DE19502194A1 - Prepn. of eruca alcohol mono:sulphate mono:sulphonate - Google Patents
Prepn. of eruca alcohol mono:sulphate mono:sulphonateInfo
- Publication number
- DE19502194A1 DE19502194A1 DE19502194A DE19502194A DE19502194A1 DE 19502194 A1 DE19502194 A1 DE 19502194A1 DE 19502194 A DE19502194 A DE 19502194A DE 19502194 A DE19502194 A DE 19502194A DE 19502194 A1 DE19502194 A1 DE 19502194A1
- Authority
- DE
- Germany
- Prior art keywords
- mono
- eruca
- sulfation
- monosulfate
- agent
- 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- Withdrawn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
- 235000013830 Eruca Nutrition 0.000 title claims abstract description 12
- 241000801434 Eruca Species 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910021653 sulphate ion Inorganic materials 0.000 title abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 6
- 230000019635 sulfation Effects 0.000 claims description 6
- 238000005670 sulfation reaction Methods 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 230000001180 sulfating effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000011552 falling film Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims 1
- 238000004851 dishwashing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000006277 sulfonation reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- -1 oleum Chemical compound 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 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
- 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
- 206010061217 Infestation Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 239000013543 active substance Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000003010 ionic group Chemical group 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000007127 saponification reaction Methods 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis 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
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/08—Sulfation or sulfonation products of fats, oils, waxes, or higher fatty acids or esters thereof with monovalent alcohols
-
- 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
- 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
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- 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
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/20—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by addition of sulfurous acid or salts thereof to compounds having carbon-to-carbon multiple bonds
-
- 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
- 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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Erucaalkohol-mono-sulfat-mono-sulfonaten durch Umsetzung von Erucaalkoholen mit Sulfiermitteln und anschließender Neutrali sation sowie die Verwendung der hergestellten Verbindungen als oberflächenaktive Substanzen und als Pastenverflüssiger.The invention relates to a method for producing Eruca alcohol mono sulfate mono sulfonates by reacting Eruca alcohols with sulfating agents and subsequent neutralis sation and the use of the compounds produced as surface-active substances and as a paste plasticizer.
Die sogenannten Gemini-Tenside sind eine relativ neue Tensid klasse, die sich durch hervorragende oberflächenaktive Eigen schaften auszeichnen. Zu den Gemini-Tensiden zählen solche Ver bindungen, die zwei hydrophile Gruppen und zwei hydrophobe Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sog. Spacer voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. (vgl. M. Ro sen, Chemtech (1993), S. 20 ff; F. Menger, C.A.Littau, J. Am. Chem. Soc. 115 (1993), S. 10083 ff.). The so-called Gemini surfactants are a relatively new surfactant class, which is characterized by excellent surface-active properties distinguish. Such Ver bonds, the two hydrophilic groups and two hydrophobic Have groups per molecule. These groups are usually separated from each other by a so-called spacer. This spacer is usually a carbon chain that should be long enough that the hydrophilic groups are sufficiently far apart so that they can act independently of each other. (see M. Ro sen, Chemtech (1993), p. 20 ff; F. Menger, C.A. Littau, J. Am. Chem. Soc. 115 (1993), pp. 10083 ff.).
Die in den genannten Literaturstellen beschriebenen Tenside zeichnen sich durch eine ungewöhnlich geringe kritische Micell konzentration aus und die Fähigkeit, die Oberflächenspannung stark zu reduzieren. Diese Tenside sind jedoch synthetisch nur schwer, teilweise durch mehrstufige Synthesen, zugänglich. Die aufwendigen Synthesewege führen zwangsläufig zu höheren Kosten, was für eine technische Anwendung und Nutzung in industriellem Maßstab, nachteilig ist.The surfactants described in the references mentioned are characterized by an unusually low critical micell concentration off and the ability to control surface tension greatly reduce. However, these surfactants are synthetic only difficult, partly accessible through multi-stage syntheses. The elaborate synthetic routes inevitably lead to higher costs, what a technical application and use in industrial Scale, is disadvantageous.
