JP2024045015A - A method for decomposing a polymer compound, a degradable adhesive composition and a method for separating a bonded body using the same, a degradable paint composition and a method for removing a coating film using the same, and a method for removing fibers contained in fiber-reinforced plastics. How to collect - Google Patents
A method for decomposing a polymer compound, a degradable adhesive composition and a method for separating a bonded body using the same, a degradable paint composition and a method for removing a coating film using the same, and a method for removing fibers contained in fiber-reinforced plastics. How to collect Download PDFInfo
- Publication number
- JP2024045015A JP2024045015A JP2023126777A JP2023126777A JP2024045015A JP 2024045015 A JP2024045015 A JP 2024045015A JP 2023126777 A JP2023126777 A JP 2023126777A JP 2023126777 A JP2023126777 A JP 2023126777A JP 2024045015 A JP2024045015 A JP 2024045015A
- Authority
- JP
- Japan
- Prior art keywords
- polymer compound
- chemical formula
- bond
- decomposing
- degradable
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 94
- 229920000642 polymer Polymers 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims description 48
- 239000000853 adhesive Substances 0.000 title claims description 23
- 230000001070 adhesive effect Effects 0.000 title claims description 23
- 239000000835 fiber Substances 0.000 title claims description 18
- 239000003973 paint Substances 0.000 title claims description 15
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims description 14
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims description 14
- 239000011248 coating agent Substances 0.000 title description 13
- 238000000576 coating method Methods 0.000 title description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000000126 substance Substances 0.000 claims abstract description 65
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- -1 poly(diacylhydrazine) Polymers 0.000 abstract description 41
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 29
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- 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 8
- 125000004429 atom Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DXTYCZIGQMMRBS-UHFFFAOYSA-N N'-prop-2-enoylprop-2-enehydrazide Chemical compound C=CC(=O)NNC(=O)C=C DXTYCZIGQMMRBS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000009935 nitrosation Effects 0.000 description 3
- 238000007034 nitrosation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005077 diacylhydrazine group Chemical group 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFDULEKOJAEIRI-UHFFFAOYSA-N (2-acetyloxy-3-iodophenyl) acetate Chemical compound CC(=O)OC1=CC=CC(I)=C1OC(C)=O UFDULEKOJAEIRI-UHFFFAOYSA-N 0.000 description 1
- PEZNEXFPRSOYPL-UHFFFAOYSA-N (bis(trifluoroacetoxy)iodo)benzene Chemical compound FC(F)(F)C(=O)OI(OC(=O)C(F)(F)F)C1=CC=CC=C1 PEZNEXFPRSOYPL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
【課題】反応性ガスを用いた乾式処理によりポリ(ジアシルヒドラジン)を分解する方法、及びそれを用いたポリ(ジアシルヒドラジン)のさらなる応用手段を提供すること。【解決手段】下記化学式(1)で表す2価の基を備えたポリマー化合物、すなわちポリ(ジアシルヒドラジン)に窒素酸化物と接触させることにより、このポリマー化合物を分解及び低分子量化させればよい。このとき用いられる窒素酸化物は気体なので、この分解方法は乾式処理となる。なお、上記化学式(1)において、波線を付した結合は、他の原子への結合手を表す。TIFF2024045015000023.tif18154【選択図】なし[Problem] To provide a method for decomposing poly(diacylhydrazine) by dry treatment using a reactive gas, and further application means for poly(diacylhydrazine) using the same. [Solution] A polymer compound having a divalent group represented by the following chemical formula (1), i.e., poly(diacylhydrazine), can be decomposed and reduced in molecular weight by contacting the polymer compound with nitrogen oxide. Since the nitrogen oxide used in this case is a gas, this decomposition method is a dry treatment. In the above chemical formula (1), bonds marked with wavy lines represent bonds to other atoms. TIFF2024045015000023.tif18154 [Selected Figure] None
Description
特許法第30条第2項適用申請有り 刊行物名:日本化学会第103春季年会講演予稿集、第K301-3am-08頁、発行者:公益社団法人日本化学会、発行年月日:令和5年3月8日 集会名:日本化学会第103春季年会、主催者:公益社団法人日本化学会、開催日:令和5年3月24日Application for application of Article 30, Paragraph 2 of the Patent Act Publication name: Proceedings of the 103rd Spring Annual Meeting of the Chemical Society of Japan, page K301-3am-08, Publisher: The Chemical Society of Japan, Public Interest Incorporated Association, Publication date: March 8, 2020 Meeting name: 103rd Spring Annual Meeting of the Chemical Society of Japan, Organizer: The Chemical Society of Japan, Public Interest Incorporated Association, Date: March 24, 2020
本発明は、ポリマー化合物の分解方法、分解性接着剤組成物及びその接合体の分離方法、分解性塗料組成物及びその塗膜の除去方法、並びに繊維強化プラスチックに含まれる繊維を回収する方法に関するものである。 The present invention relates to a method for decomposing a polymer compound, a method for separating a degradable adhesive composition and its joined body, a method for removing a degradable paint composition and its coating film, and a method for recovering fibers contained in fiber-reinforced plastics. It is something.
近年、環境保護の観点等から、廃棄しても自然に分解されるような、生分解性高分子や光分解性高分子に代表される分解性高分子材料の開発が盛んに行われている。しかし、生分解性高分子や光分解性高分子は、通常の使用環境において経時的な劣化を伴うことが問題となっている。 In recent years, from the perspective of environmental protection, there has been active development of degradable polymer materials, such as biodegradable polymers and photodegradable polymers, which naturally decompose even when discarded. . However, a problem with biodegradable polymers and photodegradable polymers is that they deteriorate over time in normal usage environments.
このため、使用時に経時的に劣化することなく、廃棄時に速やかに分解可能なポリマー化合物が求められており、廃棄時に酸化剤により容易に分解可能な高分子化合物として、ジカルボン酸又はその反応性誘導体(酸クロライドや活性エステル誘導体)と、ヒドラジン又はジカルボン酸のジヒドラジドとを重縮合させて得られるポリ(ジアシルヒドラジン)が数例提案されている(例えば、特許文献1、2を参照)。 For this reason, there is a need for polymer compounds that do not deteriorate over time during use and can be quickly decomposed when disposed of.Dicarboxylic acids or their reactive derivatives are suitable as polymer compounds that can be easily decomposed by oxidizing agents during disposal. Several examples of poly(diacylhydrazine) obtained by polycondensing (acid chloride or active ester derivative) with hydrazine or dihydrazide of a dicarboxylic acid have been proposed (see, for example, Patent Documents 1 and 2).
このポリ(ジアシルヒドラジン)は、上記のように酸化剤により容易に分解することができるので、プラスチック製品の廃棄物問題を解消し得るばかりでなく、例えば、これを接着剤組成物に応用すれば、酸化剤を用いることで容易に接合状態を解除することのできる接着剤組成物になるし、塗料組成物に応用すれば、酸化剤を用いることで容易に塗膜を剥離することのできる塗料組成物になると期待される。 This poly(diacylhydrazine) can be easily decomposed by oxidizing agents as mentioned above, so it can not only solve the waste problem of plastic products, but also can be applied to adhesive compositions, for example. By using an oxidizing agent, it becomes an adhesive composition that can easily release the bonded state, and when applied to a paint composition, it can be used to create a paint that allows the paint film to be easily peeled off by using an oxidizing agent. It is expected that it will become a composition.
