WO1996007631A1 - Procede d'inhibition de la polymerisation d'un compose vinylique - Google Patents
Procede d'inhibition de la polymerisation d'un compose vinylique Download PDFInfo
- Publication number
- WO1996007631A1 WO1996007631A1 PCT/JP1995/001705 JP9501705W WO9607631A1 WO 1996007631 A1 WO1996007631 A1 WO 1996007631A1 JP 9501705 W JP9501705 W JP 9501705W WO 9607631 A1 WO9607631 A1 WO 9607631A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- vinyl compound
- compound
- polymerization
- acrylic acid
- Prior art date
Links
- -1 vinyl compound Chemical class 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 30
- 230000002401 inhibitory effect Effects 0.000 title abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 17
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical group [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 claims description 14
- 230000003405 preventing effect Effects 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000004715 keto acids Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 7
- 150000003751 zinc Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 32
- 230000004580 weight loss Effects 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- NFIDBGJMFKNGGQ-UHFFFAOYSA-N 2-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC=C1O NFIDBGJMFKNGGQ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- WRXVHXSRUCNYKK-UHFFFAOYSA-N CCCC1C(=CSS1)C Chemical compound CCCC1C(=CSS1)C WRXVHXSRUCNYKK-UHFFFAOYSA-N 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical group CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- ICQFAQGXJAVDED-UHFFFAOYSA-N benzene-1,4-diol;4-(methylamino)phenol Chemical compound OC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ICQFAQGXJAVDED-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- CRBWLPLGQBCCCY-UHFFFAOYSA-L copper;dicarbamate Chemical compound [Cu+2].NC([O-])=O.NC([O-])=O CRBWLPLGQBCCCY-UHFFFAOYSA-L 0.000 description 1
- WIIJVOHQGQETTP-UHFFFAOYSA-L copper;n,n-dihexylcarbamodithioate Chemical compound [Cu+2].CCCCCCN(C([S-])=S)CCCCCC.CCCCCCN(C([S-])=S)CCCCCC WIIJVOHQGQETTP-UHFFFAOYSA-L 0.000 description 1
- BTSJZPQOSLORGE-UHFFFAOYSA-L copper;n,n-dipentylcarbamodithioate Chemical compound [Cu+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC BTSJZPQOSLORGE-UHFFFAOYSA-L 0.000 description 1
- OTVBXFQXYAYGEX-UHFFFAOYSA-L copper;n,n-diphenylcarbamodithioate Chemical compound [Cu+2].C=1C=CC=CC=1N(C(=S)[S-])C1=CC=CC=C1.C=1C=CC=CC=1N(C(=S)[S-])C1=CC=CC=C1 OTVBXFQXYAYGEX-UHFFFAOYSA-L 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-N dibutyldithiocarbamic acid Chemical compound CCCCN(C(S)=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-N 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- WGMRJSBTYSJRKK-UHFFFAOYSA-N ethyl n-butylcarbamodithioate Chemical compound CCCCNC(=S)SCC WGMRJSBTYSJRKK-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PGUWOWZKJZKUGN-UHFFFAOYSA-N methyl n-ethylcarbamodithioate Chemical compound CCNC(=S)SC PGUWOWZKJZKUGN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
Definitions
- the present invention relates to a method for preventing polymerization of a vinyl compound, and more particularly, to a distillation system in a process for producing a vinyl compound, particularly acrylic acid / methacrylic acid.
- the present invention relates to a method for preventing polymerization of a vinyl compound, which effectively suppresses the polymerization, prevents corrosion of equipment, and enables stable long-term continuous operation. Background art
- vinyl compounds such as styrene, acrylinoleic acid, methacrylic acid, ester acrylate acrylate, and acrylonitrile have been used for light or light. It is known that it has the property of being easily polymerized by heat or the like.
- various distillation operations are performed in order to separate, collect, concentrate, or purify a desired vinyl compound.
- the vinyl compound is polymerized by light or heat to form a polymer-like substance as described above, various troubles are caused in the distillation step, and the vinyl compound is prolonged. It is easy to cause unfavorable situations such as making stable continuous operation impossible for a period.
- a method of performing a distillation operation in the presence of a polymerization inhibitor has been employed.
- the polymerization inhibitor include hydroquinone and methoquinone (p-methoxyphenol).
