EP0607388A1 - Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils. - Google Patents
Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils.Info
- Publication number
- EP0607388A1 EP0607388A1 EP93915893A EP93915893A EP0607388A1 EP 0607388 A1 EP0607388 A1 EP 0607388A1 EP 93915893 A EP93915893 A EP 93915893A EP 93915893 A EP93915893 A EP 93915893A EP 0607388 A1 EP0607388 A1 EP 0607388A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomers
- weight
- acid
- monoethylenically unsaturated
- use according
- 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.)
- Granted
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 18
- 238000009963 fulling Methods 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000008158 vegetable oil Substances 0.000 claims abstract description 9
- 239000010775 animal oil Substances 0.000 claims abstract description 8
- 235000013311 vegetables Nutrition 0.000 claims abstract description 8
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- 150000003009 phosphonic acids Chemical class 0.000 claims abstract 2
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract 2
- 239000010985 leather Substances 0.000 claims description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims 1
- 150000002688 maleic acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 241001465754 Metazoa Species 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 239000003999 initiator Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 241001417902 Mallotus villosus Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- -1 N-vinylcaprolacta Chemical compound 0.000 description 4
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- GQEKAPMWKCXNCF-UHFFFAOYSA-N 2,2-bis(ethenyl)-1,4-dioxane Chemical compound C=CC1(C=C)COCCO1 GQEKAPMWKCXNCF-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-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
- 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 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MYECVPCGFLCGQX-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-phenyliminopropan-2-yl)diazenyl]-2-methyl-n'-phenylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=CC=CC=1NC(=N)C(C)(C)N=NC(C)(C)C(=N)NC1=CC=CC=C1 MYECVPCGFLCGQX-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- CKKQLOUBFINSIB-UHFFFAOYSA-N 2-hydroxy-1,2,2-triphenylethanone Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C(=O)C1=CC=CC=C1 CKKQLOUBFINSIB-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
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- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
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- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical class NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000019486 Sunflower oil Nutrition 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
- ZSLGZVNTZYLIAJ-UHFFFAOYSA-N [2-methyl-1-(prop-2-enoylamino)propyl]phosphonic acid Chemical compound CC(C)C(P(O)(O)=O)NC(=O)C=C ZSLGZVNTZYLIAJ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical class CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UMGLBHQOFQXXSI-UHFFFAOYSA-N hepta-2,5-dienedioic acid Chemical compound OC(=O)C=CCC=CC(O)=O UMGLBHQOFQXXSI-UHFFFAOYSA-N 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
Definitions
- the greasing is a quality-determining process in the production of leather and especially important in the case of very soft types of leather.
- aqueous fat emulsions (licker) are used, which are generally based on petrochemical products and natural oils and fats and made water-soluble by partial sulfation or with the help of emulsifiers.
- Patent application P 42 05 839.2 describes polymeric leather greasing agents based on esterified or modified homo- or copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, which, depending on the degree of derivatization of the carboxyl groups and the "polarity of the monomers in hydrophobicized leather, to a certain extent The water-repellent properties of the leather can deteriorate, and this application also describes further prior art.
- the invention was based on the object of providing improved means for greasing and filling leather and fur skins which no longer have the disadvantages of the prior art.
- the object is achieved according to the invention by using water-soluble or water-dispersible graft copolymers of vegetable and animal oils, obtainable by free-radically initiated polymerization according to claim 1.
- Mono ere (a) are e.g. monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhy- acid dride.
- monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhy- acid dride.
- Examples of monomers containing sulfo groups include Vinyl sulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylic acid 3-sulfopropyl ester, methacrylic acid 3-sulfopropyl ester, styrene sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
- Monomers with phosphonic acid groups are, for example, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated allylamine and acrylamido-2-methylpropanephosphonic acid.
- Preferred monomers of group (a) are acrylic acid, methacrylic acid and maleic acid. It can also be advantageous to use mongrels of monomers (a).
- the acids are preferably used as such or as anhydrides; in addition, alkali metal, alkaline earth metal or ammonium salts, such as the sodium, potassium, calcium, ammonium or substituted ammonium salts, can of course also be used, the All or part of the acids can be present as salts.
