CN115368814A - Modified cellulose-based strippable film detergent and preparation method thereof - Google Patents
Modified cellulose-based strippable film detergent and preparation method thereof Download PDFInfo
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- CN115368814A CN115368814A CN202210764002.2A CN202210764002A CN115368814A CN 115368814 A CN115368814 A CN 115368814A CN 202210764002 A CN202210764002 A CN 202210764002A CN 115368814 A CN115368814 A CN 115368814A
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- modified cellulose
- film
- cellulose
- decontamination
- detergent
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 77
- 239000001913 cellulose Substances 0.000 title claims abstract description 77
- 239000003599 detergent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005202 decontamination Methods 0.000 claims abstract description 47
- 230000003588 decontaminative effect Effects 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 230000002285 radioactive effect Effects 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000011109 contamination Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000007872 degassing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003904 radioactive pollution Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyoxypropylene glycerol Polymers 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 5
- 239000000020 Nitrocellulose Substances 0.000 claims description 5
- 244000269722 Thea sinensis Species 0.000 claims description 5
- 229920001220 nitrocellulos Polymers 0.000 claims description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 239000004579 marble Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- IKMDFBPHZNJCSN-UHFFFAOYSA-N Myricetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC(O)=C(O)C(O)=C1 IKMDFBPHZNJCSN-UHFFFAOYSA-N 0.000 claims description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 235000007743 myricetin Nutrition 0.000 claims description 3
- 229940116852 myricetin Drugs 0.000 claims description 3
- PCOBUQBNVYZTBU-UHFFFAOYSA-N myricetin Natural products OC1=C(O)C(O)=CC(C=2OC3=CC(O)=C(O)C(O)=C3C(=O)C=2)=C1 PCOBUQBNVYZTBU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 3
- PJNMPPJFADRLBM-UHFFFAOYSA-N 1,1,1,2-tetrafluoro-4-(3,4,4,4-tetrafluorobutoxy)butane Chemical compound FC(F)(F)C(F)CCOCCC(F)C(F)(F)F PJNMPPJFADRLBM-UHFFFAOYSA-N 0.000 claims description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 240000006409 Acacia auriculiformis Species 0.000 claims description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 13
- 230000001680 brushing effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 241001478802 Valonia Species 0.000 description 1
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a modified cellulose-based strippable film detergent and a preparation method thereof, belonging to the technical field of radioactive contamination removal. Adding the modified cellulose, the decontamination assistant and the film-forming assistant into a solvent, stirring and dissolving, uniformly mixing, and performing ultrasonic degassing treatment to obtain the modified cellulose-based strippable detergent. And spraying, brushing and coating the decontaminating agent on the surface of the material with radioactive contamination, naturally drying, curing to form a film, and then stripping to finish the decontaminating process. The modified cellulose-based strippable film detergent prepared by the method is used in an environment of-30 ℃, and the single-time decontamination efficiency can reach 99% at most; the tensile strength of the decontamination film reaches 20-65 MPa. The strippable membrane detergent has good applicability at low temperature, high drying and curing speed and high decontamination efficiency, and realizes the pressing decontamination of radioactive contaminated surfaces.
Description
Technical Field
The invention relates to a modified cellulose-based strippable membrane detergent and a preparation method thereof, belonging to the technical field of radioactive contamination removal and being used for removing surface-contaminated radionuclides.