- P-t-butyl catechol, t-butyl hydroquinone And phenothiazine are used.
- Acrylinoleic acid, methacrylic acid, etc. are very easily polymerizable compounds, and these polymerization inhibitors always provide a sufficient effect. The fact is that it has not been done.
- copper dibutyldithiocarbamate is a compound that can extremely effectively prevent the polymerization of acrylic acid and methacrylic acid in the liquid phase.
- it has fatal drawbacks such as corrosion of equipment (for example, material SUS316), and has been difficult to use in industrialized plants.
- An object of the present invention is to provide a method for preventing polymerization of vinyl compounds, which prevents equipment corrosion and enables stable continuous operation for a long period of time.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, focused on an excellent polymerization preventing effect of a metal salt of dithiocarbamate represented by copper dibutyldithiocarbamate. It has been found that the purpose can be achieved by using water and a specific corrosion inhibitor such as water. The present invention has been completed based on such findings.
- the present invention relates to preventing polymerization of a vinyl compound by using a dithiocarbamic acid metal salt in a vinyl compound production process.
- the present invention relates to preventing polymerization of a bullet compound by using a metal dithiocarbamate in a process for producing a vinyl compound, and (a) an alcohol together with a metal dithiocarbamate.
- the present invention also provides a method for preventing polymerization of a vinyl compound.
- Examples of the vinyl compound to which the method of the present invention can be applied include styrene acrylate, methacrylate, acrylate, methacrylate, and acrylate. Among them, acrylonitrile and methacrylic acid are particularly preferable.
- metal dithiocarbamate is used as a polymerization inhibitor for the vinyl compound. This dichocarbamine
- R 1 and R 2 are each an alkyl group having 1 to 8 carbon atoms or a phenyl group.
- the alkyl group having 1 to 8 carbon atoms may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group And so on.
- R 1 and R 2 may be the same or different.
- M represents a metal, such as nickel, zinc, copper, iron, and transition metals (Mn, Co, etc.).
- N indicates the valence of the metal M.
- dithiol-lubamic acid metal salt represented by the above general formula (I) examples include, for example, dimethyl dithiol-carbamic acid ⁇ , getyl dil-lactic acid rubamic acid m, and dipropyl dithiol-carbamic acid Copper oxide, dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diphenyldithiocarbamate, methylethyldithiocarbamate Acid, methylpropyldithiol 'copper phosphate, methylbutyldithiolcarbamate, methylpentyldithiolcarbamate, copper methyl dimethyldithiolcarbamate.Methylphenyldithiolcarbamate.
- Copper propyl citrate Luba mate butyl pentyl dithiocarbamate Copper butyl, butyl hexyl dithiocalate, butyl phenyl dithiocalate ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Iron salts.
- Various transition metal (Mn. C0, etc.) salts Among these metal salts of dithiolrubamate, copper salts of dithiolrubamate are preferred, and copper dibutyldithiocarbamate is particularly preferred.
- the metal dithiocarbamate may be used singly or in combination of two or more.
- the amount of addition is usually selected within the range of 0.01 to 11% by weight, preferably 0.05 to 0.5% by weight, based on the vinyl compound. Devour. If this amount is less than 0.01% by weight, the effect of preventing polymerization is not sufficiently exhibited. On the other hand, if it exceeds 1% by weight, the effect is not improved for the amount, but it is economically disadvantageous.
- water may be allowed to coexist with the above-mentioned metal salt of dibasic rubamate in order to suppress corrosion of equipment.
- the amount of water needs to be adjusted so as to be in the range of 0.05 to 5% by weight based on the vinyl compound. If the amount of water is less than 0.05% by weight, the effect of inhibiting corrosion is not sufficiently exhibited. On the other hand, if it exceeds 5% by weight, the separation costs a great deal of energy and is economically disadvantageous. From the standpoint of corrosion prevention and economy, the preferred water scene is in the range of 0.07 to 0.5% by weight relative to the vinyl compound.
- an alcohol in order to suppress the corrosion of equipment, (a) an alcohol, (a) an inorganic acid or a salt thereof, (c) an aromatic carboxylic acid or a At least one selected from salts and (ii) salts containing zinc may be used.
- the alcohol used as the component (a) may be, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol.