- Monomers (b) which can be copolymerized with the monomers (a) include, in particular, N-vinylpyrrolidone, N-vinylcaprolacta, N-vinylimidazole, l-vinyl-2-methylimidazole, N-vinylformamide, N- Vinyl-N-methylformamide, vinyl acetate, vinyl propionate, styrene, acrylic acid and methacrylic acid esters with Ci- to C 3 o-alcohols, hydroxy-C 2 - to C ⁇ -alkyl esters of acrylic acid or methacrylic acid, acrylamide, methacrylamide or mono- and dialkylamides of acrylic acid and methacrylic acid with 1 to 20 carbon atoms in the alkyl radicals.
- olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
- olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
- a further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c).
- the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
- These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the preferred amount of monomers (c) is 0.05 to 2% by weight.
- the use of the monomers of group (c) during the copolymerization increases the K values of the copolymers.
- Suitable compounds of this type are, for example, methylene bisacrylic acid, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least two polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
- Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols with a molecular weight of up to 3,000, are preferably used.
- component B includes all vegetable and animal oils. There are, for example, olive oil, rapeseed oil, soybean oil, sunflower oil, safflower oil, linseed oil, capelan oil or sperm oil.
- the monomers (a) and optionally (b) and / or (c) are polymerized by free radicals in the presence of component B. It may be favorable for the effect of the graft polymer formed to use two or more of the oils specified under B.
- the polymerization can be carried out in the presence or in the absence of inert solvents or diluents, with the absence of diluents being preferred.
- Inert solvents are, for example, aromatic hydrocarbons such as toluene, xylene, o-, -, p-xylene and isomer mixtures of xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, Cyclooctane, methylcyclohexane or mixtures of the hydrocarbons mentioned and gasoline fractions which contain no polymerizable monomers.
- aromatic hydrocarbons such as toluene, xylene, o-, -, p-xylene and isomer mixtures of xylene or ethylbenzene
- aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane,
- chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the named inert are suitable Solvents.
- the graft polymerization can be carried out continuously or batchwise, in general initiators which form free radicals are also used.
- Suitable radical-forming initiators are preferably those which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which disintegrate at different temperatures, namely firstly using an initiator which already disintegrates at a lower temperature for the start of the polymerization and then complete the main polymerization with an initiator that decomposes at a higher temperature. For example, the following initiators can be used.
- Acetylcyclohexanesulfonyl peroxide diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tert-butyl perneodecanoate, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2- methyl- N-phenylpropionamidine) dihydrochloride, 2,2'-azobis- (2-methylpropionamidine) dihydrochloride.
- a redox system such as salts or complexes of heavy metals, for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used , the half-lives of the radical initiators indicated can be reduced.
- tert-butylhydroperoxide can be activated with the addition of 5 ppm copper (II) acetylacetonate in such a way that polymerisation can take place at 100 ° C.
- the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is used. 0.01 to 5% of the reducing compounds are added as redox components. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often beneficial to use a combination of peroxide, and Use reducing agent and heavy metal as a redox catalyst.
- the polymerization of the monomers (a) and the optionally used monomers (b) and / or (c) can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
- the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used.
- high-energy UV lamps such as carbon arc lamps, mercury vapor lamps or xenon lamps
- low-UV light sources such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.
- Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
- Allyl compounds such as allyl alcohol, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols are also suitable as regulators. If the polymerization is carried out in the presence of regulators, from 0.05 to 20% by weight, based on the monomers used in the polymerization, is required.
- the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts thereof zen, water-soluble -PO (OH) "groups containing compounds and / or their water-soluble salts.
- Phosphorous acid is preferably used.
- the phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of 0.01 to 5% by weight. %, based on the monomers (A) used Possible phosphorus compounds are described in EP-A-0 175 317.
- the copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization.
- the reactants which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range from 40 to 150 ° C.
- the monomers (A) are therefore added continuously or batchwise to the polymerizing mixture to the extent that the graft polymerization is readily controllable in the desired temperature range.
