JP4371207B2 - 脂環式スピロ型ポリイミド - Google Patents
脂環式スピロ型ポリイミド Download PDFInfo
- Publication number
- JP4371207B2 JP4371207B2 JP2003336860A JP2003336860A JP4371207B2 JP 4371207 B2 JP4371207 B2 JP 4371207B2 JP 2003336860 A JP2003336860 A JP 2003336860A JP 2003336860 A JP2003336860 A JP 2003336860A JP 4371207 B2 JP4371207 B2 JP 4371207B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyimide
- reaction
- formula
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920001721 polyimide Polymers 0.000 title claims description 68
- 239000004642 Polyimide Substances 0.000 title claims description 56
- 125000002723 alicyclic group Chemical group 0.000 title description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 22
- 125000000962 organic group Chemical group 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 238000000034 method Methods 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000013078 crystal Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 20
- -1 diamine compounds Chemical class 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 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 15
- 235000019253 formic acid Nutrition 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 13
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 12
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000009719 polyimide resin Substances 0.000 description 10
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 150000003949 imides Chemical class 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006358 imidation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000004891 communication Methods 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 239000012776 electronic material Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 0 COc(c(*)c1)cc(OC)c1N Chemical compound COc(c(*)c1)cc(OC)c1N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OPDFONQUVKFARR-UHFFFAOYSA-N 4,5-dimethoxy-5-methylcyclohexa-1,3-diene-1,3-diamine Chemical compound COC1=C(N)C=C(N)CC1(C)OC OPDFONQUVKFARR-UHFFFAOYSA-N 0.000 description 2
- QCUFYNVGYPPUQR-UHFFFAOYSA-N 4,5-dimethoxybenzene-1,3-diamine Chemical compound COC1=CC(N)=CC(N)=C1OC QCUFYNVGYPPUQR-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].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 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical group NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- JDGFELYPUWNNGR-UHFFFAOYSA-N 1,2,3,3a,4,5,6,6a-octahydropentalene-1,3,4,6-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C2C(C(=O)O)CC(C(O)=O)C21 JDGFELYPUWNNGR-UHFFFAOYSA-N 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- VKJPEQCHHVDANB-UHFFFAOYSA-N pyridine 1,1,3,3-tetramethylurea Chemical compound N1=CC=CC=C1.CN(C(N(C)C)=O)C VKJPEQCHHVDANB-UHFFFAOYSA-N 0.000 description 1