- N Butyl phenol alcohol. Isobutyl phenol alcohol, n-octyl alcohol. Primary alcohol having 1 to 10 carbon atoms such as 2-ethylhexyl alcohol, ethylene glycol cornole, propylene glycol; 1 .4 Mono-butanediol; polyhydric alcohols such as 1,6-hexanediol, phenol, cresol, xylene phenol, benzyl alcohol, phenethyl alcohol, etc. Among them, polyhydric alcohols are preferable.
- oxo acids are preferred, and specific examples thereof include boric acid, phosphoric acid, nitric acid, and sulfuric acid.
- phosphoric acid is preferred.
- salts include nickel salts, zinc salts, copper salts, iron salts, and various transition metal (Mn, C0, etc.) salts.
- aromatic carboxylic acid or a salt thereof used as the component (c) include, for example, benzoic acid, naphthalene carboxylic acid, salicylic acid, and p-hydroxybenzoic acid.
- Examples include oxinaphthoic acid and the like, nickel salts, zinc salts, copper salts, iron salts, and various transition metal (Mn, Co, etc.) salts.
- examples of the salt containing zinc as the component (2) include zinc formate, zinc acetate and zinc dithiocarbamate.
- These corrosion inhibiting substances K may be used alone or in combination of two or more.
- the amount used is based on the vinyl compound.
- the corrosion inhibitor is in the range of 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of inhibiting corrosion is not sufficiently exhibited, and if it exceeds 5% by weight, the effect is not sufficiently improved for the amount. May occur. From the viewpoint that corrosion is effectively suppressed and other disadvantages are not caused, the preferred amount of the corrosion inhibitor is preferably 0.01 to 3% by weight relative to the vinyl compound, Particularly preferred is a range of 0.1 to 1% by weight.
- the amount of the phosphoric acid to be used depends on the above-mentioned metal salt of dithiocarbamic acid, especially dithiocarbamic acid. It is preferable that the ratio is 0.1 or more (weight ratio) with respect to the acid copper salt.
- the metal salt of dithiocarbamic acid and water or, the treatment temperature of vinyl compounds containing dithiol metal salts of metal salts and corrosion inhibitors varies depending on the type of vinyl compound, but in the case of acrylic acid or methacrylic acid, It is usually in the range of 50 to 130 ° C. When the treatment temperature is within this range, the polymerization preventing effect and the corrosion preventing effect are sufficiently exhibited.
- Comparative Example 1 acrylic acid was replaced with copper dibutyldithiocarbamate. At the same time, 3,630 weight ppm of acetic acid manganese (relative to acrylic acid) was dissolved (water content in acrylic acid: 240 weight ppm) and added to the flask. The experiment was performed in the same manner as in Comparative Example 1 except that the gas was supplied. As a result, the weight loss of the test piece over 10 days was 0.080 g.
- Comparative Example 1 zinc dibutyldithiocarbamate 3.500 wt ppm (vs. acrylic acid) was dissolved in acrylic acid together with copper dibutyldithiocarbamate. The experiment was carried out in the same manner as in Comparative Example 1 except that water was supplied to Flasco with a water content of 970 wt ppm (vs. acrylic acid). As a result, the weight loss of the test piece over 10 days was 0.001 g.
- Comparative Example 1 100,000 ppm by weight of ethylene glycol (with respect to acrylic acid) was dissolved in acrylic acid together with copper dibutyldithiocarbamate (acrynolic acid). The experiment was carried out in the same manner as in Comparative Example 1 except that the water content of lylic acid (il 20 wt ppm) was supplied to Frasco. As a result, the weight loss of test pieces over 10 days was 0.003 g.
- Comparative Example 1 1,700 weight ppm of zinc phosphate (vs. acrylic acid) was dissolved in acrylic acid together with copper dibutyldithiocarbamate (acrylic acid). Water content in phosphoric acid: 140 ppm by weight) Other than that, the experiment was performed in the same manner as in Comparative Example 1. As a result, the weight loss of the test piece over 10 days was 0.009 g.
- Comparative Example 1 8.5% by weight of phosphoric acid (vs. acrylic acid) was dissolved in acrylic acid together with copper dibutyldithiocarbamate (acrylic acid). The experiment was carried out in the same manner as in Comparative Example 1 except that the water content in the acid was 3222 wt ppm) and supplied to Flasco. As a result, the amount of nobleness of the test piece over 10 days was 0.001 g.