- a type of addition of the monomers of component (A) is preferred, in which the compounds of component (B) or at least some of the compounds of component (B) are first combined with at least one monomer of group (a) in the polymerization reactor Submitted reactor and heated to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) and optionally the monomers (b) and, if appropriate, (c) and the initiator are added over a period of about 1 to 10, preferably 2 to 8 hours and, if necessary, a controller.
- capelan oil with 1% ditertiary butyl peroxide can be heated to 150 ° C. for 2 hours in a weak stream of N 2 and then acrylic acid is metered in at 150 ° C. in the course of 3 hours.
- the grafted vegetable or animal oil is converted into an aqueous dispersion.
- the dispersion can be made using conventional emulsifiers such as fatty alcohol ethoxylates, dodecylbenzene sulfonates, dioctyl sulfosuccinate or alkyl sulfonates can be carried out in suitable apparatus.
- Emulsifier-free dispersion is particularly preferred by partially or completely neutralizing the carboxyl groups of the graft polymer with alkalis, alkaline earths, ammonia or amines and thus obtaining stable aqueous dispersions.
- These dispersions have a solids content of 5 to 80% and preferably 20 to 70% and can thus be used directly for the treatment of leather and furskins.
- the drying residue can be determined, for example, in a drying cabinet (2 h at 120 ° C.).
- graft polymers to be used according to the invention it is possible to produce very soft leather without the addition of conventional liquors.
- the water-repellent properties of hydrophobic leather are not adversely affected when these products are used.
- the mechanical properties, such as tensile strength, as well as the light fastness and heat yellowing resistance of such leather, are very positively influenced by the use of these graft polymers.
- the good fixation in the leather causes great resistance to extractability with solvents or water. This leads to so-called washable leathers, i.e. leathers that do not lose their properties such as softness, firmness and suppleness after washing; in contrast, this property is not to be expected for leathers that are greased with conventional licker.
- aqueous dispersion to be used according to the invention preferably contains no additional emulsifiers.
- leather and furs which are to be made hydrophobic and are treated with products containing emulsifiers, are known to have to undergo complex processes after treatment with these agents, e.g. Post-treatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, i.e. to fix.
- the graft polymer dispersions described above are suitable for the treatment of all conventional tanned hides.
- the tanned skins are usually removed before the treatment. acidifies. They may have been stained before treatment. However, coloring can also be carried out only after the oiling has taken place according to the invention.
- the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the graft polymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. treated for a period of 0.1 to 5, in particular 0.5 to 2 h. This treatment takes place, for example, by drumming in a barrel.
- the required amount of graft polymer dispersion, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
- the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
- the pH of the treatment liquor is adjusted to a value of 3 to 5, preferably 3.5 to 4, by adding acids, preferably an organic acid such as formic acid.
- the lung Behand ⁇ with the present invention aqueous dispersions to be used discontinuously before or after the retanning step the advertising used.
- Example 2 Similar to Example 1, 100 g of capelan oil and 1 g of tert-butyl perethylhexanoate are heated to 150 ° and stirred for 1 hour. Then 10 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 hours. After cooling, the mixture is diluted with 310 g of water and 7.2 g of 50% sodium hydroxide solution and the mixture is intensively dispersed for 10 minutes with the Ultra-Turrax. The dispersion obtained has a pH of 8.9, a drying residue of 25% and a Brookfield viscosity of 16 mPa-s at 23 ° C.
- rapeseed oil are heated to 150 ° C. under a weak stream of N 2 . Then 20 g of acrylic acid (100%) and the solution of 1 g of tert-butyl perethylhexanoate in 10 g of rapeseed oil are uniformly metered in at 150 ° C. within 1 h. The mixture is then stirred at 150 ° for 2 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated again at 150 ° C. for 2 h.
- 100 g of the graft polymer thus obtained are diluted with 76 g of water and dispersed intensively for 10 minutes.
- the white viscous dispersion has a pH of 3.5 and a drying residue of 55.9%.