Tenside mit zwei hydrophilen Gruppen können beispielsweise als Nebenprodukte bei der Sulfierung von ungesättigten Fettalkoho len erhalten werden, wobei neben der Sulfatierung der Hydroxyl gruppe auch die Addition der Schwefelsäure an der Doppelbindung erfolgt (vgl. Morák et. al.; Tenside Detergents 15 (1978), 6, S. 299 ff.). Das bekannte Verfahren erfolgt batchweise, indem der Fettalkohol im Reaktionskolben vorgelegt und das Sul fiermittel zugetropft wird. Um höhere Gehalte an Tensiden mit zwei hydrophilen Gruppen zu erhalten, müßte die Menge Sulfier mittel erhöht werden, was jedoch zu unerwünschten Nebenproduk ten und einer unerwünschten Verfärbung des Reaktionsproduktes fuhren würde. Ein weiterer Nachteil ist, daß ein Batch-Verfah ren für die industrielle Anwendung zu aufwendig ist.Surfactants with two hydrophilic groups can be used, for example, as By-products in the sulfation of unsaturated fatty alcohol len are obtained, in addition to the sulfation of the hydroxyl group also the addition of sulfuric acid to the double bond (Morák et al .; Tenside Detergents 15 (1978), 6, P. 299 ff.). The known method is carried out in batches by the fatty alcohol is placed in the reaction flask and the sul Lubricant is added dropwise. To have higher levels of surfactants To get two hydrophilic groups would have to be the amount of sulfonation medium be increased, but this leads to undesirable by-product ten and an undesirable discoloration of the reaction product would drive. Another disadvantage is that a batch process ren is too expensive for industrial use.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein Ver fahren zur Herstellung von neuen Gemini-Tensiden zur Verfügung zu stellen, wodurch die Tenside in hohen Ausbeuten und auf eine einfache und kostengünstige Weise erhalten werden können. The present invention was based, a Ver continue to produce new Gemini surfactants to provide, whereby the surfactants in high yields and on a simple and inexpensive way can be obtained.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Erucaalkohol-mono-sulfat-mono-sulfonaten, das sich dadurch auszeichnet, daß man technische Erucaalkohole mit einer Jodzahl von 70 bis 100 kontinuierlich mit einem Sulfier mittel in einem molaren Verhältnis von funktioneller sulfierba rer Gruppe zu Sulfiermittel von 1 : 0,95 bis 1 : 1,8 umsetzt und anschließend mit einer wäßrigen Base neutralisiert.The present invention relates to a method for Production of Erucaalkohol-mono-sulfat-mono-sulfonaten, the is characterized in that technical Eruca alcohols with an iodine number of 70 to 100 continuously with a sulfier medium in a molar ratio of functional sulfierba rer group to sulfate from 1: 0.95 to 1: 1.8 and then neutralized with an aqueous base.
Überraschenderweise wurde festgestellt, daß bei der Sulfierung von technischen Erucaalkoholen Verbindungen in guter Ausbeute und hohen Sulfiergraden erhalten werden, die im Molekül zwei an ionische Gruppen, nämlich eine Sulfat- und eine Sulfonat gruppe, enthalten. Die erhaltenen Verbindungen sind sogenannte Gemini-Tenside, wobei die beiden anionischen Gruppen in der Regel in einem Abstand von etwa 9 Kohlenstoffatomen angeordnet sind, was gewährleistet, daß diese beiden hydrophilen Gruppen relativ unabhängig voneinander agieren können.Surprisingly, it was found that the sulfonation of technical Eruca alcohol compounds in good yield and high degrees of sulfonation are obtained, which are two in the molecule to ionic groups, namely a sulfate and a sulfonate group, included. The compounds obtained are so-called Gemini surfactants, the two anionic groups in the Usually arranged at a distance of about 9 carbon atoms are what ensures that these two hydrophilic groups can act relatively independently of each other.
