DE3941061A1 - Anionic surfactant - obtd. by sulphating opt. poly:alkoxylated fatty acid sorbitan ester] used in prepn. of surfactant - Google Patents
Anionic surfactant - obtd. by sulphating opt. poly:alkoxylated fatty acid sorbitan ester] used in prepn. of surfactantInfo
- Publication number
- DE3941061A1 DE3941061A1 DE3941061A DE3941061A DE3941061A1 DE 3941061 A1 DE3941061 A1 DE 3941061A1 DE 3941061 A DE3941061 A DE 3941061A DE 3941061 A DE3941061 A DE 3941061A DE 3941061 A1 DE3941061 A1 DE 3941061A1
- Authority
- DE
- Germany
- Prior art keywords
- anionic surfactants
- fatty acid
- alkoxylated
- sorbitan
- residue
- 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.)
- Withdrawn
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 28
- 239000000194 fatty acid Substances 0.000 title claims abstract description 28
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 28
- -1 fatty acid sorbitan ester Chemical class 0.000 title claims abstract description 26
- 239000003945 anionic surfactant Substances 0.000 title claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 title claims description 8
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical group OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 150000002190 fatty acyls Chemical group 0.000 claims abstract description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 16
- 230000019635 sulfation Effects 0.000 claims description 14
- 238000005670 sulfation reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003925 fat Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- CNVZJPUDSLNTQU-UHFFFAOYSA-N Petroselaidic acid Natural products CCCCCCCCCCCC=CCCCCC(O)=O CNVZJPUDSLNTQU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229940068965 polysorbates Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/26—Carbohydrates, e.g. sugar alcohols, amino sugars, nucleic acids, mono-, di- or oligo-saccharides; Derivatives thereof, e.g. polysorbates, sorbitan fatty acid esters or glycyrrhizin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Birds (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Gegenstand der Erfindung sind anionische Tenside erhältlich durch Sulfatierung gegebenenfalls alkoxylierter Fettsäuresorbitanester und nachfolgende Neutralisation mit Basen, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung zur Herstellung oberflächen aktiver Mittel.The invention relates to anionic surfactants obtainable from Sulfation of optionally alkoxylated fatty acid sorbitan esters and subsequent neutralization with bases, a process for their Manufacturing and their use for manufacturing surfaces active funds.
Fettsäuresorbitanester stellen eine wichtige Gruppe nichtionischer Tenside dar, die man z. B. durch Veresterung von Fettsäuren oder Umesterung von Fettsäuremethylestern mit Sorbit erhält. Durch An lagerung von Ethylenoxid an die freien Hydroxylgruppen der Fett säuresorbitanester, lassen sich ferner Polyethoxylate erhalten, die als Polysorbate bekannt sind [J. Falbe (Hrsg.), Surfactants in Consumer Products, Springer-Verlag, Berlin, 1987, S. 100]. Beide Gruppen von Verbindungen sind ökotoxikologisch unbedenklich und finden daher Verwendung als Emulgatoren in Kosmetik, Nahrungs mittelindustrie und Pharmazie.Fatty acid sorbitan esters represent an important group of nonionics Are surfactants, which one z. B. by esterification of fatty acids or Transesterification of fatty acid methyl esters with sorbitol. By To Storage of ethylene oxide on the free hydroxyl groups of the fat acid sorbitan esters, polyethoxylates can also be obtained, known as polysorbates [J. Falbe (ed.), Surfactants in Consumer Products, Springer-Verlag, Berlin, 1987, p. 100]. Both Groups of compounds are ecotoxicologically safe and therefore find use as emulsifiers in cosmetics, food medium industry and pharmacy.
Von Nachteil ist jedoch, daß insbesondere nicht- oder nur niedrigalkoxylierte Fettsäuresorbitanester eine unzureichende Hydrophilie aufweisen und somit für die Herstellung von ober flächenaktiven Mitteln, die eine hohe Wasserlöslichkeit erfordern, wie z. B. flüssige Waschmittel, Spülmittel oder Haarshampoos, un geeignet sind.The disadvantage, however, is that in particular not or only low alkoxylated fatty acid sorbitan esters are inadequate Have hydrophilicity and thus for the production of upper surfactants that require high water solubility, such as B. liquid detergent, dish soap or hair shampoo, un are suitable.