- Example 1 100 g of rapeseed oil and 1 g of tert-butyl perethylhexanoate are heated for 1 hour at 150 ° C. under a weak N 2 stream. Then 18 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 h. It is then cooled and 105 g of the product are mixed with 90 g of water and 8 g of 50% sodium hydroxide solution and dispersed intensively for 10 minutes with the Ultra-Turrax. A homogeneous viscous dispersion is formed with a drying residue of 52.7% and a pH of 5.5.
- Example 1 100 g of capelan oil are heated to 150 ° in a weak N 2 stream and then 20 g of acrylic acid and a solution of 1 g of tert-butyl perethylhexanoate in 10 g of capelan oil are uniformly added at 150 ° C. in the course of 1 h. The mixture is then heated for a further 1 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated for a further 1 h. The mixture is then cooled and 103 g of the product, after adding 90 g of water and 9 g of 50% sodium hydroxide solution, are dispersed intensively for 10 minutes using Ultra-Turrax. The viscous homogeneous dispersion has a pH of 7.0 and the drying residue is 49.1%.
- Example 6 20 g of methacrylic acid are used instead of acrylic acid. 115 g of the graft polymer obtained, 95 g of water and 14 g of 50% sodium hydroxide solution are intensively dispersed for 10 minutes with the Ultra-Turrax. The viscous dispersion has a pH of 7.1 and a drying residue of 51.2%.
- Example 5 The product from Example 4 was used analogously to the procedure given in Example 3. The leather thus obtained showed soft and round grip properties.
- Example 5 The product from Example 5 was used analogously to the procedure given in Example 1.
- the leather thus obtained was characterized by a round, soft handle.
- Example 6 The product from Example 6 was used analogously to the procedure given in Example 1. The result was similarly advantageous as in the previous examples.
- Example 7 The product from Example 7 was used analogously to the procedure given in Example 3. The result was a soft leather with a comfortable grip.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4224456A DE4224456A1 (de) | 1992-07-24 | 1992-07-24 | Verwendung von Pfropfpolymeren zum Fetten und Füllen von Leder und Pelzfellen |
DE4224456 | 1992-07-24 | ||
PCT/EP1993/001831 WO1994002650A1 (fr) | 1992-07-24 | 1993-07-13 | Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0607388A1 true EP0607388A1 (fr) | 1994-07-27 |
EP0607388B1 EP0607388B1 (fr) | 1997-10-08 |
Family
ID=6463993
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93915893A Expired - Lifetime EP0607388B1 (fr) | 1992-07-24 | 1993-07-13 | Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils |
Country Status (7)
Country | Link |
---|---|
US (1) | US5620748A (fr) |
EP (1) | EP0607388B1 (fr) |
JP (1) | JPH06511284A (fr) |
AU (1) | AU662071B2 (fr) |
DE (2) | DE4224456A1 (fr) |
ES (1) | ES2108289T3 (fr) |
WO (1) | WO1994002650A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4402029A1 (de) * | 1994-01-25 | 1995-07-27 | Basf Ag | Wäßrige Lösungen oder Dispersionen von Copolymerisaten |
DE19625984C2 (de) * | 1996-06-28 | 1999-07-29 | Stockhausen Chem Fab Gmbh | Wäßrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung in der Lederherstellung |
KR100346466B1 (ko) * | 1999-12-06 | 2002-07-27 | 현대자동차주식회사 | 페이스트형 방음용 밀봉재 조성물 |
FR2836485B1 (fr) * | 2002-02-28 | 2004-07-30 | Coatex Sas | Utilisations de polymeres acryliques greffes dans le domaine des substrats a base de collagene. substrats, peaux et cuirs ainsi obtenus |
BR0318684A (pt) * | 2003-12-25 | 2006-12-12 | Council Scient Ind Res | processo transformado para a fabricação de couros |