Die erfindungsgemäß eingesetzten technischen Erucaalkohole sind im Handel erhältliche Verbindungen und können beispielsweise durch Hydrierung von Erucasäuren, niederen Erucasäureestern oder Erucasäureglyceriden nativen Ursprungs gewonnen werden. Werden Erucaalkohole nativen Ursprungs eingesetzt, so liegen diese in der Regel im Gemisch mit anderen Fettalkoholen vor, wobei die Gemische auch Anteile an ungesättigten Fettalkoholen enthalten können.The technical erucalcohols used according to the invention are commercially available compounds and can for example by hydrogenation of erucic acids, lower erucic acid esters or erucic acid glycerides of native origin. If erucalcohols of native origin are used, so lie these usually in a mixture with other fatty alcohols, the mixtures also containing unsaturated fatty alcohols can contain.
Die Umsetzung zum Erucaalkohol-mono-sulfat-mono-sulfonat er folgt durch kontinuierliche Umsetzung des Erucaalkohols mit dem Sulfiermittel. Reaktoren, die nach dem Fallfilmprinzip arbei ten, haben sich als besonders geeignet erwiesen. The implementation of the Erucaalkohol-mono-sulfate-mono-sulfonate he follows through continuous reaction of the Eruca alcohol with the Sulfating agent. Reactors that work according to the falling film principle ten, have proven to be particularly suitable.
Die Sulfierung der Erucaalkohole kann man mit üblichen Sul fiermitteln, wie z. B. Schwefelsäure, Oleum, Chlorsulfonsäure, Aminosulfonsäure und gasförmigem Schwefeltrioxid im Gemisch mit einem Inertgas erfolgen, wobei Chlorsulfonsäure und gasförmiges Schwefeltrioxid bevorzugt sind. Beim Einsatz von Schwefeltrioxid wird dieses mit Luft oder Stickstoff verdünnt und vorzugsweise wird ein Gasgemisch mit ca. 1 bis 8, insbeson dere 3 bis 5 Vol.-% Schwefeltrioxid eingesetzt.The sulfation of the Erucaalkohole can with usual Sul lubricants such. B. sulfuric acid, oleum, chlorosulfonic acid, Aminosulfonic acid and gaseous sulfur trioxide mixed with an inert gas, chlorosulfonic acid and gaseous Sulfur trioxide are preferred. When using Sulfur trioxide is diluted with air or nitrogen and preferably a gas mixture with about 1 to 8, in particular 3 to 5 vol .-% sulfur trioxide used.
Das molare Einsatzverhältnis von funktioneller sulfierbarer Gruppe zu Sulfiermittel kann 1 : 0,95 bis 1 : 1,8 und vor zugsweise 1 : 1,0 bis 1 : 1,3 betragen. Üblicherweise wird die Sulfierung bei 20 bis 98°C durchgeführt. Im Hinblick auf die Viskosität der Ausgangsverbindungen einerseits und die Farb qualität der resultierenden Sulfierprodukte andererseits, hat sich ein Temperaturbereich von 25 bis 70°C als optimal erwie sen.The molar ratio of functional sulfatable Group to sulfating agent can be 1: 0.95 to 1: 1.8 and above preferably 1: 1.0 to 1: 1.3. Usually the Sulfation carried out at 20 to 98 ° C. In terms of Viscosity of the starting compounds on the one hand and the color quality of the resulting sulfonation products, on the other hand, has a temperature range of 25 to 70 ° C proved to be optimal sen.