Background
Decontamination plays an extremely important role in the decommissioning of nuclear facilities and the treatment of nuclear emergency radioactive contamination, and the application of the surface radioactive contamination decontaminating agent and decontamination technology has important significance for ecological environment protection and human health. The strippable membrane decontamination technology has a plurality of technologies, wherein the strippable membrane decontamination technology has certain advantages in a plurality of technical means by the advantages of high decontamination rate, suppression effect on pollutants, prevention of secondary diffusion of the pollutants, less generated wastes, simple operation, capability of mechanical operation and the like. However, most of the existing strippable detergents and decontamination technologies are used at normal temperature, and the problems of poor spraying property, long curing film forming time, radioactive pollution suppression (or control), low decontamination efficiency, poor mechanical property and the like exist under the low-temperature cold condition (below-30 ℃ below), the environmental radioactive pollution control and decontamination requirements in cold regions cannot be met, and the strippable detergents and decontamination technologies are difficult to popularize and apply in the radioactive pollution decontamination of the surfaces in the low-temperature cold regions. Therefore, aiming at the characteristics of radioactive pollution control and decontamination in cold regions, the cellulose raw material selected by the invention develops the modified cellulose-based strippable membrane decontaminating agent which can be sprayed, quickly cured to form a membrane and decontaminate the surface radionuclide pollution with high strength in a low-temperature environment through chemical modification, compound decontamination auxiliary agent, film-forming auxiliary agent and the like, is low in cost, high in efficiency and degradable, is convenient to recover and reduces secondary pollution.
The biomass such as the cellulose and the derivatives thereof belongs to non-petrochemical resources, has the characteristics of rich resources, renewability, environmental protection and degradability, but the cellulose and the derivatives thereof have long film forming time at low temperature and poor film mechanical property, and are limited in the application of strippable fouling films. Therefore, the invention improves the decontamination rate, low-temperature fluidity, spraying property, film forming property and mechanical strength of the decontaminating agent by carrying out esterification crosslinking modification on cellulose and compounding the decontaminating auxiliary agent, shortens the curing time, overcomes the defect of the application of the existing strippable film decontaminating agent at low temperature, enlarges the application range, and realizes the creation and application of the high-strength modified cellulose-based strippable film decontaminating agent which can be quickly cured to form a film at low temperature.
Disclosure of Invention
The invention aims to provide a modified cellulose-based strippable film detergent and a preparation method thereof aiming at the characteristics of radioactive pollution control and decontamination in cold regions, wherein cellulose is selected as a film forming raw material, and a decontamination assistant, a film forming assistant and the like are chemically modified and compounded.
According to the technical scheme adopted by the invention, the modified cellulose-based strippable film detergent comprises the following raw materials in parts by weight:
3 to 25 portions of modified cellulose
0.1 to 3 portions of decontamination auxiliary agent
0.1 to 1 portion of film forming additive
100 portions of solvent
The modified cellulose is more than one of ethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and nitrocellulose;
the decontamination auxiliary agent is more than one of tea polyphenol, myricetin, gallic acid, valonia extract, tannic acid, black wattle extract, citric acid, aspartic acid and glutamic acid;
the film forming auxiliary agent is more than one of glycerol, span 20, diethyl phthalate, castor oil, tween 80, emulsified silicone oil, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene ethylene oxide glycerol ether;
the solvent is one or more of ethyl acetate, ethanol, hydrofluoroether and acetone.
The preparation method of the modified cellulose strippable membrane detergent comprises the following steps:
step one, dissolving
Dissolving cellulose in a solvent according to the weight ratio of 1-4: 3-20 to form a cellulose solution;
step two, modification
Heating the cellulose solution to 40-60 ℃, adding isocyanate and 0.01-0.05 part of dibutyltin dilaurate catalyst into the cellulose solution according to the ratio of 2-3: 1-7, reacting for 1-5 h, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying at 100-150 ℃ for 2-8 h to obtain a modified cellulose product;
step three, preparation of detergent
Adding 3-25 parts of modified cellulose, 0.1-3 parts of decontamination assistant and 0.1-1 part of film-forming assistant into 100 parts of solvent by weight, stirring and dissolving for 5-24 h, mixing uniformly, and performing ultrasonic 40kHZ degassing treatment for 0.2-1 h to obtain the strippable film decontaminating agent.
The isocyanate is more than one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
The volume ratio of the solvents of ethyl acetate, ethanol, hydrofluoroether and acetone is 1-10: 0-5: 0-3.
The hydrofluoroether is more than one of 1, 2-tetrafluoroethylethyl ether and 1, 2-tetrafluoroethylethyl-2, 2-trifluoroethyl ether.