Das zu lösende technische Problem bestand somit darin, Tenside auf Basis von gegebenfalls alkoxylierten Fettsäuresorbitanestern zu entwickeln, die als entscheidendes Merkmal eine hohe Wasserlös lichkeit aufweisen.The technical problem to be solved was, therefore, surfactants Basis of optionally alkoxylated fatty acid sorbitan esters develop that as a key feature a high water solubility exhibit
Gegenstand der Erfindung sind anionische Tenside erhältlich durch Sulfatierung von gegebenenfalls alkoxylierten Fettsäuresorbitan estern der allgemeinen Formel (I),The invention relates to anionic surfactants obtainable from Sulfation of optionally alkoxylated fatty acid sorbitan esters of the general formula (I),
R-CO-[S] (I)R-CO- [S] (I)
in der R-CO für einen Fettacylrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen und [S] für einen gegebenen falls alkoxylierten Sorbitanrest steht, und anschließende Neutra lisation mit Basen.in the R-CO for a fatty acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and [S] for a given if alkoxylated sorbitan residue, and subsequent neutra lization with bases.
Zur Herstellung von Fettsäuresorbitanestern geht man von Sorbit, einem Hydrierprodukt der Glucose aus, das über sechs freie Hydro xylgruppen verfügt. Der Sorbit wird bei 200 bis 250°C entweder mit einer Fettsäure verestert [Boll.Chim.farm. 88, 413 (1949)] oder aber mit einem Fettsäuremethylester umgeestert [J. Rech. Centre Na tional de la Recherche Sci., Paris, 227 (1950)]. Hierbei geht der Sorbit zunächst unter Abspaltung von Wasser in 1,4- bzw. 3,6-Sorbitan (Anhydrosorbit), ein cyclisches Polyol mit vier Hy droxylgruppen über, welches dann mit dem Acylierungsmittel abrea gieren kann. Die Veresterung findet dabei vorzugsweise an der primären Hydroxylfunktion statt [Tenside Detergents 5, 266 (1968)]. Fettsäuresorbitanester können ferner Veresterungsprodukte enthalten, die sich vom dimeren 1,4 : 3,6-Dianhydro-sorbit (Isosor bid) ableiten. Sorbitol is used to produce fatty acid sorbitan esters, a hydrogenation product of glucose, which has six free hydro xyl groups. The sorbitol is either at 200 to 250 ° C a fatty acid esterified [Boll.Chim.farm. 88, 413 (1949)] or but transesterified with a fatty acid methyl ester [J. Right Center tional de la Recherche Sci., Paris, 227 (1950)]. Here goes the Sorbitol initially with the elimination of water in 1,4- or 3,6-Sorbitan (anhydrosorbitol), a cyclic polyol with four hy droxyl groups, which then abrea with the acylating agent can greed. The esterification takes place preferably on the primary hydroxyl function instead of [Tenside Detergents 5, 266 (1968)]. Fatty acid sorbitan esters can also be esterification products contain, which differ from the dimeric 1,4: 3,6-dianhydro-sorbitol (isosor bid).
Zur Veresterung des Sorbitans werden gesättigte oder ungesättigte Fettsäuren R-COOH oder Fettsäuremethylester R-COOCH3 verwendet, bei denen R-CO für einen Fettacylrest mit 6 bis 22 Kohlenstoff atomen und 0, 1, 2 oder 3 Doppelbindungen steht. Typische Bei spiele sind Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Öl säure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachidonsäure, Behensäure, Erucasäure sowie diese enthaltende technische Schnitte oder die entsprechenden Methylester. Sulfate von gebenenfalls alkoxylierten Fettsäuresorbitanestern mit beson ders günstigen Schaum-, Spül- und Wascheigenschaften werden er halten, wenn R-CO für einen gesättigten Fettacylrest mit 12 bis 18 Kohlenstoffatomen steht.For the esterification of sorbitan, saturated or unsaturated fatty acids R-COOH or fatty acid methyl ester R-COOCH 3 are used, in which R-CO represents a fatty acyl radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidonic acid, behenic acid, erucic acid and technical sections containing them or the corresponding methyl esters. Sulfates of optionally alkoxylated fatty acid sorbitan esters with particularly favorable foaming, rinsing and washing properties will be retained if R-CO stands for a saturated fatty acyl radical with 12 to 18 carbon atoms.