上記のように、ポリ(ジアシルヒドラジン)が酸化剤で容易に分解される特性を応用することで、様々な製品展開が期待される。ところで、上記特許文献にもある通り、ポリ(ジアシルヒドラジン)は、酸素分子のようなラジカル性の酸化剤では分解されない一方で、次亜塩素酸ナトリウムのような酸化剤で容易に分解される性質がある。このような酸化剤の多くは水溶液の状態で酸化作用を発現するものであり、ゆえに、ポリ(ジアシルヒドラジン)を酸化剤で分解しようとすると、その水溶液を用いた湿式での処理を行わなければならない。しかしながら、ポリ(ジアシルヒドラジン)の応用製品の適用先が水の使用を嫌う場合も考えられる。そのため、上記のような湿式処理だけでなく、反応性ガスを用いた乾式処理でポリ(ジアシルヒドラジン)を分解する手段を提供できれば、その用途をさらに拡大できると考えられる。 As described above, the application of the property of poly(diacylhydrazine) being easily decomposed by an oxidizing agent is expected to lead to the development of various products. Meanwhile, as described in the above patent document, poly(diacylhydrazine) is not decomposed by radical oxidizing agents such as oxygen molecules, but is easily decomposed by oxidizing agents such as sodium hypochlorite. Many of these oxidizing agents exhibit an oxidizing effect in the form of an aqueous solution, and therefore, when attempting to decompose poly(diacylhydrazine) with an oxidizing agent, a wet treatment using the aqueous solution must be performed. However, there may be cases where the application destination of poly(diacylhydrazine) does not like the use of water. Therefore, if a means for decomposing poly(diacylhydrazine) can be provided not only by the above-mentioned wet treatment but also by a dry treatment using a reactive gas, its uses can be further expanded.
本発明は、以上の状況に鑑みてなされたものであり、反応性ガスを用いた乾式処理によりポリ(ジアシルヒドラジン)を分解する方法、及びそれを用いたポリ(ジアシルヒドラジン)のさらなる応用手段を提供することを目的とする。なお、本明細書において、ポリ(ジアシルヒドラジン)とは、下記化学式(1)で表す2価の基(ジアシルヒドラジン構造)を複数備えた化合物を表すものとし、必ずしも下記化学式(1)で表す2価の基を繰り返し構造として含む化合物のみを意味するものではない。 The present invention has been made in view of the above circumstances, and aims to provide a method for decomposing poly(diacylhydrazine) by dry treatment using a reactive gas, and further application means of poly(diacylhydrazine) using the method. In this specification, poly(diacylhydrazine) refers to a compound having multiple divalent groups (diacylhydrazine structures) represented by the following chemical formula (1), and does not necessarily mean only compounds containing the divalent group represented by the following chemical formula (1) as a repeating structure.
本発明者は、以上の課題を解決するために鋭意検討を重ねた結果、下記化学式(1)で表す2価の基を備えたポリマー化合物、すなわちポリ(ジアシルヒドラジン)を窒素酸化物と接触させることで容易に分解されることを見出し、本発明を完成するに至った。具体的には、本発明は、以下のようなものを提供する。 As a result of extensive research into solving the above problems, the inventors discovered that a polymer compound having a divalent group represented by the following chemical formula (1), i.e., poly(diacylhydrazine), can be easily decomposed by contacting it with nitrogen oxides, and thus completed the present invention. Specifically, the present invention provides the following:
(1)本発明は、下記化学式(1)で表す2価の基を備えたポリマー化合物に窒素酸化物を接触させる工程を含むことを特徴とするポリマー化合物の分解方法である。
(2)また本発明は、上記ポリマー化合物が、エポキシ樹脂の硬化物、ビニルポリマーの架橋体及びポリウレタンからなる群より選択される少なくとも1つである(1)項記載のポリマー化合物の分解方法である。 (2) The present invention also relates to a method for decomposing a polymer compound according to item (1), in which the polymer compound is at least one selected from the group consisting of a cured product of an epoxy resin, a crosslinked product of a vinyl polymer, and a polyurethane.
(3)本発明は、下記化学式(1)で表す2価の基を備えたポリマー化合物を含むことを特徴とし、窒素酸化物と接触させることで分解することを特徴とする分解性接着剤組成物でもある。
(4)本発明は、上記(3)項記載の分解性接着剤組成物の硬化物により接着されている接合体において、上記硬化物に窒素酸化物を接触させることを特徴とする接合体の分離方法でもある。 (4) The present invention provides a bonded body bonded by a cured product of the degradable adhesive composition described in item (3) above, which is characterized in that the cured product is brought into contact with nitrogen oxide. It is also a separation method.
(5)本発明は、下記化学式(1)で表す2価の基を備えたポリマー化合物を含むことを特徴とし、窒素酸化物と接触させることで分解することを特徴とする分解性塗料組成物でもある。
(6)本発明は、上記(5)項記載の分解性塗料組成物により形成された塗膜を備えた塗装面に窒素酸化物を接触させることを特徴とする塗装面からの塗膜の除去方法でもある。 (6) The present invention also relates to a method for removing a coating film from a painted surface, characterized by contacting a painted surface having a coating film formed from the decomposable coating composition described in (5) above with nitrogen oxides.
(7)本発明は、下記化学式(1)で表す2価の基を備えたポリマー化合物をマトリクスとして含む繊維強化プラスチックに窒素酸化物を接触させることで上記マトリクスを分解させ、上記繊維強化プラスチックに含まれている繊維を分離回収することを特徴とする繊維強化プラスチックに含まれる繊維を回収する方法でもある。
本発明によれば、反応性ガスを用いた乾式処理によりポリ(ジアシルヒドラジン)を分解する方法、及びそれを用いたポリ(ジアシルヒドラジン)のさらなる応用手段が提供される。 According to the present invention, a method for decomposing poly(diacylhydrazine) by dry treatment using a reactive gas, and further application means for poly(diacylhydrazine) using the method are provided.
以下、本発明のポリマー化合物の分解方法の一実施態様、分解性接着剤組成物の一実施形態、それを用いてなる接合体の分離方法の一実施態様、分解性塗料組成物の一実施形態、それを用いてなる塗膜の除去方法、及び繊維強化プラスチックに含まれる繊維を回収する方法の一実施態様についてそれぞれ説明する。なお、本発明は、以下の実施形態や実施態様に何ら限定されるものではなく、本発明の範囲において適宜変更を加えて実施することができる。 Hereinafter, one embodiment of the method for decomposing a polymer compound of the present invention, one embodiment of the degradable adhesive composition, one embodiment of the method for separating a joined body using the same, and one embodiment of the degradable paint composition. , a method for removing a coating film using the same, and a method for recovering fibers contained in fiber-reinforced plastics will be described. Note that the present invention is not limited to the following embodiments and embodiments, and can be implemented with appropriate modifications within the scope of the present invention.
<ポリマー化合物の分解方法>
まずは、本発明のポリマー化合物の分解方法の一実施態様について説明する。本発明のポリマー化合物の分解方法は、下記化学式(1)で表す2価の基を備えたポリマー化合物に窒素酸化物を接触させる工程を含むことを特徴とする。なお、下記化学式(1)において、波線を付した結合は、他の原子への結合手を表す。また、「下記化学式(1)で表す2価の基を備えた」ポリマー化合物とは、ポリマー化合物の分子中に下記化学式(1)で表す構造を含む化合物であることを意味する。
<Method for Decomposing Polymer Compound>
First, one embodiment of the method for decomposing a polymer compound of the present invention will be described. The method for decomposing a polymer compound of the present invention is characterized by including a step of contacting a polymer compound having a divalent group represented by the following chemical formula (1) with nitrogen oxide. In the following chemical formula (1), the bond with a wavy line represents a bond to another atom. In addition, a polymer compound "having a divalent group represented by the following chemical formula (1)" means a compound containing a structure represented by the following chemical formula (1) in the molecule of the polymer compound.