The using method of the detergent comprises the following steps:
spraying a decontaminating agent on the surface of a material with radioactive contamination at the temperature of-30 to 30 ℃, drying and curing to form a film for 0.5 to 6 hours, and then stripping the film to finish the decontaminating process;
the material with radioactive pollution is metal, plastic, quartz glass, organic glass, ceramic tile, alkyd paint plate, marble or cement.
The invention has the beneficial effects that:
(1) The modified cellulose detergent is modified aiming at the defects of poor film forming stripping performance, low mechanical property and the like of cellulose in a low-temperature environment, a cellulose molecular chain contains a large amount of hydroxyl, and isocyanate-NCO is adopted to perform a crosslinking reaction with the hydroxyl, so that cellulose macromolecular chains are connected together to form a crosslinked network structure, the mechanical property after film forming is improved, the film body stripping performance is improved, and the decontamination efficiency is improved.
(2) The prepared strippable film detergent is added with a film forming additive, so that the detergent has the characteristics of good flowability, strong spraying performance, short curing and film forming time, excellent film forming performance, high mechanical strength of a film, good strippable performance and the like in a low-temperature environment.
(3) The addition of the decontamination auxiliary agents such as tea polyphenol, citric acid, aspartic acid and the like in the prepared decontaminating agent increases a large number of reactive sites, and comprehensively improves the decontamination rate of the strippable membrane decontaminating agent on radioactive pollution. The structure of the decontamination auxiliary agent such as tea polyphenol, citric acid, aspartic acid and the like contains various active groups, such as phenolic hydroxyl, carboxyl, amino and the like, and can generate chelation reaction with heavy metal ions and radioactive nuclide to form a complex or chelate so as to achieve the purpose of removing the radioactive nuclide.
(4) The raw material of the strippable membrane detergent mainly comprises modified cellulose, the solvent mainly comprises ethyl acetate, absolute ethyl alcohol, hydrofluoroether and acetone, and the strippable membrane is stripped after the detergent forms a membrane and decontaminates. The strippable film has a certain suppression effect on radioactive pollution, can prevent secondary diffusion of the radioactive pollution, is convenient for mechanical recovery of a high-strength film body, can be partially degraded, is convenient for sealing, storing and curing treatment, reduces secondary pollution, and meets the requirement of green sustainable development.
The preparation and use methods of the high-strength modified cellulose-based strippable film detergent provided by the invention have the advantages that the raw material cost of each component is low, the detergent can be cured to form a film within 0.5-6 h at the ambient temperature of-30 ℃, the mechanical property of the film body can reach 65MPa to the maximum, the mechanical stripping and the recovery after stripping are facilitated, and the secondary pollution is avoided. And the detergent has simple preparation process and wide raw material sources. The decontamination rate of the surface radioactive pollution by adopting the high-strength modified cellulose-based strippable membrane decontaminating agent provided by the invention reaches up to 99 percent, thereby achieving the purpose of efficiently decontaminating the surface radioactive pollution.
Drawings
FIG. 1 shows the decontamination rate and film formation time of modified cellulose-based strippable stain removers for radioactive contamination of different surfaces at different temperatures
In the figure: 96339632j for detergency ratio, 9632j for film forming time;
the ordinate (left) is the detergency, in%; the ordinate (right) is the film forming time in units h;
the abscissa is the contaminated substrate, respectively.
FIG. 2 is a comparison of mechanical properties of the modified cellulose-based strippable detergent after film formation with those of pure cellulose after film formation
In the figure: -delta-pure cellulose, -a-tangle-solidup-a-strippable membrane detergent;
the ordinate is tensile strength in MPa; the abscissa is the elongation at break in%.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The modified cellulose is prepared by dissolving nitrocellulose and cellulose acetate butyrate (mass ratio is 1: 1) in a mixed solvent of ethyl acetate and ethanol according to a ratio of 3: 11, stirring the dissolved cellulose solution in a three-neck flask with a condenser, heating to 50 ℃, adding isophorone diisocyanate and 0.01 part of dibutyltin dilaurate catalyst into a four-neck flask according to a ratio of 2: 5, reacting for 5 hours, cooling, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying in a vacuum oven at 130 ℃ for 8 hours to obtain the modified cellulose or the modified cellulose.