Die Fettsäuresorbitanester können auch in Form ihrer Alkylenoxid anlagerungsprodukte vorliegen. Die Alkoxylierung mit Ethylenoxid, Propylenoxid oder Gemischen dieser Alkylenoxide kann nach den be kannten großtechnischen Verfahren erfolgen. Hierbei findet nicht nur die Anlagerung des Alkylenoxids an freie, nichtveresterte Hy droxylgruppen statt, es kann vielmehr davon ausgegangen werden, daß unter basischen Reaktionsbedingungen Alkylenoxidgruppen auch in Carbonylesterbindungen eingeschoben werden (Schick,M.J., Non ionic Surfactants, Vol. 1, New York, Marcel Dekker, 1967). In die Sulfatierung werden solche Produkte eingesetzt, bei denen [S] in der allgemeinen Formel (I) für einen alkoxylierten Sorbitanrest steht, der sich durch Anlagerung von durchschnittlich 1 bis 30 Mol eines Alkylenoxids an 1 Mol Sorbitan ergibt. Infolge der niedrigen Viskosität empfielt es sich von Fettsäuresorbitanestern auszuge hen, die durchschnittlich 10 bis 20 Mol Ethylenoxid enthalten. Da nicht nur die Acylierung, sondern auch die Alkoxylierung einem statistischen Verlauf unterliegt, muß der durchschnittliche Alkoxylierungsgrad nicht notwendigerweise eine ganze Zahl darstel len, sondern kann vielmehr auch gebrochene Zahlenwerte - auch solche kleiner 1 - annehmen.The fatty acid sorbitan esters can also be in the form of their alkylene oxide add-on products are available. The alkoxylation with ethylene oxide, Propylene oxide or mixtures of these alkylene oxides can be according to the known large-scale processes. This does not take place only the addition of the alkylene oxide to free, non-esterified Hy droxyl groups instead, it can rather be assumed that under basic reaction conditions also alkylene oxide groups can be inserted into carbonyl ester bonds (Schick, M.J., Non ionic Surfactants, Vol. 1, New York, Marcel Dekker, 1967). In the Sulfation products are used in which [S] in of the general formula (I) for an alkoxylated sorbitan residue stands, which is accumulated by an average of 1 to 30 mol of an alkylene oxide to 1 mole of sorbitan. As a result of the low Viscosity is recommended to be extracted from fatty acid sorbitan esters hen containing an average of 10 to 20 moles of ethylene oxide. There not only the acylation but also the alkoxylation subject to statistical development, the average Degree of alkoxylation is not necessarily an integer len, but rather can also be broken numerical values - too less than 1 - assume.
Die Sulfatierung freier, gegebenenfalls alkoxylierter Hydroxyl funktionen der Fettsäuresorbitanester kann mit üblichen Sul fieragentien, wie z. B. Schwefelsäure, Oleum, Chlorsulfonsäure oder Amidosulfonsäure erfolgen. Vorzugsweise werden die gegebe nenfalls alkoxylierten Fettsäuresorbitanester jedoch mit gasför migem Schwefeltrioxid bei Temperaturen von 30 bis 100°C, vorzugs weise 50 bis 98°C umgesetzt, wobei die Reaktion kontinuierlich oder diskontinuierlich in üblichen, für die Sulfierung von Fett alkoholen, Fettsäureestern, Alkylbenzol oder Olefinen geeigneten Reaktoren, insbesondere vom Typ der Fallfilmreaktoren durchgeführt wird. Dabei wird das Schwefeltrioxid mit Luft oder Stickstoff verdünnt, vorzugsweise in Form eines Gasgemisches mit ca. 1 bis 8 Vol.-% SO3, und mit dem gegebenenfalls alkoxylierten Fettsäure sorbitanester in Kontakt gebracht. Das molare Einsatzverhältnis von Ester zu Schwefeltrioxid beträgt 1 : 0.5 bis 1 : 3.5. Zur Erzielung hellfarbiger Produkte mit ausreichend hohem Sulfiergrad ist es jedoch sinnvoll, ein Verhältnis von 1 : 1.0 bis 1 : 2.5 zu wählen.The sulfation of free, optionally alkoxylated hydroxyl functions of the fatty acid sorbitan esters can be carried out with conventional sulfation agents, such as, for. B. sulfuric acid, oleum, chlorosulfonic acid or amidosulfonic acid. However, the optionally alkoxylated fatty acid sorbitan esters are reacted with gaseous sulfur trioxide at temperatures from 30 to 100 ° C., preferably from 50 to 98 ° C., the reaction being carried out continuously or batchwise in the customary manner for the sulfonation of fatty alcohols, fatty acid esters, alkylbenzene or Suitable olefins reactors, in particular of the type of falling film reactors is carried out. The sulfur trioxide is diluted with air or nitrogen, preferably in the form of a gas mixture with about 1 to 8% by volume of SO 3 , and brought into contact with the optionally alkoxylated fatty acid sorbitan ester. The molar ratio of ester to sulfur trioxide is 1: 0.5 to 1: 3.5. However, to achieve light-colored products with a sufficiently high degree of sulfonation, it makes sense to choose a ratio of 1: 1.0 to 1: 2.5.