ポリマー化合物が上記化学式(1)で表す構造を備えると、窒素酸化物と接触した際に下記の化学反応を経て分解する。下記の化学反応では、一酸化窒素及び二酸化窒素により分解される例を示したが、下記の化学反応式で表す通り、上記化学式(1)で表す構造に含まれる窒素原子がニトロソ化されることがこの分解反応の引き金となっており、このようなニトロソ化を引き起こすことのできる窒素酸化物であれば特に限定されない。 When a polymer compound has the structure represented by the above chemical formula (1), it decomposes through the following chemical reaction when it comes into contact with nitrogen oxides. In the chemical reaction below, an example is shown in which the polymer compound is decomposed by nitric oxide and nitrogen dioxide, but as shown in the chemical reaction formula below, the decomposition reaction is triggered by the nitrosation of the nitrogen atom contained in the structure represented by the above chemical formula (1), and there are no particular limitations on the nitrogen oxide that can cause such nitrosation.
上記化学反応式に示すように、化学式(1)で表す構造を備えたポリマー化合物は、窒素酸化物と接触することでニトロソ化される。このニトロソ化を受けることにより上記破線で囲んだ部分が優れた脱離基となり、環境中に存在する水分子がこの脱離基に隣接するカルボニル基を攻撃することでその脱離基が脱離して分子が切断される。その後、脱離した化合物は脱水によりアジドに変換される。これらの反応を経て、ポリマー化合物は分解されて低分子量化する。 As shown in the above chemical reaction formula, the polymer compound having the structure represented by chemical formula (1) is nitrosated by contacting with nitrogen oxide. By undergoing this nitrosation, the part surrounded by the broken line above becomes an excellent leaving group, and water molecules present in the environment attack the carbonyl group adjacent to this leaving group, causing the leaving group to leave. The molecule is cleaved. Thereafter, the eliminated compound is converted to azide by dehydration. Through these reactions, the polymer compound is decomposed and its molecular weight is reduced.
分解対象となるポリマー化合物としては、上記化学式(1)で表す構造を備えたものであれば特に限定されない。また、上記化学式(1)で表す構造は、ポリマー化合物の繰り返し単位として主鎖に含まれてもよいし、ポリマー化合物の側鎖に含まれてもよいし、ポリマー鎖同士を架橋する架橋構造に含まれてもよい。このようなポリマー化合物の一例としては、エポキシ樹脂の硬化物、ビニルポリマーの架橋体、ポリウレタン等を挙げることができる。なお、エポキシ樹脂の硬化物やビニルポリマーの架橋体等は、複数のポリマー鎖が架橋されて極めて大きな分子量をもつ硬化物となる。厳密には、こうした硬化物をポリマー化合物と呼ばない場合もあるかもしれないが、本発明では、こうした硬化物も含めた高分子化合物をポリマー化合物と呼ぶ。 The polymer compound to be decomposed is not particularly limited as long as it has the structure represented by the above chemical formula (1). The structure represented by the above chemical formula (1) may be included in the main chain of the polymer compound as a repeating unit, in the side chain of the polymer compound, or in a crosslinked structure that crosslinks polymer chains. Examples of such polymer compounds include cured epoxy resins, crosslinked vinyl polymers, and polyurethanes. In addition, cured epoxy resins and crosslinked vinyl polymers are cured products with extremely large molecular weights, in which multiple polymer chains are crosslinked. Strictly speaking, such cured products may not be called polymer compounds, but in the present invention, polymer compounds including such cured products are called polymer compounds.
エポキシ樹脂の硬化物は、ポリエポキシ化合物とポリオール化合物とアミン等の硬化触媒とを含むエポキシ樹脂を硬化させたものである。本発明におけるエポキシ樹脂の硬化物は、その分子中に上記化学式(1)で表す構造を備える。エポキシ樹脂の多くは、ビスフェノールAのようなビスフェノール化合物がポリオール化合物として用いられる。こうしたビスフェノール化合物として、例えば、下記のような合成経路で得た化合物を用いることにより、エポキシ樹脂の硬化体であるポリマー化合物中に上記化学式(1)で表す構造を導入することができる。なお、なお、下記では説明のために4種類のビスフェノ-ル化合物を例に挙げたが、本発明はこれらに限定されるものではない。 The cured epoxy resin is obtained by curing an epoxy resin containing a polyepoxy compound, a polyol compound, and a curing catalyst such as an amine. The cured epoxy resin in the present invention has a structure represented by the above chemical formula (1) in its molecule. In many epoxy resins, a bisphenol compound such as bisphenol A is used as a polyol compound. By using such a bisphenol compound, for example, a compound obtained by the following synthetic route, the structure represented by the above chemical formula (1) can be introduced into the polymer compound, which is the cured epoxy resin. Note that, for the sake of explanation, four types of bisphenol compounds are given below as examples, but the present invention is not limited to these.
ビスフェノール化合物のようなポリフェノール化合物を合成するには、上記のように、フェノールのカルボン酸ヒドラジドを合成し、次いでビスアセトキシヨードベンゼン等のような酸化剤を用いて、酸化的に縮合させればよい。ここで用いる酸化剤としては、この他に、過硫酸水素カリウム、硫酸水素カリウム、及び硫酸カリウムの複塩、ビス(トリフルオロアセトキシ)ヨードベンゼン、並びにヨードソベンゼン等を例示することができる。 To synthesize a polyphenol compound such as a bisphenol compound, a phenol carboxylic acid hydrazide is synthesized as described above, and then oxidatively condensed using an oxidizing agent such as bisacetoxyiodobenzene. Other examples of the oxidizing agent used here include potassium hydrogen persulfate, potassium hydrogen sulfate, and potassium sulfate double salts, bis(trifluoroacetoxy)iodobenzene, and iodosobenzene.
上記のような手順で得た、上記化学式(1)で表す2価の基を備えたビスフェノール化合物は、イミダゾール等のような塩基触媒の存在下で、例えば下記のようにポリエポキシ化合物と反応して硬化する。 The bisphenol compound having a divalent group represented by the chemical formula (1) obtained by the above procedure is reacted with a polyepoxy compound as described below in the presence of a base catalyst such as imidazole. harden.
上記化学反応式のように反応して硬化した状態のポリマー化合物の主鎖には上記化学式(1)で表す2価の基が含まれており、既に説明した通り、窒素酸化物と接触させることにより(C=O)-NH間の結合が切断されて分解し低分子量化する。このようにして硬化物が低分子量化されると、それは非常に脆い状態になるので容易に除去することが可能になる。 The main chain of the polymer compound that is cured by reacting as shown in the chemical reaction formula above contains a divalent group represented by the chemical formula (1) above, and as already explained, it can be brought into contact with nitrogen oxides. The bond between (C=O)-NH is broken and decomposed, resulting in a lower molecular weight. When the molecular weight of the cured product is reduced in this way, it becomes very brittle and can be easily removed.