Adding 18 parts of modified cellulose into 100 parts of solvent according to the parts by weight, stirring and dissolving for 24 hours, adding 2 parts of polyvinyl acetate, 1 part of tea polyphenol, 0.01 part of polyoxypropylene ethylene oxide glycerol ether and 0.01 part of glycerol into the solution, stirring and dissolving for 0.5-10 hours, and carrying out ultrasonic degassing treatment for 1 hour to obtain the detergent. The solvent is ethyl acetate, absolute ethyl alcohol and hydrofluoroether in a ratio of 3: 1.
The using method comprises the following steps: spraying the modified cellulose-based strippable detergent on the surface of a material with radioactive contamination at the temperature of-30 ℃, drying and curing the material at the temperature of-30 ℃ to form a film for 6 hours, and then stripping the film to finish the decontamination process.
Example 2
The modified cellulose is prepared by stirring and dissolving cellulose acetate and ethyl cellulose (the mass ratio is 2: 1) in a mixed solvent of ethyl acetate and ethanol according to the ratio of 4: 19, filling the dissolved cellulose solution into a three-neck flask with a condenser pipe, heating to 50 ℃, adding isophorone diisocyanate and 0.04 part of dibutyltin dilaurate catalyst into a four-neck flask according to the ratio of 3: 7, reacting for 3 hours, cooling, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying in a vacuum oven at 120 ℃ for 6 hours to obtain a modified cellulose product.
Adding 13 parts by weight of modified cellulose into 100 parts by weight of solvent, stirring and dissolving for 20 hours, then adding 0.8 part of nitric acid, 1.2 parts of hydrogen peroxide decontamination auxiliary agent and 0.08 part of polyoxypropylene ethylene oxide glycerol ether into the solution, stirring and dissolving for 8 hours, and carrying out ultrasonic degassing treatment for 1 hour to obtain the decontaminating agent. The solvent is ethyl acetate, absolute ethyl alcohol and hydrofluoroether with the ratio of 3: 0.5: 1: 0.5.
The using method comprises the following steps: spraying the modified cellulose-based strippable detergent on the surface of a material with radioactive contamination at the temperature of minus 20 ℃, drying and curing the material at the temperature of minus 20 ℃ to form a film for 5 hours, and then stripping the film to finish the decontamination process.
Example 3
The modified cellulose is prepared by stirring and dissolving cellulose acetate propionate and nitrocellulose (mass ratio is 1: 1) in a mixed solvent of ethyl acetate and ethanol according to the ratio of 2: 13, filling the dissolved cellulose solution into a three-neck flask with a condenser pipe, heating to 45 ℃, adding isophorone diisocyanate and 0.02 part of dibutyltin dilaurate catalyst into a four-neck flask according to the ratio of 2: 7, reacting for 3 hours, cooling, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying in a vacuum oven at 130 ℃ for 5 hours.
Adding 10 parts by weight of modified cellulose into 100 parts by weight of solvent, stirring and dissolving for 16 hours, then adding 0.5 part of potassium permanganate, 1.5 parts of myricetin, 0.05 part of span 20 and diethyl phthalate into the solution, stirring and dissolving for 5 hours, and carrying out ultrasonic degassing treatment for 0.5 hour to obtain the detergent. The solvent is ethyl acetate, absolute ethyl alcohol and hydrofluoroether with the ratio of 1.5: 0.5.
The using method comprises the following steps: the modified cellulose base strippable detergent is sprayed on the surface of a material with radioactive contamination at 0 ℃, and is dried and solidified into a film at 0 ℃ for 2 hours, and then the film is stripped, so that the decontamination process is completed.