- Comparative Example 1 3.300 heavy fumaric acid (vs. acrylic acid) was dissolved in acrylic acid together with dibutyldithiocarbamic acid (acrylic acid) (acrylic acid). The experiment was carried out in the same manner as in Comparative Example 1, except that the water content in the acid was 200 wt. As a result, the weight loss of the test beads over 10 days was 0.001 g.
- Comparative Example 1 100,000 ppm by weight of benzoic acid (based on acrylic acid) was dissolved in acrylic acid together with copper dibutyldithiocarbamate (in acrylic acid). The experiment was conducted in the same manner as in Comparative Example 1 except that the water content was 135 ppm by weight) and supplied to FLUSCO. As a result, the weight loss of test pieces in 10 days was 0.002 g.
- Comparative Example 1 copper dibutyldithiocarbamate was dissolved at 500 ppm by weight (based on acrylic acid) in acrylic acid, and 50 ppm Sppm (based on acrylic acid) was dissolved in acrylic acid.
- glycolic acid glycolic acid
- the inside temperature of the flask was maintained at 130 ° C. went.
- the weight loss of test pieces in 10 days was 0.0001 g.
- Comparative Example 1 copper dibutyldithiocarbamate was added to acrylic acid. Dissolve 150,000 double SppiD (vs. acrylic acid) and dissolve 40,000 double ippni (vs. acrylic acid) The experiment was carried out in the same manner as in Comparative Example 1 except that the temperature was kept at 130 ° C. and the temperature inside the flask was kept at 130 ° C. As a result, the weight loss of the test beads in 10 days was 0.022 g.
- Comparative Example 1 was the same as Comparative Example 1, except that the prescribed amounts of copper dibutyl dithiocarbamate and phosphoric acid shown in Table 2 were dissolved in acrylic acid and supplied to the flask. The experiment was performed as in 1. As a result, the weight loss of the test beads in 10 days was 0.001 g. Table 2
- the polymerization of a vinyl compound particularly in a distillation system in a production process of acrylic acid / methacrylic acid, can be effectively suppressed.
- corrosion of equipment can be prevented, and stable long-term continuous operation is possible.
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Polymerisation Methods In General (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50936796A JP3544985B2 (ja) | 1994-09-09 | 1995-08-29 | ビニル化合物の重合防止方法 |
| US08/793,600 US5886220A (en) | 1994-09-09 | 1995-08-29 | Process for preventing polymerization of vinyl compound |
| EP95929240A EP0781755A4 (en) | 1994-09-09 | 1995-08-29 | METHOD FOR INHIBITING THE POLYMERIZATION OF VINYL DERIVATIVES |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21570594 | 1994-09-09 | ||
| JP6/215705 | 1994-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996007631A1 true WO1996007631A1 (fr) | 1996-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1995/001705 WO1996007631A1 (fr) | 1994-09-09 | 1995-08-29 | Procede d'inhibition de la polymerisation d'un compose vinylique |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998011048A1 (fr) * | 1996-09-16 | 1998-03-19 | Elf Atochem S.A. | Procede perfectionne de purification de l'acide acrylique |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886220A (en) * | 1994-09-09 | 1999-03-23 | Idemitsu Petrochemical Co., Ltd. | Process for preventing polymerization of vinyl compound |
| GB9819600D0 (en) * | 1998-09-08 | 1998-11-04 | Marks A H & Co Ltd | Chemical compositions |
| CN100497290C (zh) * | 2001-12-05 | 2009-06-10 | 三菱化学株式会社 | (甲基)丙烯酸酯的精制方法 |
| KR101906096B1 (ko) * | 2012-08-24 | 2018-10-08 | 미쯔비시 케미컬 주식회사 | 카복실산 철의 제조 방법 |
| US9781841B2 (en) | 2015-03-27 | 2017-10-03 | Det International Holding Limited | Soldering apparatus with automatic aligning function |