Nach der Sulfatierung wird die saure Reaktionsmischung gemeinsam mit einer wässrigen Base in wenig Wasser eingerührt und bei pH = 6.5 bis 7.5 neutralisiert. Als Basen kommen Alkalimetallhydroxide wie Natrium-, Kalium- und Lithiumhydroxid, Erdalkalimetalloxide und -hydroxide wie Magnesiumhydroxid, Calciumoxid und Calciumhy droxid, Ammoniak, Mono-, Di- und Tri-C2-4-Alkanolamine, beispiels weise Mono-, Di- und Triethanolamin sowie primäre, sekundäre oder tertiäre C1-4-Alkylamine in Betracht. Die Neutralisationsbasen gelangen dabei in Form 5 bis 55 gew.-%iger wässriger Lösungen zum Einsatz, wobei 25 bis 50 gew.-%ige Natri umhydroxidlösungen bevorzugt sind.After sulfation, the acidic reaction mixture is stirred into a little water together with an aqueous base and neutralized at pH = 6.5 to 7.5. As bases come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C 2-4 -alkanolamines, for example mono-, di- and Triethanolamine as well as primary, secondary or tertiary C 1-4 alkylamines. The neutralization bases are used in the form of 5 to 55% by weight aqueous solutions, with 25 to 50% by weight sodium hydroxide solutions being preferred.
Die Struktur der anionischen Tenside, die durch Sulfatierung von gegebenfalls alkoxylierten Fettsäuresorbitanestern und nachfol gende Neutralisation mit Basen erhalten werden, ist noch nicht abschließend geklärt. Geht man von Fettsäuresorbitanestern mit ge sättigtem Fettacylrest aus, werden ausschließlich Produkte mit Sulfatstruktur erhalten. Es kann ferner davon ausgegangen werden, daß insbesondere bei überstöchiometrischem Einsatz von Schwefel trioxid die Sulfatierung von mehr als einer Hydroxylgruppe statt findet. Leiten sich die Fettsäuresorbitanester von ungesättigten Fettsäuren oder deren Methylestern ab, kann fener der Angriff des Schwefeltrioxids - wenngleich nur untergeordnet - auch an einer oder mehreren Doppelbindungen des Fettacylrestes erfolgen. In diesen Fällen erhält man anionische Tenside, die nicht nur Sul fat-, sondern auch Sulfonatstruktur aufweisen.The structure of the anionic surfactants by sulfation of optionally alkoxylated fatty acid sorbitan esters and successor sufficient neutralization with bases is not yet finally clarified. If one starts from fatty acid sorbitan esters with ge saturated fatty acyl residue, only products with Preserved sulfate structure. It can also be assumed that especially when using stoichiometric sulfur trioxide the sulfation of more than one hydroxyl group instead finds. The fatty acid sorbitan esters are derived from unsaturated ones Fatty acids or their methyl esters can also attack the Sulfur trioxide - even if only subordinate - on one or more double bonds of the fatty acyl radical. In In these cases, anionic surfactants are obtained which are not only sul fat, but also have sulfonate structure.