- JREWFSHZWRKNBM-UHFFFAOYSA-N pyridine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C(C(O)=O)=C1C(O)=O JREWFSHZWRKNBM-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].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 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- BFPFOLJFUVTHEP-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].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 BFPFOLJFUVTHEP-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
(A)第1工程:式[4]
で表されるアセチレンジカルボン酸ジアルキルをルテニウム触媒を用いて式[6]
で表されるトリシクロ[4.2.1.02,5]ノナ−3−エン−3,4−ビス(アルコキシカルボニル)−7−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)化合物(NESF化合物と略記する。)を製造する。
で表されるトリシクロ[4.2.1.02,5]ノナン−3,4−ビス(アルコキシカルボニル)−7−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)化合物(NASF化合物と略記する。)を製造する。
第3工程:NASF化合物を、加水分解又は有機酸分解して式[8]
第4工程:NATCまたはNCAFを脱水することによってODSFを製造する方法。
(B)第5工程:第1工程で得られたNESF化合物を、加水分解、又は有機酸分解し、式[10]
第6工程:NECFまたはNETCを還元してNCAFまたはNATCを製造する。
NCAFまたはNATCは、第4工程の脱水反応によってODSFに誘導することができる。
で表される繰り返し単位を少なくとも10モル%含有し、数平均分子量が少なくとも5000であるポリアミック酸に関する。そして、本発明の第二実施態様は、前記のポリアミック酸を熱または化学的に脱水閉環することにより得られる式[2]
で表される繰り返し単位を少なくとも10モル%含有し、数平均分子量が少なくとも5000であるポリイミドに関する。
第1工程の付加反応から順に説明する。
で表されるジハロゲノトリス(トリフェニルホスフィン)ルテニウム、又はジハロゲノテトラキス(トリフェニルホスフィン)ルテニウムであり、より具体的にはジクロロトリス(トリフェニルホスフィン)ルテニウム、ジブロモトリス(トリフェニルホスフィン)ルテニウム、ジヨウドトリス(トリフェニルホスフィン)ルテニウム、ジクロロテトラキス(トリフェニルホスフィン)ルテニウム、ジブロモテトラキス(トリフェニルホスフィン)ルテニウム及びジヨウドテトラキス(トリフェニルホスフィン)ルテニウム等が挙げられる。
で表されるトリハロゲノルテニウムで、具体的には三塩化ルテニウム、三臭化ルテニウム、三沃化ルテニウム等が挙げられる。実用的には安価な三塩化ルテニウム及び三臭化ルテニウムが挙げられる。
更に金属酸化物としては、ルテニウム黒及びパラジウム黒である。
で表されるポリイミド樹脂において、繰り返し単位の少なくとも10mol%が下記式[2]
の構成単位からなる新規なポリイミド樹脂を提供するものであり、更には、一般式[14]で表されるポリイミド樹脂において、少なくとも10mol%の式[3]で表されるODSFを含むテトラカルボン酸二無水物と、ジアミンとを重縮合させ、次いで、脱水閉環反応により得られる繰り返し単位の少なくとも10mol%が上記式[2]で示されるポリイミド樹脂の製造方法を提供するものである。
また、ポリイミド膜と基板の密着性を更に向上させる目的で、得られたポリイミド溶液にカップリング剤等の添加剤を加えることはもちろん好ましい。
尚、実施例で用いた分析法は以下の通りである。
機種:Shimadzu GC−17A,Column:キャピラリカラム CBP1−W25−100(25mx0.53mmφx1μm),カラム温度:100℃(保持2min.)〜8℃/min.(昇温速度)〜290℃(保持10min.),注入口温度:290℃,検出器温度:290℃,キャリアガス:ヘリウム,検出法:FID法。
機種:LX−1000 (JEOL Ltd.),検出法:FAB法。
機種 :INOVA500 (VARIAN Corp.),測定溶媒:CDCl3,d6−DMSO
標準物質:tetramethylsilane(TMS)。
機種:INOVA500 (VARIAN Corp.),測定溶媒:CDCl3,d6−DMSO
標準物質:CDCl3(δ:77.1ppm)。
ヤナコ機器開発研究所:MP−J3。
1H−NMR(500MHz,CDCl3,δppm):1.23(dd,J1=3.05Hz,J2=12.82Hz,1H),1.51(d,J=11.91Hz,1H),2.16(d,J=11.91Hz,1H),2.35(dd,J=4.58Hz,J2=12.82Hz,1H),2.42(d,J=4.28Hz,1H),2.53(s,1H),2.75(dd,J1=7.64Hz,J2=10.69Hz,2H),2.86(d,J=2.75Hz,1H),3.11(d,J=18.64Hz,1H),3.75(d,J=6.41Hz,6H).
13C−NMR(125MHz,CDCl3,δppm):29.76,34.49,38.20,41.50,42.34,42.44,45.66,50.10,52.06(2),140.39,142.60,160.74,160.86,168.97,176.11.