ビニルポリマーの架橋体は、例えば、(A)エチレン性不飽和結合を備えたモノマーと、(B)分子内に上記化学式(1)で表す2価の基を備えた、2以上のエチレン性不飽和結合を有する架橋剤とをラジカル重合させることで得られる。このような架橋剤は、例えば、下記化学反応式のように塩化(メタ)アクリロイルとヒドラジンとを塩基存在下で反応させることで得られる。なお、本明細書において、(メタ)アクリロイルとは、アクリロイル及び/又はメタクリロイルを意味する。 A crosslinked vinyl polymer can be obtained, for example, by radical polymerization of (A) a monomer having an ethylenically unsaturated bond and (B) a crosslinking agent having two or more ethylenically unsaturated bonds and a divalent group represented by the above chemical formula (1) in the molecule. Such a crosslinking agent can be obtained, for example, by reacting (meth)acryloyl chloride with hydrazine in the presence of a base, as shown in the following chemical reaction formula. In this specification, (meth)acryloyl means acryloyl and/or methacryloyl.
上記のようにして得た架橋剤は、例えば、アゾビスイソブチロニトリル(AIBN)のような重合開始剤の存在下、エチレン性不飽和結合を備えたモノマー(例えば、ビニルモノマー)とともに重合してビニルポリマーの架橋体を形成させる。この架橋体は、架橋部分に上記化学式(1)で表す2価の基を備え、窒素酸化物と接触することで架橋部分が切断される。 The crosslinking agent obtained as described above is polymerized together with a monomer having an ethylenically unsaturated bond (for example, a vinyl monomer) in the presence of a polymerization initiator such as azobisisobutyronitrile (AIBN). to form a crosslinked vinyl polymer. This crosslinked product has a divalent group represented by the above chemical formula (1) in the crosslinked portion, and the crosslinked portion is cut by contacting with nitrogen oxide.
エチレン性不飽和結合を備えたモノマーとしては、エチレン、スチレン、アクリル酸、アクリル酸エステル、メタアクリル酸エステル、アクリルアミド、N-置換アクリルアミド、N,N-二置換アクリルアミド、アクリロニトリル、ブタジエン、酢酸ビニル等を挙げることができる。 Monomers with ethylenically unsaturated bonds include ethylene, styrene, acrylic acid, acrylic esters, methacrylic esters, acrylamide, N-substituted acrylamide, N,N-disubstituted acrylamide, acrylonitrile, butadiene, vinyl acetate, etc. can be mentioned.
また、重合開始剤としては、加熱によりラジカルを発生させるものが挙げられ、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩;過酸化水素、t-ブチルパーオキシド、メチルエチルケトンパーオキシド等の過酸化物;アゾニトリル化合物、アゾアミジン化合物、環状アゾアミジン化合物、アゾアミド化合物、アルキルアゾ化合物、2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロリド、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]ジヒドロクロリド等のアゾ化合物等が挙げられる。 Polymerization initiators include those that generate radicals when heated, such as persulfates, such as sodium persulfate, potassium persulfate, and ammonium persulfate; peroxides, such as hydrogen peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide; and azo compounds, such as azonitrile compounds, azoamidine compounds, cyclic azoamidine compounds, azoamide compounds, alkylazo compounds, 2,2'-azobis(2-amidinopropane) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride.
ポリウレタンは、ジイソシアナート化合物とジオール化合物との重縮合反応により合成されるポリマー化合物である。このジオール化合物として、上記化学式(1)で表す構造を備えたものを用いることにより、上記化学式(1)で表す構造を備えたポリウレタンを得ることができる。このようなジオール化合物としては、例えば、化学式(1)の構造を備えたビスフェノール化合物等として既に説明したものと同様に、アルコールのカルボン酸ヒドラジドの酸化的な縮合反応によって合成することができる。なお、アルコールのカルボン酸ヒドラジドは、フェノールのカルボン酸ヒドラジドと同様に、アルコールのカルボン酸をエステル化した後、ヒドラジンと反応させることによって容易に合成することができる。この合成で用いるアルコールのカルボン酸としては、グリコール酸、乳酸、酒石酸、クエン酸等多くの化合物が知られており、これらを制限なく用いることができる。 Polyurethane is a polymer compound synthesized by a polycondensation reaction between a diisocyanate compound and a diol compound. By using a diol compound having the structure represented by the above chemical formula (1), a polyurethane having the structure represented by the above chemical formula (1) can be obtained. Such a diol compound can be synthesized, for example, by an oxidative condensation reaction of a carboxylic acid hydrazide of an alcohol, in the same manner as the bisphenol compound having the structure of chemical formula (1). Note that, like the carboxylic acid hydrazide of phenol, the carboxylic acid hydrazide of alcohol can be easily synthesized by esterifying the carboxylic acid of alcohol and then reacting it with hydrazine. As the alcohol carboxylic acid used in this synthesis, many compounds such as glycolic acid, lactic acid, tartaric acid, and citric acid are known, and these can be used without restriction.
ポリマー化合物の分解に用いる窒素酸化物としては、一酸化窒素、二酸化窒素、三酸化窒素、亜酸化窒素、三酸化二窒素、四酸化二窒素、五酸化二窒素等を挙げることができ、これらの中でも、一酸化窒素及び二酸化窒素を好ましく挙げることができる。これら窒素酸化物は、分解対象であるポリマー化合物に気体の状態で接触される。このため、本発明の分解方法は、上記特許文献のように次亜塩素酸塩の水溶液を用いた湿式処理ではなく、乾式処理により実行することが可能であり、分解対象が水を嫌う物体に適用されている場合であっても問題無く適用可能である。このような用途の一例としては、BGA(ボールグリッドアレイ)チップを電気回路基板に実装する際のアンダーフィルとすることが挙げられる。BGAチップを電気回路基板に実装した場合、チップと電気回路基板との間の熱膨張率の違いにより、基板への素子実装の際のリフロー工程等で熱負荷がかかった際にBGAチップの端子が電気回路基板のパッドからずれてしまって電気接続不良を生じることがある。こうした不良の修復や、またはその他の理由により、アンダーフィルにより固定されたチップを外して、再度基板へ実装し直す場合がある。このよう場面において、窒素酸化物の気体をこれに接触させる乾式処理により、アンダーフィルを容易に除去することができる。 Examples of nitrogen oxides used to decompose polymer compounds include nitric oxide, nitrogen dioxide, nitrogen trioxide, nitrous oxide, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide, etc., and among these, nitric oxide and nitrogen dioxide are preferred. These nitrogen oxides are contacted in a gaseous state with the polymer compound to be decomposed. For this reason, the decomposition method of the present invention can be carried out by a dry process, not a wet process using an aqueous solution of hypochlorite as in the above patent document, and can be applied without problems even when the decomposition target is an object that dislikes water. One example of such an application is as an underfill when mounting a BGA (ball grid array) chip on an electric circuit board. When a BGA chip is mounted on an electric circuit board, due to the difference in thermal expansion coefficient between the chip and the electric circuit board, when a thermal load is applied during a reflow process or the like when mounting elements on the board, the terminals of the BGA chip may shift from the pads of the electric circuit board, resulting in poor electrical connection. In order to repair such a defect or for other reasons, the chip fixed by the underfill may be removed and remounted on the board. In such cases, the underfill can be easily removed by a dry process in which it is exposed to nitrogen oxide gas.
窒素酸化物により分解されたポリマー化合物は、非常に脆くなり、容易に除去することが可能となる。このため、ポリマー化合物が、接着剤として用いられていた場合には接着対象から容易にそれを除去することが可能であるし、塗膜を形成していた場合には塗装面から容易にそれを除去することが可能である。 Polymer compounds decomposed by nitrogen oxides become very brittle and can be easily removed. Therefore, if the polymer compound is used as an adhesive, it can be easily removed from the object to be bonded, and if it forms a coating, it can be easily removed from the painted surface.