Die Sulfatierungsprodukte liegen nach der Neutralisation in Ab hängigkeit des Alkoxylierungsgrades entweder als blanke Flüssig keiten oder cremige Pasten vor und können in an sich bekannter Weise durch Zusatz von Wasserstoffperoxid- oder Natriumhypochlo ritlösung gebleicht werden. Dabei werden, bezogen auf den Fest stoffgehalt in der Lösung der Sulfierprodukte, 0.2 bis 2 Gew.-% Wasserstoffperoxid, berechnet als 100 gew.-%ige Substanz, oder entsprechende Mengen Natriumhypochlorit eingesetzt. Der pH-Wert der Lösungen kann unter Verwendung geeigneter Puffermittel, z. B. mit Natriumphosphat oder Citronensäure konstant gehalten werden. Zur Stabilisierung empfiehlt sich ferner eine Konservierung, z. B. mit Formaldehydlösung, p-Hydroxybenzoat, Sorbinsäure oder anderen bekannten Konservierungsstoffen.The sulfation products are in Ab after neutralization dependence of the degree of alkoxylation either as a bare liquid or creamy pastes and can be made in a known manner Way by adding hydrogen peroxide or sodium hypochlo solution can be bleached. Here, based on the festival substance content in the solution of the sulfonation products, 0.2 to 2% by weight Hydrogen peroxide, calculated as 100% by weight substance, or appropriate amounts of sodium hypochlorite are used. The pH the solutions can be prepared using suitable buffering agents, e.g. B. be kept constant with sodium phosphate or citric acid. Preservation is also recommended for stabilization, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or others known preservatives.
Die Sulfatierungsprodukte zeichnen sich durch eine deutliche Er niedrigung der Oberflächenspannung des Wassers aus und fördern die Benetzung fester Grenzflächen mit Wasser. Ferner eignen sie sich zur Emulgierung von Ölen und Fetten in wässrigen Systemen.The sulfation products are characterized by a clear Er lowering the surface tension of the water and promote the Wetting solid interfaces with water. They are also suitable for emulsifying oils and fats in aqueous systems.
Die Erfindung betrifft daher auch die Verwendung anionischer Tenside, erhältlich durch Sulfatierung von gegebenenfalls alkoxy lierten Fettsäuresorbitanestern und nachfolgender Neutralisation mit Basen, zur Herstellung oberflächenaktiver Mittel.The invention therefore also relates to the use of anionic Surfactants obtainable by sulfating optionally alkoxy gated fatty acid sorbitan esters and subsequent neutralization with bases, for the production of surface-active agents.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern. The following examples are intended to illustrate the subject matter of the invention explain.
Allgemeine Arbeitsvorschrift zur Sulfatierung von Fettsäuresor bitanestern. In einem 1-l-Sulfierreaktor mit Mantelkühlung und Gaseinleitungsrohr wurden 1.0 Mol Fettsäuresorbitanester A, B, C, D, E oder F vorgelegt und bei T = 50 bis 98°C mit 1.0 bis 3.5 Mol gasförmigem Schwefeltrioxid umgesetzt. Das Schwefeltrioxid wurde durch Erhitzen aus einer entsprechenden Menge 65 gew.-%igen Oleums ausgetrieben, mit Stickstoff auf eine Konzentration von 5 Vol.-% verdünnt und innerhalb von 50 bis 100 min in das Ausgangsprodukt eingeleitet. Das rohe Sulfierprodukt wurde anschließend mit wässriger, 25 gew.-%iger Natronlauge neutralisiert, wobei der pH-Wert zwischen 6.5 und 7.5 gehalten wurde. Die Kenndaten der Produkte sind in Tab. 1 zusammengefaßt.General working procedure for the sulfation of fatty acid sor bitanest. In a 1 liter sulfonation reactor with jacket cooling and 1.0 mol of fatty acid sorbitan esters A, B, C, D, E or F submitted and at T = 50 to 98 ° C with 1.0 to 3.5 mol gaseous sulfur trioxide implemented. The sulfur trioxide was by heating from an appropriate amount of 65% by weight oleum expelled, with nitrogen to a concentration of 5 vol .-% diluted and within 50 to 100 min in the starting product initiated. The crude sulfonation product was then with neutralized aqueous, 25 wt .-% sodium hydroxide solution, the pH was kept between 6.5 and 7.5. The characteristics of the Products are summarized in Tab. 1.