Mp.(℃):130〜131。
100mLガラス製四つ口反応器に、RuCl3・3H2O0.53g(4mol%)、トリフェニルホスフィン1.57g(12mol%)及び1,4−ジオキサン27gを仕込み内温84℃(油浴90℃)で2時間攪拌した。続いてBHSF8.90g(50mmol)を添加してから、DMA14.2g(100mmol)を2時間かけて滴下した。内温84℃(油浴90℃)で20時間攪拌後、ガスクロマトグラフィー分析すると未反応BHSF26.3%が残余しNESFが73.7%生成していた。そこで更に内温を103℃(油浴120℃)に昇温し20時間攪拌した結果、ガスクロマトグラフィー分析すると未反応BHSF9.4%が残余しNESFが90.6%生成していた。
100mLガラス製四つ口反応器に、BHSF5.34g(30mmol)、RuCl3・3H2O0.314g(4mol%)及び1,4−ジオキサン17gを仕込み内温100℃(油浴130℃)でDMA8.5g(60mmol)を45分かけて滴下した。更に内温100℃(油浴130℃)で24時間攪拌後、ガスクロマトグラフィー分析すると未反応BHSF9.5%が残余し、NESFが90.5%生成していた。反応後濃縮してから得られた残渣にトルエンを加えて加温溶解させた。不溶分は濾過にて除去した後、濾液を濃縮すると油状物10.2gが得られた。酢酸エチルとn−ヘプタンから晶析させるとNESF4.12gが得られた。
100mLガラス製四つ口反応器に、BHSF5.34g(30mmol)、RuCl3・3H2O0.314g(4mol%)及び1,4−ジオキサン48gを仕込み内温100℃(油浴120℃)でDMA6.4g(45mmol)を1時間かけて滴下した。更に内温100℃(油浴120℃)で6時間攪拌後、ガスクロマトグラフィー分析すると未反応BHSF26.9%が残余し、NESFが73.1%生成していた。そこで更にDMA2.13g(15mmol)を滴下し、内温100℃(油浴120℃)で20時間攪拌後、ガスクロマトグラフィー分析すると未反応BHSF6.2%が残余し、NESFが93.8%生成していた。反応後濃縮してから得られた残渣をシリカゲルカラムクロマトグラフィー(溶離液:酢酸エチル/n−ヘプタン)で主留分8.69gを得た。この留分を酢酸エチルとn−ヘプタンから晶析させるとNESF4.63gが得られた。
1H−NMR(500MHz,CDCl3,δppm):1.09(dd,J1=2.90Hz,J2=12.98Hz,1H),2.18(dd,J1=1.22Hz,J2=12.23Hz,1H),2.21(dd,J1=4.78Hz,J2=13.03Hz,1H),2.31(d,J=12.22Hz,1H),2.52(t,J=7.33Hz,1H),2.65〜2.71(m,3H),2.85(s,1H),2.97(d,J=18.33Hz,1H),3.62(d,J=2.75Hz,6H),3.63〜3.66(m,3H).
13C−NMR(125MHz,CDCl3,δppm):33.65,37.85,38.27,38.63,39.07,39.90,41.44,42.11,45.53,50.05,51.44,51.59,169.26,170.71,170.79,176.03.
Mp.(℃):136〜137。
100mLハステロイ製オートクレーブに、NESF4.10g(12.8mmol)、5%Pd/C(54.4%含水品)0.36g(4.0質量%)及び酢酸エチル41gを仕込んだ後、窒素置換後水素初圧5MPaで撹拌を開始しながら昇温し、80℃で8時間反応させた。室温まで冷却すると結晶が析出していたので、1,4−ジオキサンを加えて溶解してから、濾過により触媒を除去してから濃縮、乾燥させると、NASF結晶4.08g(12.6mmol)(収率98.4%)が得られた。
1H−NMR(500MHz,CDCl3,δppm):0.781(dd,J1=2.14Hz,J2=2.83Hz,1H),1.48(d,J=11.00Hz,1H),2.04(d,J=11.00Hz,1H),2.19(dd,J1=4.73Hz,J2=12.98Hz,1H),2.37〜2.51(m,4H),2.64(s,1H),2.74(t,J=7.79Hz,1H),3.50〜3.62(m,2H),12.08(brs,4H).
13C−NMR(125MHz,CDCl3,δppm):32.79,36.75,37.36,38.76(2),39.59,40.18,40.99,44.36,49.38,172.25,172.58,172.87,177.28.