<分解性接着剤組成物>
次に本発明の分解性接着剤組成物について説明する。本発明の分解性接着剤組成物は、下記化学式(1)で表す2価の基を備えたポリマー化合物を含むことを特徴とし、窒素酸化物と接触させることで分解することを特徴とする。なお、化学式(1)において、波線を付した結合は、他の原子への結合手を表す。
<Degradable adhesive composition>
Next, the degradable adhesive composition of the present invention will be explained. The degradable adhesive composition of the present invention is characterized by containing a polymer compound having a divalent group represented by the following chemical formula (1), and is characterized by being decomposed by contacting with nitrogen oxides. In addition, in chemical formula (1), a bond with a wavy line represents a bond to another atom.
すなわち、本発明の分解性接着剤組成物は、上記本発明のポリマー化合物の分解方法にて説明したポリマー化合物を含むものである。したがって、この接着剤組成物により形成された硬化物は、上記ポリマー化合物を含むものであり、窒素酸化物に接触させることで分解し低分子量化する。分解し低分子量化した硬化物は、最早硬化物としての堅牢性を失っており、非常に脆く容易に除去することが可能である。なお、窒素酸化物については、上記本発明の分解方法にて述べた通りなので、ここでの説明を省略する。 That is, the degradable adhesive composition of the present invention contains the polymer compound described in the above method for decomposing a polymer compound of the present invention. Therefore, the cured product formed from this adhesive composition contains the above-mentioned polymer compound, and when brought into contact with nitrogen oxides, it decomposes and becomes lower in molecular weight. The cured product that has been decomposed and reduced in molecular weight has lost its robustness as a cured product and is extremely brittle and can be easily removed. Note that the nitrogen oxides are as described above in the decomposition method of the present invention, so the explanation here will be omitted.
本発明の分解性接着剤組成物は、上記ポリマー化合物と溶剤とを含み、溶剤が蒸発することでポリマー化合物の硬化物となるタイプの組成物でもよいし、上記ポリマー化合物の前駆体を含み化学反応により硬化物となるタイプの組成物でもよい。後者のタイプの組成物の一例としては、ポリエポキシ化合物とポリオール化合物とアミンなどの硬化触媒とを含んだいわゆるエポキシ接着剤組成物や、(A)エチレン性不飽和結合を備えたモノマーと、(B)分子内に上記化学式(1)で表す2価の基を備えた、2以上のエチレン性不飽和結合を有する架橋剤と、(C)重合開始剤とを含んだビニル系接着剤組成物を挙げることができる。なお、本発明の分解性接着剤組成物は、これらに限定されるものではない。 The degradable adhesive composition of the present invention may be a type of composition that contains the above-mentioned polymer compound and a solvent and becomes a cured product of the polymer compound when the solvent evaporates, or it may be a composition that contains a precursor of the above-mentioned polymer compound and that becomes a cured product of the polymer compound when the solvent evaporates. It may be a type of composition that becomes a cured product upon reaction. An example of the latter type of composition is a so-called epoxy adhesive composition containing a polyepoxy compound, a polyol compound, and a curing catalyst such as an amine, or a monomer having (A) an ethylenically unsaturated bond; B) A vinyl adhesive composition containing a crosslinking agent having two or more ethylenically unsaturated bonds and having a divalent group represented by the above chemical formula (1) in the molecule, and (C) a polymerization initiator. can be mentioned. Note that the degradable adhesive composition of the present invention is not limited to these.
エポキシ接着剤組成物は、ポリエポキシ化合物、ポリオール化合物、及びアミン等の硬化触媒を含み、その硬化物として上記化学式(1)で表す2価の基を備えたポリマー化合物を与える。ポリエポキシ化合物としては、エポキシ接着剤組成物用途として数多くの市販品が存在するので、それを入手して用いることができる。また、ポリオール化合物としては、既に説明したような、化学式(1)で表す2価の基を備えたビスフェノール化合物を好ましく挙げることができる。硬化触媒としてのアミン化合物としては、イミダゾール等を好ましく挙げることができる。これらの成分が反応して、化学式(1)で表す2価の基を備えたポリマー化合物となる硬化物を与えることや、それが窒素酸化物と接触した際に分解することについては既に説明した通りなので、ここでの説明を省略する。 The epoxy adhesive composition contains a polyepoxy compound, a polyol compound, and a curing catalyst such as an amine, and provides a polymer compound having a divalent group represented by the above chemical formula (1) as a cured product. Since there are many commercially available polyepoxy compounds for use in epoxy adhesive compositions, they can be obtained and used. Further, as the polyol compound, a bisphenol compound having a divalent group represented by the chemical formula (1) as described above can be preferably mentioned. Preferred examples of the amine compound as a curing catalyst include imidazole and the like. It has already been explained that these components react to give a cured product that becomes a polymer compound with a divalent group represented by the chemical formula (1), and that it decomposes when it comes into contact with nitrogen oxides. As this is true, we will omit the explanation here.
ビニル系接着剤組成物は、(A)エチレン性不飽和結合を備えたモノマー、(B)分子内に上記化学式(1)で表す2価の基を備えた、2以上のエチレン性不飽和結合を有する架橋剤、及び(C)重合開始剤を含み、その硬化物として上記化学式(1)で表す2価の基を備えたポリマー化合物を与える。これらの各成分については、上記ビニルポリマーの架橋体の説明にて既に述べた通りなので、ここでの説明を省略する。また、この硬化物が上記化学式(1)で表す構造を備え、それが窒素酸化物と接触した際に分解することについても既に述べた通りである。 The vinyl adhesive composition includes (A) a monomer having an ethylenically unsaturated bond, (B) two or more ethylenically unsaturated bonds having a divalent group represented by the above chemical formula (1) in the molecule. and (C) a polymerization initiator, and provides a polymer compound having a divalent group represented by the above chemical formula (1) as a cured product thereof. Since each of these components has already been described in the description of the crosslinked vinyl polymer, the description thereof will be omitted here. Further, as already mentioned, this cured product has the structure represented by the above chemical formula (1), and decomposes when it comes into contact with nitrogen oxides.
<接合体の分解方法>
上記分解性接着剤組成物の硬化物により接着されている接合体において、その硬化物に窒素酸化物を接触させることを特徴する接合体の分離方法もまた、本発明の一つである。これについては、上記分解性接着剤組成物の説明にて既に述べた通りなので、ここでの説明を省略する。
<Method of disassembling the joined body>
The present invention also provides a method for separating a bonded structure bonded with the cured product of the decomposable adhesive composition, the method comprising contacting the cured product with nitrogen oxide. This has already been described in the description of the decomposable adhesive composition, and therefore will not be described here.
<分解性塗料組成物>
次に本発明の分解性接着剤組成物について説明する。本発明の分解性塗料組成物は、下記化学式(1)で表す2価の基を備えたポリマー化合物を含むことを特徴とし、その塗膜が窒素酸化物と接触することで分解することを特徴とする。なお、化学式(1)において、波線を付した結合は、他の原子への結合手を表す。
<Degradable coating composition>
Next, the decomposable adhesive composition of the present invention will be described. The decomposable coating composition of the present invention is characterized by containing a polymer compound having a divalent group represented by the following chemical formula (1), and by the fact that the coating film thereof decomposes upon contact with nitrogen oxides. In addition, in chemical formula (1), the bond with a wavy line represents a bond to another atom.