Der Aniontensidgehalt (WAS) und die Unsulfierten Anteile (US) wurden nach den DGF-Einheitsmethoden, Stuttgart, 1950-1984, H-III-10 bzw. G-II-6b ermittelt. Der Sulfatgehalt wurde als Natri umsulfat berechnet, die Bestimmung des Wassergehaltes erfolgte nach der Fischer-Methode. The anionic surfactant content (WAS) and the unsulfonated proportions (US) were based on the DGF standard methods, Stuttgart, 1950-1984, H-III-10 and G-II-6b determined. The sulfate content was called Natri Calculated sulfate, the determination of the water content was made according to the Fischer method.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3941061A DE3941061A1 (en) | 1989-12-13 | 1989-12-13 | Anionic surfactant - obtd. by sulphating opt. poly:alkoxylated fatty acid sorbitan ester] used in prepn. of surfactant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3941061A DE3941061A1 (en) | 1989-12-13 | 1989-12-13 | Anionic surfactant - obtd. by sulphating opt. poly:alkoxylated fatty acid sorbitan ester] used in prepn. of surfactant |
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| DE3941061A1 true DE3941061A1 (en) | 1991-06-20 |
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| DE3941061A Withdrawn DE3941061A1 (en) | 1989-12-13 | 1989-12-13 | Anionic surfactant - obtd. by sulphating opt. poly:alkoxylated fatty acid sorbitan ester] used in prepn. of surfactant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993025646A1 (en) * | 1992-06-17 | 1993-12-23 | Lion Corporation | Detergent composition having low skin irritability |
| EP0770607A1 (en) * | 1995-10-26 | 1997-05-02 | Henkel Kommanditgesellschaft auf Aktien | Sorbitan esterquats and their use as surface active agents especially for hair and personal care |
| US5686603A (en) * | 1995-05-04 | 1997-11-11 | Lever Brothers Company, Division Of Conopco, Inc. | Sulfated polyhydroxy compounds as anionic surfactants and a process for their manufacture |
| EP1104767A1 (en) * | 1999-11-30 | 2001-06-06 | Stichting Dienst Landbouwkundig Onderzoek | Mono- and disaccharide derivatives containing both fatty acid ester and sulfate ester groups |
-
1989
- 1989-12-13 DE DE3941061A patent/DE3941061A1/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993025646A1 (en) * | 1992-06-17 | 1993-12-23 | Lion Corporation | Detergent composition having low skin irritability |
| US5681803A (en) * | 1992-06-17 | 1997-10-28 | Lion Corporation | Detergent composition having low skin irritability |
| US5686603A (en) * | 1995-05-04 | 1997-11-11 | Lever Brothers Company, Division Of Conopco, Inc. | Sulfated polyhydroxy compounds as anionic surfactants and a process for their manufacture |
| EP0770607A1 (en) * | 1995-10-26 | 1997-05-02 | Henkel Kommanditgesellschaft auf Aktien | Sorbitan esterquats and their use as surface active agents especially for hair and personal care |
| EP1104767A1 (en) * | 1999-11-30 | 2001-06-06 | Stichting Dienst Landbouwkundig Onderzoek | Mono- and disaccharide derivatives containing both fatty acid ester and sulfate ester groups |
| WO2001040240A3 (en) * | 1999-11-30 | 2002-02-07 | Covaccine B V | Mono- and disaccharide derivatives |
| CN100345592C (en) * | 1999-11-30 | 2007-10-31 | 科瓦奇娜公司 | Monosaccharide and Disaccharide Derivatives |
| US8052981B2 (en) | 1999-11-30 | 2011-11-08 | Protherics Medicines Development Limited | Mono- and disaccharide derivatives |
| CN101108250B (en) * | 1999-11-30 | 2012-01-11 | 普罗塞力克斯药品开发有限公司 | Mono- and disaccharide derivatives |
| US8637659B2 (en) | 1999-11-30 | 2014-01-28 | Protherics Medicines Development Limited | Mono-and disaccharide derivatives |
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