Mp.(℃):189〜190。
1H−NMR(500MHz,CDCl3,δppm):1.35〜1.39(m,2H),1.96(d,J=11.00Hz,1H),2.13(dd,J1=4.74Hz,J2=12.99Hz,1H),2.24(d,J=4.28Hz,1H),2.50(t,J=1.68Hz,1H),2.75(d,J=3.05Hz,1H),2.92〜2.97(m,2H),3.28(d,J=18.64Hz,1H),11.80(brs,2H).
13C−NMR(125MHz,CDCl3,δppm):29.28,33.95,37.77,41.09,41.55,42.13,44.74,49.83,141.98,143.04,162.60,162.68,170.90,177.54.
Mp.(℃):270〜272。
1H−NMR(500MHz,d6−DMSO,δppm):0.95(dd,J1=2.14Hz,J2=12.83Hz,1H),1.20(d,J=10.64Hz,1H),1.41(d,J=10.69Hz,1H),2.10(d,J=4.27Hz,1H),2.30(s,1H),2.32(dd,J1=4.89Hz,J2=14.14Hz,1H),2.59(dd,J1=16.50Hz,J2=27.49Hz,2H),2.71(d,J=3.06Hz,1H),2.97(d,J=2.75Hz,1H),9.42(brs,4H).
13C−NMR(125MHz,d6−DMSO,δppm):29.24,34.01,38.13,38.99,40.79,41.75,45.34,49.60,142.50,143.03,162.80,162.88,172.90,177.11.
Mp.(℃):244〜246。
1H−NMR(500MHz,d6−DMSO,δppm):1.24(dd,J1=1.83Hz,J2=12.83Hz,1H),2.00(dd,J1=4.58Hz,J2=12.83Hz,1H),2.07(d,J=9.16Hz,1H),2.25(d,J=11.31Hz,1H),2.45〜2.49(m,2H),2.66(d,J=8.55Hz,1H),2.84(d,J=18.02Hz,2H),3.16(d,J=18.33Hz,1H),3.60(t,J=4.28Hz,2H),12.11(brs,2H).
13C−NMR(125MHz,d6−DMSO,δppm):37.40,37.54,38.25,38.70,39.92,40.44,42.00,49.75,66.37,170.96,172.07,172.23,177.54.
Mp.(℃):213〜214。
1H−NMR(500MHz,d6−DMSO,δppm):1.29(dd,J1=3.36Hz,J2=13.14Hz,1H),1.65(d,J1=13.14Hz,1H),2.00(dd,J1=4.58Hz,J2=12.13Hz,1H),2.19(d,J=12.83Hz,1H),2.33(d,J=3.28Hz,1H),2.68(s,1H),2.81(t,J=8.24Hz,1H),2.89(d,J=18.33Hz,1H),3.03(t,J=8.25Hz,1H),3.18(d,J=18.33Hz,1H),3.71〜3.77(m,2H).
13C−NMR(125MHz,d6−DMSO,δppm):31.98,36.59,37.94,38.38,40.22,40.71,40.96,42.09,44.01,49.38,170.53,172.79,173.09,177.06.
Mp.(℃):253〜254。
実施例14(ODSF−DDEポリアミド酸及びポリイミドの合成)
この白色粉末の赤外吸収スペクトル(KBrにて測定:添付チャート参照)から1708.79,1773.41cm−1(5員環イミド)を確認した。また、1H−NMRからイミド化率75.7%を算出した。
この白色粉末の赤外吸収スペクトル(KBrにて測定:添付チャート参照)から1708.07,1773.39cm−1(5員環イミド)を確認した。また、1H−NMRからイミド化率71.6%を算出した。
この白色粉末の赤外吸収スペクトル(KBrにて測定:添付チャート参照)から1715.32,1781.44cm−1(5員環イミド)を確認した。また、1H−NMRからイミド化率80.1%を算出した。
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