すなわち、本発明の分解性塗料組成物は、上記本発明のポリマー化合物の分解方法にて説明したポリマー化合物を含むものである。なお、この分解性塗料組成物において、ポリマー化合物は、塗膜を形成させるためのバインダーとして機能する成分となる。したがって、この塗料組成物により形成された塗膜は、窒素酸化物に接触させることで分解し低分子量化する。塗膜を形成するバインダーが分解し低分子量化することにより、塗膜が脆くなり、塗装面から塗膜を容易に除去することができるようになる。なお、窒素酸化物については、上記本発明の分解方法にて述べた通りなので、ここでの説明を省略する。 That is, the decomposable coating composition of the present invention contains the polymer compound described in the above-mentioned method for decomposing a polymer compound of the present invention. In this decomposable coating composition, the polymer compound is a component that functions as a binder for forming a coating film. Therefore, the coating film formed by this coating composition is decomposed and reduced in molecular weight when contacted with nitrogen oxides. The decomposition and reduction in molecular weight of the binder that forms the coating film makes the coating film brittle, making it easier to remove from the painted surface. Note that nitrogen oxides are as described in the above-mentioned method for decomposing the coating film of the present invention, so a description thereof will be omitted here.
本発明の分解性塗料組成物は、バインダーとしての上記ポリマー化合物と顔料と溶剤とを含み、溶剤が蒸発することにより、ポリマー化合物が造膜し塗膜を形成させる。このポリマー化合物が窒素酸化物と接触することにより分解し低分子量化することは既に説明した通りである。 The decomposable coating composition of the present invention contains the above-mentioned polymer compound as a binder, a pigment, and a solvent, and when the solvent evaporates, the polymer compound forms a coating film. As already explained, when this polymer compound comes into contact with nitrogen oxides, it decomposes and becomes a low molecular weight compound.
<塗装面からの塗膜の除去方法>
上記分解性塗料組成物により形成された塗膜を備えた塗装面に窒素酸化物を接触させることを特徴とする塗装面からの塗膜の除去方法もまた、本発明の一つである。これについては、上記分解性接着剤組成物の説明にて既に述べた通りなので、ここでの説明を省略する。
<How to remove paint film from painted surface>
Another aspect of the present invention is a method for removing a paint film from a painted surface, which comprises bringing nitrogen oxide into contact with a painted surface provided with a paint film formed from the above-mentioned decomposable paint composition. Since this has already been described in the description of the decomposable adhesive composition, the explanation here will be omitted.
<繊維強化プラスチックに含まれている繊維を回収する方法>
次に、本発明の繊維強化プラスチックに含まれている繊維を回収する方法について説明する。本発明の繊維強化プラスチックに含まれている繊維を回収する方法は、下記化学式(1)で表す2価の基を備えたポリマー化合物をマトリクスとして含む繊維強化プラスチックに窒素酸化物を接触させることでマトリクスを分解させ、前記繊維強化プラスチックに含まれている繊維を分離回収することを特徴とする。なお、化学式(1)において、波線を付した結合は、他の原子への結合手を表す。
<Method for recovering fibers contained in fiber-reinforced plastics>
Next, a method for recovering fibers contained in a fiber-reinforced plastic of the present invention will be described. The method for recovering fibers contained in a fiber-reinforced plastic of the present invention is characterized in that a fiber-reinforced plastic containing a polymer compound having a divalent group represented by the following chemical formula (1) as a matrix is contacted with nitrogen oxide to decompose the matrix, and the fibers contained in the fiber-reinforced plastic are separated and recovered. In addition, in chemical formula (1), bonds marked with wavy lines represent bonds to other atoms.
繊維強化プラスチック(以下、FRPとも呼ぶ。)は、軽量ではあるものの弾性率が小さく強度の低いプラスチックに、弾性率が大きく、引張強度の高いガラス繊維や炭素繊維等の強化材を組み合わせることで強度を高めた複合材料であり、良好な機械的性質等を示すことから、運輸機器、住宅設備用機器、プ-ル、建材など幅広い分野で用いられている。特に、炭素繊維を強化材とした炭素繊維強化プラスチック(以下、CFRPとも呼ぶ。)は、軽量かつ鋼鉄に匹敵する強度を備えるとされ、自動車や航空機等において従来用いられてきた鋼板を置き換える素材として広く用いられている。 Fiber reinforced plastics (hereafter referred to as FRP) are composite materials that have been strengthened by combining lightweight plastics, which have a low elastic modulus and low strength, with reinforcing materials such as glass fiber or carbon fiber, which have a high elastic modulus and high tensile strength, and exhibit good mechanical properties. As such, they are used in a wide range of fields, including transportation equipment, housing equipment, pools, and building materials. In particular, carbon fiber reinforced plastics (hereafter referred to as CFRP), which use carbon fiber as a reinforcing material, are lightweight and have strength comparable to that of steel, and are widely used as a material to replace the steel plates that have traditionally been used in automobiles, aircraft, etc.
しかしながら、FRPは、その優れた耐久性や強度ゆえに廃棄物処理の問題を生じがちである。また、CFRPに用いられる炭素繊維は、優れた特性を示す一方で非常に高価であり、廃棄されるCFRPから炭素繊維を回収して再利用が可能であれば、環境面でもコスト面でも大変有用である。本発明は、このような要請に応えるものであり、上記化学式(1)で表す2価の基を備えたポリマー化合物をマトリクスとして含むFRPに窒素酸化物を接触させることで、マトリクスであるポリマー化合物を分解して低分子量化させる。低分子量化したマトリクスは容易に崩壊させることができるので、マトリクスの中に含まれている繊維を容易に取り出すことが可能になる。 However, due to its excellent durability and strength, FRP tends to cause waste disposal problems. In addition, while the carbon fibers used in CFRP have excellent properties, they are very expensive. If it were possible to recover and reuse carbon fibers from discarded CFRP, it would be very useful in terms of both the environment and cost. The present invention responds to such demands, and by contacting nitrogen oxide with FRP containing a polymer compound having a divalent group represented by the above chemical formula (1) as a matrix, the polymer compound matrix is decomposed and reduced in molecular weight. The reduced molecular weight matrix can be easily disintegrated, making it possible to easily extract the fibers contained in the matrix.
FRPは、ガラス繊維や炭素繊維等の繊維にマトリクスとなる材料を含浸させ、これを所望の形状に成形した後に硬化させたものであるのが一般的である。こうした繊維としては、ガラス繊維、炭素繊維、アラミド繊維等を挙げることができ、これらの中でも炭素繊維を好ましく挙げることができる。これら繊維としては、繊維が一方向に並んだ一方向材や、平織、綾織、朱子織等の織布材や、不織布材等が例示される。 FRP is generally made by impregnating fibers such as glass fibers or carbon fibers with a matrix material, molding this into a desired shape, and then curing it. Examples of such fibers include glass fibers, carbon fibers, aramid fibers, etc. Among these, carbon fibers are preferred. Examples of these fibers include unidirectional materials in which fibers are arranged in one direction, woven materials such as plain weave, twill weave, and satin weave, and nonwoven materials.
