簡便に製造することができる。
[合成例1]
1−(5−ノルボルネン−2−イル)−2,2,4,4,4−ペンタフルオロブタン−1,3,3−トリオール(下記構造式)の合成
なお、本反応においては反応後の酸処理によりケトンが水和され、生成物が水和物として得られた。
(IR、NMR分析結果)
IR (KBr):
ν =3409,3288,3062,2979,2946,2923,2879,1486,1454,1423,1338,1311,1255,1241,1207,1172,1153,1112,1076,1025,900,842,711cm−1
1H−NMR(300MHz in DMSO−δ6) 主要な異性体のスペクトル:
δ=0.72(1H,m),1.18(1H,br.d,J=8.0Hz),1.29(1H,br.d,J=8.0Hz),1.74(1H,ddd,J=12.0,9.0,3.7Hz),2.44(1H,m),2.77(1H,m),3.02(1H,m),3.52(1H,ddd,J=22.0,10.6,7.4Hz),6.02(1H,dd,J=5.7,2.8Hz),6.19(1H,dd,J=5.7,3.0Hz),,6.29(1H,d,J=7.4Hz),7.37(1H,s),7.96(1H,d,J=1.9Hz).
19F−NMR(283MHz in CDCl3) 主要な異性体のスペクトル:
δ=−130.0(1F),−120.6(1F),−82.0(3F).
(IR、NMR分析結果)
IR (薄膜):
ν =1785cm−1 (C=O)
13C−NMR(75MHz in DMSO−δ6)
主要異性体のスペクトル:
δ=182.3(カルボニル炭素).
(IR、NMR分析結果)
IR (KBr):
ν =3421,3068,2977,2877,1454,1378,1338,1278,1209,1184,1168,1147,1011,1076,1041,1031,1020,846,831,721cm−1
1H−NMR(300MHz in DMSO−δ6) 主要な異性体のスペクトル:
δ=0.75(1H,m),1.10−1.35(2H,m),1.75(1H,m),2.41(1H,m),2.77(1H,m),2.85−3.30(2H,m),4.50(1H,m)5.45−5.90(1H,m),5.99(1H,m),6.18(1H,m),7.12(1H,m).
19F−NMR(283MHz in DMSO−δ6) 主要な異性体のスペクトル:
δ=−120.8(1F),−116.4(1F),−73.5(3F).
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定を、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
この化合物の同定は、IRとNMRで分析して行った。
(重合体の合成)
200mLのフラスコ中に1−(5−ノルボルネン−2−イル)−2,2,4,4,4−ペンタフルオロブタン−1,3−ジオール([実施例2]にしたがって合成)を7.32g、α−トリフルオロメチルアクリル酸tert−ブチルを12.68g仕込み、酢酸エチル3.53gに溶解させ、十分に系中の酸素を除去した後、開始剤AIBN(2,2’−アゾビスイソブチロニトリル)を0.33g仕込み、65℃まで昇温して24時間重合反応を行った。
得られた重合体を精製するために、反応混合物をヘキサン中に注ぎ、得られた重合体を沈澱させた。更に得られた重合体をTHF(テトラヒドロフラン)に溶かし、ヘキサン2L中に注いで重合体を沈澱させる操作を二回繰り返した後、重合体を分離し、乾燥させた。
このようにして得られた11.9gの白色の重合体は、光散乱法により重量平均分子量が8,200であり、GPC溶出曲線より分散度(=Mw/Mn)が1.5の重合体であることが確認できた。1H−NMRの測定結果より、得られた重合体中の、1−(5−ノルボルネン−2−イル)−2,2,4,4,4−ペンタフルオロブタン−1,3−ジオールと、α−トリフルオロメチルアクリル酸tert−ブチルの含有比(モル比)は40:60であることがわかった。
得られた重合体1gをプロピレングリコールモノメチルエーテルアセテート(以下、PGMEAと略記)20gに十分に溶解させ、0.2μmのフィルターで濾過して重合体の溶液を調製した。
この重合体の溶液をMgF2基板にスピンコーティングして塗布後、ホットプレートを用いて100℃で90秒間ベークし、厚さ100nmのポリマー膜をMgF2基板上に作成した。この基板を真空紫外光度計(日本分光製、VUV−200S)に設置し、波長248nm、193nm、157nmにおける透過率を測定した。その結果、透過率は、波長248nmでは99%、波長193nmでは94%、波長157nmでは52%であり、波長200nm以下、特に波長160nm以下でも高い透明性を確保できることがわかった。