Example 4
The modified cellulose is prepared by stirring and dissolving cellulose acetate butyrate in a mixed solvent of ethyl acetate and ethanol according to the ratio of 1: 10, loading a dissolved cellulose solution into a three-neck flask with a condensing tube, heating to 50 ℃, adding isophorone diisocyanate and 0.01 part of dibutyltin dilaurate catalyst into a four-neck flask according to the ratio of 3: 5, reacting for 4 hours, cooling, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying in a vacuum oven at 100 ℃ for 6 hours to obtain a modified cellulose product.
Adding 8 parts by weight of modified cellulose into 100 parts by weight of solvent, stirring and dissolving for 13 hours, then adding 3 parts by weight of polyvinyl acetate, 0.05 part by weight of emulsified silicone oil and 0.05 part by weight of polyoxyethylene polyoxypropylene ether into the solution, stirring and dissolving for 4 hours, and carrying out ultrasonic degassing treatment for 1 hour to obtain the detergent. The solvent is ethyl acetate, anhydrous alcohol, hydrofluoroether and acetone at a ratio of 1: 1.
The using method comprises the following steps: the modified cellulose base strippable detergent is sprayed on the surface of a material with radioactive contamination at 10 ℃, and is dried and solidified into a film at 10 ℃ for 0.5h, and then the film is stripped, thus completing the decontamination process.
Example 5
The modified cellulose is prepared by stirring and dissolving ethyl cellulose and nitrocellulose (mass ratio is 1: 1) in a mixed solvent of ethyl acetate and ethanol according to the proportion of 3: 11, filling the dissolved cellulose solution into a three-neck flask with a condenser pipe, heating to 40 ℃, adding isophorone diisocyanate and 0.03 part of dibutyltin dilaurate catalyst into a four-neck flask according to the proportion of 2: 5, reacting for 2 hours, cooling, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying in a vacuum oven at 100 ℃ for 4 hours to obtain a modified cellulose product.
Adding 11 parts by weight of modified cellulose into 100 parts by weight of solvent, stirring and dissolving for 9 hours, then adding 2.5 parts by weight of polyvinyl acetate and 0.1 part by weight of polyoxypropylene glycerol ether into the solution, stirring and dissolving for 4 hours, and carrying out ultrasonic degassing treatment for 1 hour to obtain the detergent. The solvent is ethyl acetate and hydrofluoroether in a ratio of 1: 1.
The using method comprises the following steps: the modified cellulose base strippable detergent is sprayed on the surface of a material with radioactive contamination at the temperature of 30 ℃, and after being dried and cured into a film for 0.5 hour at the temperature of 30 ℃, the film is stripped, and the decontamination process is finished.
The modified cellulose-based peelable type detergents prepared in examples 1 to 5 were verified for their stain removal efficiency by the method comprising:
decontamination of U (VI) contaminated panel surfaces:
cloth dyeing: spreading appropriate amount of uranyl nitrate powder on 10cm-10cm plate (stainless steel plate SS, ceramic plate CT, glass plate GP, plastic plate PE, marble MA, cement CE), and standing for 7 days to obtain contaminated sample plate;
decontamination: respectively spraying the modified cellulose-based strippable detergent prepared in the examples 1 to 5 on the polluted sample plate, forming a film at the temperature corresponding to the examples, and stripping the film to finish the decontamination process;
testing the contaminated sample plate by using a BH2306 alpha and beta surface contamination measuring instrument;
firstly, 6 samples (stainless steel plate SS, ceramic plate CT, glass plate GP, plastic plate PE, marble MA, cement CE) to be polluted are tested by a surface pollution tester (BH 2306 alpha, beta)Background value, average value of 10 tests and recorded as A 0 The method comprises the following steps of uniformly dropwise adding a 2mL uranyl nitrate solution with the concentration of 5g/L on four materials to-be-polluted plates, naturally drying the plates to obtain a uranium pollution sample plate, measuring the pollution radioactive pollution value of the pollution sample plate by using a pollution tester, testing for 10 times, taking an average value, and recording the average value as A 1 . Measuring the residual pollution value of the decontaminated plate, taking an average value A after 10 times of tests 2 . And calculating the decontamination rate. The formula for calculating the detergency ratio is as follows:
(wherein A is 0 Is the background value, A 1 Is the radioactive contamination value before decontamination, A 2 Is the value of radioactive contamination remaining after decontamination).