マトリクスを構成するポリマー化合物としては、上記化学式(1)で表す2価の基を備えるものであれば限定されない。このようなポリマー化合物として、エポキシ樹脂の硬化物や、ビニルポリマーの架橋体を好ましく挙げることができる。これらをマトリクスとするFRPは、使用時には十分な耐久性を示す一方で、使用後は窒素酸化物を接触させることによりマトリクスを簡単に除去できる。 The polymer compound constituting the matrix is not limited as long as it has a divalent group represented by the above chemical formula (1). Preferred examples of such polymer compounds include cured products of epoxy resins and crosslinked products of vinyl polymers. FRP with these as a matrix exhibits sufficient durability during use, but after use, the matrix can be easily removed by contacting with nitrogen oxide.
エポキシ樹脂の硬化物は、ポリエポキシ化合物とポリオール化合物とアミンなどの硬化触媒とを含むエポキシ樹脂を硬化させたものである。この硬化前のエポキシ樹脂を上記の繊維に含浸させ、その後、エポキシ樹脂を硬化させることでFRPとなる。 A cured epoxy resin is made by curing an epoxy resin that contains a polyepoxy compound, a polyol compound, and a curing catalyst such as an amine. The fibers are impregnated with this uncured epoxy resin, and then the epoxy resin is cured to produce FRP.
例えば、通常のエポキシ樹脂ではビスフェノ-ルA等のようなビスフェノ-ル化合物がポリオール化合物として使われるが、こうしたビスフェノ-ル化合物の分子内に上記化学式(1)で表す2価の基を導入することを好ましく挙げられる。このようなポリオール化合物については、上記本発明のポリマー化合物の分解方法の説明で述べたものを用いることができる。 For example, in ordinary epoxy resins, bisphenol compounds such as bisphenol A are used as polyol compounds, but by introducing a divalent group represented by the above chemical formula (1) into the molecules of such bisphenol compounds. I would like to mention that. As such a polyol compound, those described in the explanation of the method for decomposing a polymer compound of the present invention can be used.
ビニルポリマーの架橋体は、(A)エチレン性不飽和結合を備えたモノマーと、(B)分子内に上記化学式(1)で表す2価の基を備えた、2以上のエチレン性不飽和結合を有する架橋剤とをラジカル重合させることで得られる。これら(A)と(B)とラジカル重合開始剤とを混合して液状の重合性組成物を調製し、この重合性組成物を繊維に含浸させてから、これを加熱して重合性組成物を硬化させることでFRPとなる。これら、(A)、(B)及びラジカル重合開始剤については、上記本発明のポリマー化合物の分解方法の説明で述べたものを用いることができる。 The crosslinked vinyl polymer is obtained by radical polymerization of (A) a monomer having an ethylenically unsaturated bond and (B) a crosslinking agent having two or more ethylenically unsaturated bonds and a divalent group represented by the above chemical formula (1) in the molecule. These (A) and (B) are mixed with a radical polymerization initiator to prepare a liquid polymerizable composition, which is then impregnated into fibers and heated to harden the polymerizable composition, thereby forming an FRP. As for these (A), (B) and radical polymerization initiator, those described above in the description of the method for decomposing a polymer compound of the present invention can be used.
以下、実施例を示すことにより、さらに具体的に本発明を説明するが、本発明は、以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail by showing Examples, but the present invention is not limited to the following Examples.
・モデル化合物による検証
まずは、ジアシルヒドラジン部位(上記化学式(1)で表す2価の基)を備えたモデル化合物1を用いて、これに窒素酸化物を接触させたときの生成物を調べた。亜硝酸ナトリウム6.911g(0.1002mol)に濃硫酸10mLを少しずつ加え、発生した一酸化窒素と二酸化窒素の混合気体を、アルゴン気流を用いて無水塩化カルシウム管を通して化合物1(0.0309g、0.1029mmol)に20分間吹き付けた。得られた生成物を薄層クロマトグラフィーで展開したところ、化合物1のスポットは消失し、新たに2種類の化合物に対応するスポットが確認された。これらの化合物について1H-NMRスペクトル及びIRスペクトルにて確認したところ、化合物2及び3であることが確認された。このことから、上記化学式(1)で表す2価の基を備えた化合物が、窒素酸化物を接触させることにより分解することを確認した。 First, a model compound 1 having a diacylhydrazine moiety (a divalent group represented by the above chemical formula (1)) was used to investigate the product produced when nitrogen oxide was brought into contact with the model compound 1. 10 mL of concentrated sulfuric acid was added little by little to 6.911 g (0.1002 mol) of sodium nitrite, and the generated gas mixture of nitrogen monoxide and nitrogen dioxide was passed through an anhydrous calcium chloride tube using an argon stream to form compound 1 (0.0309 g, 0.1029 mmol) for 20 minutes. When the obtained product was developed by thin layer chromatography, the spot of compound 1 disappeared, and spots corresponding to two types of compounds were newly confirmed. When these compounds were confirmed by 1 H-NMR spectrum and IR spectrum, they were confirmed to be compounds 2 and 3. From this, it was confirmed that the compound having the divalent group represented by the above chemical formula (1) decomposes when brought into contact with nitrogen oxide.
・ジアクリロイルヒドラジン4の合成
ヒドラジン一水和物20g(0.4mol)と水酸化ナトリウム40g(1mol)を水400mLに溶解させ、この溶液に、0℃で、アクリル酸クロリド80g(0.88mol)をテトラヒドロフラン100mLに溶解させた溶液を30分間かけて滴下した。析出した結晶を濾取し、少量の冷水で洗浄した。濾液は、連続抽出装置を用いて酢酸エチルで抽出し、この抽出液からも結晶を析出させた。得られた結晶を合わせ、真空乾燥することで、40g(収率70%)のジアクリロイルヒドラジン4を無色結晶として得た。 20 g (0.4 mol) of hydrazine monohydrate and 40 g (1 mol) of sodium hydroxide were dissolved in 400 mL of water, and in this solution, 80 g (0.88 mol) of acrylic acid chloride was dissolved in 100 mL of tetrahydrofuran at 0°C. The solution was added dropwise over 30 minutes. The precipitated crystals were collected by filtration and washed with a small amount of cold water. The filtrate was extracted with ethyl acetate using a continuous extraction device, and crystals were also precipitated from this extract. The obtained crystals were combined and vacuum dried to obtain 40 g (yield 70%) of diacryloylhydrazine 4 as colorless crystals.
・アクリル系硬化物の調製とその分解反応
N,N-ジメチルアクリルアミド(DMA)と、上記の手順で合成したジアクリロイルヒドラジン4と、2,2’-アゾビスイソブチロニトリル(AIBN)とを、モル比で95:5:2となるように混合して重合性組成物を調製した。この重合性組成物を基板に塗布してから100℃で加熱することで、基板上に硬化膜を形成させた。得られた硬化膜に、上記と同様の手順で調製した一酸化窒素と二酸化窒素の混合気を20分間接触させたところ、その硬化膜が脆くなり、少しの力を加えただけで粉々になった。
Preparation of acrylic cured material and its decomposition reaction A polymerizable composition was prepared by mixing N,N-dimethylacrylamide (DMA), diacryloylhydrazine 4 synthesized by the above procedure, and 2,2'-azobisisobutyronitrile (AIBN) in a molar ratio of 95:5:2. This polymerizable composition was applied to a substrate and then heated at 100°C to form a cured film on the substrate. When the obtained cured film was contacted with a mixture of nitric oxide and nitrogen dioxide prepared by the same procedure as above for 20 minutes, the cured film became brittle and was broken into pieces by the application of even a small force.