得られた重合体を用いて常法によりフォトレジスト材料の溶液を調製した。次に、DUV−30(Brewer Science社製)を85nmの膜厚で成膜したシリコンウエーハ上に、調製したフォトレジスト材料の溶液をスピンコーティング後、ホットプレートを用いて100℃で90秒間ベークし、フォトレジスト膜の厚みを200nmの厚さにした。これにF2レーザー(VUVES、リソテック社製)で露光量を変化させながら露光し、露光後直ちに120℃で90秒間ベークし、2.38%のテトラメチルアンモニウムヒドロキシドの水溶液で60秒間現像を行って、露光量と残膜率の関係を求めた。膜厚が0になった露光量をEthとして、レジストの感度、そのときの傾きのtanθをγとして求めた。VUVES露光の結果、露光量の増大に従って膜厚が減少し、ポジ型レジストの特性を示すことがわかった。また、KrFスキャナー(S203B、ニコン社製、NA0.68、σ0.75、2/3輪帯照明、Crマスク)を用いて露光を行い、150nmラインアンドスペース1:1で解像している最小のマスク寸法のパターンを求め、限界解像度とした。
その結果、Ethは、7.0mJ/cm、γは13、限界解像度は125nmであり、現像特性が非常に優れているものであることが判った。
得られた重合体2gをPGMEA10gに溶解させ、0.2μmサイズのフィルターで濾過した後、重合体の溶液をスピンコートでシリコン基板上に300nmの厚さに製膜した。そして、CHF3/CF4系とCl2/BCl3系の2系統のガスを用いて、それぞれのガスにより、エッチング耐性の評価を行った。
その結果、CHF3/CF4系ガスでのエッチング速度は、170nm/min、Cl2/BCl3系ガスでのエッチング速度は、201nm/minであり、ドライエッチングに対するエッチング耐性にも優れていることが判った。
Claims (3)
- 下記一般式(3)、(4)、(5)、および(6)のいずれかで示される含フッ素重合性環状オレフィン化合物。
- 下記一般式(7)、または(8)で示されるアルデヒドまたはケトン含有環状オレフィン化合物と、下記一般式(9)で示される1,1,3,3,3−ペンタフルオロ−2−プロペニルオキシ金属化合物とを、炭化水素類、エーテル類、非プロトン性極性溶媒類のうちから選択される単独あるいは2種類以上を混合した溶媒中で付加反応させることを特徴とする、下記一般式(3)、または(4)で示される含フッ素重合性環状オレフィン化合物の製造法。
- 下記一般式(3)、または(4)で示される含フッ素重合性環状オレフィン化合物と、R 1 ’−Zで示される化合物とを、炭化水素類、エーテル類、ニトリル類、ケトン類、エステル類、非プロトン性極性溶媒類のうちから選択される単独若しくは2種類以上を混合した溶媒中、または、無溶媒で付加反応させることを特徴とする、下記一般式(5)’、または(6)’で示される含フッ素重合性環状オレフィン化合物の製造法。
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JP2003318803A JP4383810B2 (ja) | 2003-09-10 | 2003-09-10 | 含フッ素重合性環状オレフィン化合物 |
US10/918,465 US7012161B2 (en) | 2003-09-10 | 2004-08-16 | Compound, fluorine-containing polymerizable cyclic olefin compound |
KR1020040072004A KR100648123B1 (ko) | 2003-09-10 | 2004-09-09 | 불소 함유 중합성 환상 올레핀 화합물 |
TW093127414A TWI291948B (en) | 2003-09-10 | 2004-09-09 | Novel compound, fluorine-containing polymerizable cyclic olefin compound |
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JPH024722A (ja) * | 1988-06-23 | 1990-01-09 | Mitsui Petrochem Ind Ltd | 弗素含有環状オレフィン化合物及びその製法 |
US6124074A (en) * | 1999-03-11 | 2000-09-26 | International Business Machines Corporation | Photoresist compositions with cyclic olefin polymers and hydrophobic non-steroidal multi-alicyclic additives |
JP4402304B2 (ja) * | 1999-05-04 | 2010-01-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | フッ素化ポリマー、フォトレジストおよびミクロリソグラフィーのための方法 |
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TW200517366A (en) | 2005-06-01 |
KR100648123B1 (ko) | 2006-11-24 |
US20050054883A1 (en) | 2005-03-10 |
US7012161B2 (en) | 2006-03-14 |
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