| CN116421594A (zh) * | 2022-01-04 | 2023-07-14 | 中南大学 | 一种nlrp3炎性小体抑制剂及其应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS50101313A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | 1974-01-16 | 1975-08-11 | ||
| JPH0551403A (ja) * | 1990-11-09 | 1993-03-02 | Nippon Shokubai Co Ltd | ビニル化合物の重合防止剤および重合防止方法 |
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| US4021310A (en) * | 1972-12-22 | 1977-05-03 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for inhibiting the polymerization of acrylic acid or its esters |
| JPS5129328A (en) * | 1974-08-29 | 1976-03-12 | Sumitomo Chemical Co | Aruminiumu mataha aruminiumugokin no hyomenniseiseisaseta yokyokusankahimaku no denkaichakushokuhoho |
| US4532011A (en) * | 1984-03-02 | 1985-07-30 | The Goodyear Tire & Rubber Company | Inhibiting polymerization of vinylaromatic monomers |
| US5128484A (en) * | 1987-12-28 | 1992-07-07 | Sokubai Kagaku Kogyo, Co., Ltd. | Acrylonitrile maleimides solution composition of improved shelf life and method for production thereof |
| GB9000436D0 (en) * | 1990-01-09 | 1990-03-07 | Shell Int Research | Process for shortstopping an emulsion polymerization |
| CN1031269C (zh) * | 1990-11-09 | 1996-03-13 | 株式会社日本触媒 | 用于乙烯系化合物的聚合抑制方法 |
| DE69111382T2 (de) * | 1990-11-09 | 1996-03-28 | Nippon Catalytic Chem Ind | Polymerisationsinhibitor und Inhibierungsmethode für Vinylverbindungen. |
| US5130471A (en) * | 1991-09-06 | 1992-07-14 | Heiman John C | Stabilized acrylic monomer compositions |
| US5322960A (en) * | 1993-04-15 | 1994-06-21 | Nippon Shokubai Co., Ltd. | Method for inhibiting polymerization of (meth) acrylic acid and esters thereof |
| US5886220A (en) * | 1994-09-09 | 1999-03-23 | Idemitsu Petrochemical Co., Ltd. | Process for preventing polymerization of vinyl compound |
-
1995
- 1995-08-29 US US08/793,600 patent/US5886220A/en not_active Expired - Lifetime
- 1995-08-29 JP JP50936796A patent/JP3544985B2/ja not_active Expired - Lifetime
- 1995-08-29 EP EP95929240A patent/EP0781755A4/en not_active Ceased
- 1995-08-29 WO PCT/JP1995/001705 patent/WO1996007631A1/ja active IP Right Grant
- 1995-08-29 EP EP00110689A patent/EP1043303A1/en not_active Withdrawn
- 1995-08-29 CN CN95194943A patent/CN1069305C/zh not_active Expired - Lifetime
- 1995-08-29 KR KR1019970701130A patent/KR100408362B1/ko not_active Expired - Fee Related
- 1995-09-02 TW TW084109193A patent/TW289033B/zh not_active IP Right Cessation
- 1995-09-06 MY MYPI9502643 patent/MY115982A/en unknown
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1998
- 1998-12-15 US US09/210,885 patent/US6051735A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50101313A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | 1974-01-16 | 1975-08-11 | ||
| JPH0551403A (ja) * | 1990-11-09 | 1993-03-02 | Nippon Shokubai Co Ltd | ビニル化合物の重合防止剤および重合防止方法 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0781755A4 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998011048A1 (fr) * | 1996-09-16 | 1998-03-19 | Elf Atochem S.A. | Procede perfectionne de purification de l'acide acrylique |
| FR2753445A1 (fr) * | 1996-09-16 | 1998-03-20 | Atochem Elf Sa | Procede perfectionne de purification de l'acide acrylique |
| US6352619B1 (en) | 1996-09-16 | 2002-03-05 | Atofina | Method for purifying acrylic acid |
| CN1109012C (zh) * | 1996-09-16 | 2003-05-21 | 阿托菲纳公司 | 改进的丙烯酸提纯方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100408362B1 (ko) | 2004-03-24 |
| KR970705532A (ko) | 1997-10-09 |
| CN1157606A (zh) | 1997-08-20 |
| MY115982A (en) | 2003-10-31 |
| US5886220A (en) | 1999-03-23 |
| EP1043303A1 (en) | 2000-10-11 |
| EP0781755A1 (en) | 1997-07-02 |
| TW289033B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1996-10-21 |
| EP0781755A4 (en) | 1998-04-29 |
| US6051735A (en) | 2000-04-18 |
| CN1069305C (zh) | 2001-08-08 |
| JP3544985B2 (ja) | 2004-07-21 |
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