・エポキシ系硬化物の調製とその分解とその分解反応
特開2011-236381号公報の段落0054~0057の手順に従って、下記化学式で示す1,2-ビス[3-(4-ヒドロキシフェニル)プロパニル]ヒドロシン(化合物5)を得た。
ビスフェノールA型エポキシ樹脂(Epon828、Shell社製、エポキシ当量184~194)50質量部、ビスフェノールF型エポキシ樹脂(830LVP、大日本イ
ンキ化学工業株式会社製、エポキシ当量163)50質量部、化合物5を80質量部、イミダゾール5質量部、シリカフィラー(シリカアエロジールR972、日本アエロジル社製)3質量部、チクソ剤(ステリアリン酸アミド)2質量部、及びシリコーンカップリング剤(KBM803、信越化学工業株式会社製)1質量部を混合し、エポキシ樹脂組成物を調製した。このエポキシ樹脂組成物を基板に塗布してから180℃で加熱することで、基板上に硬化膜を形成させた。得られた硬化膜に、上記と同様の手順で調製した一酸化窒素と二酸化窒素の混合気を20分間接触させたところ、その硬化膜が脆くなり、少しの力を加えただけで粉々になった。
An epoxy resin composition was prepared by mixing 50 parts by mass of bisphenol A type epoxy resin (Epon 828, Shell, epoxy equivalent 184-194), 50 parts by mass of bisphenol F type epoxy resin (830LVP, Dainippon Ink & Chemicals, epoxy equivalent 163), 80 parts by mass of compound 5, 5 parts by mass of imidazole, 3 parts by mass of silica filler (Silica Aerosil R972, Nippon Aerosil), 2 parts by mass of a thixotropic agent (steric acid amide), and 1 part by mass of a silicone coupling agent (KBM803, Shin-Etsu Chemical Co., Ltd.). This epoxy resin composition was applied to a substrate and then heated at 180°C to form a cured film on the substrate. The obtained cured film was contacted with a mixture of nitric oxide and nitrogen dioxide prepared by the same procedure as above for 20 minutes, and the cured film became brittle and was broken into pieces by applying only a small force.
以上に示す通り、上記化学式(1)で表す2価の基を備えたポリマー化合物、すなわちポリ(ジアシルヒドラジン)は、窒素酸化物と接触させることにより分解して、容易に除去可能なものになることがわかる。 As shown above, it can be seen that the polymer compound having a divalent group represented by the above chemical formula (1), i.e., poly(diacylhydrazine), decomposes when contacted with nitrogen oxides, becoming easily removable.
・ポリジアシルヒドラジンの合成
ジヒドラジド6(2.50g、10.0mmol)のジメチルホルムアミド(DMF;10mL)溶液にテレフタル酸クロリド7(2.03g、10.0mmol)を加え、空気に触れないように栓をして2時間撹拌した。得られた溶液にDMF(40mL)を加えて薄め、激しく撹拌しながらメタノール(500mL)に注ぎ、生じた沈殿を濾過してからメタノールでよく洗浄し、真空乾燥することでポリジアシルヒドラジン8を得た。 Add terephthalic acid chloride 7 (2.03 g, 10.0 mmol) to a solution of dihydrazide 6 (2.50 g, 10.0 mmol) in dimethylformamide (DMF; 10 mL), cover with a stopper to prevent exposure to air, and stir for 2 hours. did. The resulting solution was diluted by adding DMF (40 mL), poured into methanol (500 mL) with vigorous stirring, the resulting precipitate was filtered, washed well with methanol, and dried under vacuum to obtain polydiacylhydrazine 8. Ta.
・ポリジアシルヒドラジンの分解
ポリジアシルヒドラジン8の粉末に上記と同様の手順で調製した一酸化窒素と二酸化窒素の混合気を1時間接触させた。生成物は見かけ上変化がないが、メタノールに完全に溶解した。ポリジアシルヒドラジン8はメタノールに不溶であることから、ポリジアシルヒドラジン8が低分子化合物にまで分解していることを確認した。
- Decomposition of polydiacylhydrazine A mixture of nitrogen monoxide and nitrogen dioxide prepared in the same manner as above was brought into contact with the powder of polydiacylhydrazine 8 for 1 hour. The product was apparently unchanged but completely dissolved in methanol. Since polydiacylhydrazine 8 is insoluble in methanol, it was confirmed that polydiacylhydrazine 8 was decomposed into low molecular weight compounds.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022150423 | 2022-09-21 | ||
JP2022150423 | 2022-09-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2024045015A true JP2024045015A (en) | 2024-04-02 |
Family
ID=90479650
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2023126777A Pending JP2024045015A (en) | 2022-09-21 | 2023-08-03 | A method for decomposing a polymer compound, a degradable adhesive composition and a method for separating a bonded body using the same, a degradable paint composition and a method for removing a coating film using the same, and a method for removing fibers contained in fiber-reinforced plastics. How to collect |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2024045015A (en) |
-
2023
- 2023-08-03 JP JP2023126777A patent/JP2024045015A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8217096B2 (en) | Photocurable pressure-sensitive adhesive composition | |
KR100436804B1 (en) | Energy active salt with fluorocarbon anion | |
JP2007055993A5 (en) | ||
ES2588021T3 (en) | Impact resistance enhancing agent for epoxy resin compositions | |
WO2005087822A1 (en) | Liquid composition containing no solvent | |
JP2003183348A (en) | Curable compound and curable resin composition containing it | |
TW201704394A (en) | Cured body, electronic component, display element, and light-/moisture-curable resin composition | |
TW201604651A (en) | Photo/moisture-curable resin composition, adhesive for electronic component, and adhesive for display element | |
TW200835707A (en) | A Resin containing oxetane, an adhesive and a resist made from the resin | |
KR20150103068A (en) | Polymerizable composition including a benzoxazine and an acid-forming peroxide catalyst, article, and method | |
JP2007177203A (en) | Phosphorus-containing polymer, resin composition using it, prepreg, metal-clad laminate, sealant, photosensitive film, forming process for resist pattern, and printed wiring board | |
JP2024045015A (en) | A method for decomposing a polymer compound, a degradable adhesive composition and a method for separating a bonded body using the same, a degradable paint composition and a method for removing a coating film using the same, and a method for removing fibers contained in fiber-reinforced plastics. How to collect | |
JP4532330B2 (en) | Polyurethane acrylate and process for producing the same | |
JP2615375B2 (en) | Surface modified gas separation membrane and method for producing the same | |
JP5614389B2 (en) | Resin composition, prepreg, metal-clad laminate, sealing material, photosensitive film, resist pattern forming method and printed wiring board | |
JPH05331366A (en) | Curable composition and method for curing the same | |
JP5074046B2 (en) | Multi-branched urethane compound and method for producing the same | |
JP2950299B2 (en) | Method for producing highly heat-resistant epoxy resin composition containing benzyl-containing quinoxalinium salt | |
KR20190008547A (en) | Base generator, tester, organic salt, composition, manufacturing method of device, cured film and device | |
JPH1180595A (en) | Resin composition and varnish and their application | |
JPH10139860A (en) | Epoxy resin hardner | |
JP3456265B2 (en) | Manufacturing method of thermosetting resin | |
JP2023122265A (en) | Fiber-reinforced plastic and method for recovering fiber included therein | |
JP6057120B2 (en) | Resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method | |
KR102600082B1 (en) | Composition for organic flame retardant compounds and method for manufacturing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A80 | Written request to apply exceptions to lack of novelty of invention |
Free format text: JAPANESE INTERMEDIATE CODE: A80 Effective date: 20230804 |