US20060188729A1 (en) * | 2005-02-22 | 2006-08-24 | Kai-Volker Schubert | Washable leather with repellency |
FR2974578B1 (fr) * | 2011-04-28 | 2015-10-30 | Rhodia Operations | Corps gras copolymerise, son procede de preparation et ses applications |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA476567A (fr) * | 1951-08-28 | Shell Development Company | Pigmentation de polymers | |
CA688182A (en) * | 1964-06-09 | R. Mills Maurice | Carboxylic acid condensation products | |
US2346858A (en) * | 1941-01-14 | 1944-04-18 | Du Pont | Interpolymer |
US3392176A (en) * | 1964-01-02 | 1968-07-09 | Cargill Inc | Solventless coating vehicle and process for preparing it |
US3408319A (en) * | 1964-12-08 | 1968-10-29 | Rohm & Haas | Tanning compositions comprising aqueous solutions of unsaturated acid-unsaturated sulfated oil copolymers |
DE1800244C2 (de) * | 1968-10-01 | 1973-10-18 | Roehm Gmbh, 6100 Darmstadt | Verfahren zum gleichzeitigen Fetten und Imprägnieren von Leder |
US3639650A (en) * | 1969-03-28 | 1972-02-01 | Pacific Vegetable Oil Corp | Manufacture of maleyl-fatty acid adduct |
US3873584A (en) * | 1972-12-27 | 1975-03-25 | Said Burke By Said Kizer And D | Hydroxyl containing unsaturated drying oil polymers and processes for preparing polymers |
IT981903B (it) * | 1973-04-09 | 1974-10-10 | Duco Spa | Resine acide oleo acriliche e procedimento per la loro prepa razione |
CS173141B1 (fr) * | 1973-07-16 | 1977-02-28 | ||
CS184061B1 (en) * | 1975-03-05 | 1978-07-31 | Slavko Hudecek | Powdered hydrophilic filler for polyvinylchloride and method of makig them |
JPS52107083A (en) * | 1976-03-05 | 1977-09-08 | Kao Corp | Preparation of vinyl polymer emulsions |
FR2463780A1 (fr) * | 1979-08-24 | 1981-02-27 | Rhone Poulenc Ind | Procede de preparation de solutions aqueuses d'acides polyacryliques de faibles masses moleculaires ou de leurs sels |
US4314802A (en) * | 1979-08-24 | 1982-02-09 | Rohm And Haas Company | Process for producing leather |
US4289667A (en) * | 1980-01-21 | 1981-09-15 | The B. F. Goodrich Company | Emulsion polymerization process with low emulsifier concentration |
US4375521A (en) * | 1981-06-01 | 1983-03-01 | Communications Technology Corporation | Vegetable oil extended polyurethane systems |
DE3715421A1 (de) * | 1987-05-08 | 1988-11-24 | Henkel Kgaa | Verwendung eines fetten oeles ex helianthus annuus zur herstellung von emulgiermitteln fuer die emulsionspolymerisation |
DE4142318C2 (de) * | 1991-12-20 | 1999-01-14 | Zschimmer & Schwarz Gmbh & Co | Verwendung von Fettsäure-Umsetzungsprodukten in Leder- und Pelzfettungsmitteln und Mittel zum Fetten von Leder und Pelzfellen |
-
1992
- 1992-07-24 DE DE4224456A patent/DE4224456A1/de not_active Withdrawn
-
1993
- 1993-07-13 DE DE59307502T patent/DE59307502D1/de not_active Expired - Lifetime
- 1993-07-13 WO PCT/EP1993/001831 patent/WO1994002650A1/fr active IP Right Grant
- 1993-07-13 ES ES93915893T patent/ES2108289T3/es not_active Expired - Lifetime
- 1993-07-13 EP EP93915893A patent/EP0607388B1/fr not_active Expired - Lifetime
- 1993-07-13 US US08/193,135 patent/US5620748A/en not_active Expired - Fee Related
- 1993-07-13 AU AU45679/93A patent/AU662071B2/en not_active Ceased
- 1993-07-13 JP JP6504118A patent/JPH06511284A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9402650A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU4567993A (en) | 1994-02-14 |
DE59307502D1 (de) | 1997-11-13 |
DE4224456A1 (de) | 1994-01-27 |
EP0607388B1 (fr) | 1997-10-08 |
JPH06511284A (ja) | 1994-12-15 |
US5620748A (en) | 1997-04-15 |
AU662071B2 (en) | 1995-08-17 |
ES2108289T3 (es) | 1997-12-16 |
WO1994002650A1 (fr) | 1994-02-03 |
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