Wherein, the decontamination rate results are shown in table 1; the corresponding film formation times are shown in table 2;
table 1 example stain removal efficiency on different panels
Table 2 examples film formation times on different panels
TABLE 3 mechanical Properties of the examples
| Examples | Tensile strength MPa | Elongation at break% |
| 1 | 55.89 | 15.17 |
| 2 | 61.46 | 17.73 |
| 3 | 65.00 | 20.49 |
| 4 | 64.21 | 18.22 |
| 5 | 63.68 | 17.95 |
As can be seen from tables 1,2 and 3, the modified cellulose-based strippable detergent prepared by the invention has a decontamination rate of more than 90 percent for radioactive contamination on the surfaces of different materials, the highest single time can reach more than 99 percent, the highest tensile strength can reach 65MPa, and the curing film-forming time is 0.5-6 h. Therefore, the modified cellulose base strippable detergent is fast in curing and film forming, good in spraying performance and film forming performance and short in film forming time under the low-temperature condition; the decontamination film has high mechanical strength and the film body is easy to peel; the decontamination efficiency is high.
Claims (6)
1. The modified cellulose-based strippable film detergent is characterized by comprising the following raw materials in parts by weight:
the modified cellulose is more than one of ethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and nitrocellulose;
the decontamination auxiliary agent is more than one of tea polyphenol, myricetin, gallic acid, valonea extract, tannic acid, black wattle extract, citric acid, aspartic acid and glutamic acid;
the film forming auxiliary agent is more than one of glycerol, span 20, diethyl phthalate, castor oil, tween 80, emulsified silicone oil, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene ethylene oxide glycerol ether;
the solvent is one or more of ethyl acetate, ethanol, hydrofluoroether and acetone.
2. The modified cellulose-based peelable film stain remover according to claim 1, wherein the modified cellulose-based peelable film stain remover is prepared by the following steps:
step one, dissolving
Dissolving cellulose in a solvent according to the weight ratio of 1-4: 3-20 to form a cellulose solution;
step two, modification
Heating the cellulose solution to 40-60 ℃, adding isocyanate and 0.01-0.05 part of dibutyltin dilaurate catalyst into the cellulose solution according to the ratio of 2-3: 1-7, reacting for 1-5 h, precipitating with isoamyl alcohol, washing with toluene, and vacuum drying at 100-150 ℃ for 2-8 h to obtain a modified cellulose product;
step three, preparation of detergent
Adding 3-25 parts by weight of modified cellulose, 0.1-3 parts by weight of decontamination assistant and 0.1-1 part by weight of film forming assistant into 100 parts by weight of solvent, stirring and dissolving for 5-24 hours, mixing uniformly, and performing ultrasonic 40kHZ degassing treatment for 0.2-1 hour to obtain the strippable film decontaminating agent.
3. The modified cellulose-based peelable film stain remover according to claim 2, wherein the isocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate.
4. The modified cellulose-based peelable film detergent of claim 1, wherein the volume ratio of the solvents ethyl acetate, ethanol, hydrofluoroether and acetone is 1-10: 0-5: 0-3.
5. The modified cellulose-based peelable film stain remover according to claim 4, wherein the hydrofluoroether is one or more of 1, 2-tetrafluoroethylethyl ether, 1, 2-tetrafluoroethylethyl-2, 2-trifluoroethyl ether.
6. The modified cellulose-based peelable film stain remover according to claim 1, wherein the stain remover is used by the steps of:
spraying a decontaminating agent on the surface of a material with radioactive contamination at the temperature of-30 to 30 ℃, drying and curing to form a film for 0.5 to 6 hours, and then stripping the film to finish the decontaminating process;
the material with radioactive pollution is metal, plastic, quartz glass, organic glass, ceramic tile, alkyd paint plate, marble or cement.
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