Das bei der Sulfierung anfallende saure rohe sulfierte Produkt wird anschließend mit einer Base neutralisiert und bevorzugt auf einen pH-Wert unter 10, besonders bevorzugt von 6,5 bis 9,5 eingestellt. Ein zu hoher pH-Wert sollte vermieden werden. Es wurde festgestellt, daß bei sehr hohen pH-Werten die Esterbin dung instabil ist und bereits bei einer kurzfristigen Über schreitung eine starke Verseifung zu beobachten ist. Als Basen für die Neutralisation kommen Alkalimetallhydroxide wie Natri um-, Kalium- und Lithiumhydroxid, Erdalkalimetalloxide und -hy droxide wie Magnesiumoxid, Magnesiumhydroxid, Calciumoxid und Calciumhydroxid, Ammoniak, Mono-, Di- und Tri-C2-4-Alkanola mine, beispielsweise Mono-, Di- und Triethanolamin sowie primä re, sekundäre oder tertiäre C1-4-Alkylamine in Betracht. Die Neutralisationsbasen werden bevorzugt in Form 5 bis 55 gew.-%iger wäßriger Lösungen eingesetzt, wobei 5 bis 25 gew.-%ige wäßrige Natriumhydroxidlösungen bevorzugt sind. The acidic crude sulfonated product obtained in the sulfonation is then neutralized with a base and preferably adjusted to a pH below 10, particularly preferably from 6.5 to 9.5. A too high pH should be avoided. It was found that the ester bond is unstable at very high pH values and strong saponification can be observed even if it is exceeded for a short time. As bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C 2-4 alkanols, for example Mono-, di- and triethanolamine as well as primary, secondary or tertiary C 1-4 alkylamines can be considered. The neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, 5 to 25% by weight aqueous sodium hydroxide solutions being preferred.
Die Sulfierprodukte können nach der Neutralisation in an sich bekannter Weise durch Zusatz von Wasserstoffperoxid- oder Na triumhypochloritlösung gebleicht werden. Dabei werden, bezogen auf den Feststoffgehalt der Sulfierprodukte in der Lösung, 0,2 bis 2 Gew.-% Wasserstoffperoxid, berechnet als 100 gew.-%ige Substanz oder entsprechende Mengen Natriumhypochlorit einge setzt. Der pH-Wert der Lösungen kann unter Verwendung geeig neter Puffermittel, z. B. mit Natriumphosphat oder Zitronen säure konstant gehalten werden. Zur Stabilisierung gegen Bakte rienbefall empfiehlt sich ferner eine Konservierung, z. B mit Formaldehydlösung, p-Hydroxybenzoat, Sorbinsäure oder anderen bekannten Konservierungsstoffen.The sulfonation products can in themselves after neutralization known manner by adding hydrogen peroxide or Na trium hypochlorite solution are bleached. Here are related on the solids content of the sulfonation products in the solution, 0.2 up to 2% by weight of hydrogen peroxide, calculated as 100% by weight Substance or corresponding amounts of sodium hypochlorite puts. The pH of the solutions can be used appropriately Neter buffering agent, e.g. B. with sodium phosphate or lemons acid can be kept constant. For stabilization against bacteria Rien infestation also recommends conservation, e.g. B with Formaldehyde solution, p-hydroxybenzoate, sorbic acid or others known preservatives.
Die erfindungsgemäß hergestellten Erucaalkohol-mono-sulfat mono-sulfonate weisen grenzflächenaktive Eigenschaften auf. Sie fördern beispielsweise die Benetzung fester Oberflächen und die Emulgierung von ansonsten nicht miteinander mischbaren Phasen. Außerdem wurde festgestellt, daß sie gut als Pastenverflüssiger für hochviskose Tensidsysteme geeignet sind.The eruca alcohol monosulfate produced according to the invention mono-sulfonates have surface-active properties. she promote, for example, the wetting of solid surfaces and the Emulsification of otherwise immiscible phases. It has also been found to be good as a paste plasticizer are suitable for highly viscous surfactant systems.
Ein weiterer Gegenstand der Erfindung betrifft daher die Ver wendung der erfindungsgemäß hergestellten Verbindungen zur Her stellung von Wasch-, Spül-, Reinigungs- und Avivagemitteln so wie Mitteln zur Haar- und Körperpflege, in denen sie in Mengen von 1 bis 50, vorzugsweise 5 bis 30 Gew.-%, bezogen auf die Mittel, die enthalten sein können.Another object of the invention therefore relates to the Ver use of the compounds prepared according to the invention for provision of washing, rinsing, cleaning and finishing agents such as hair and body care products, in which they are in quantities from 1 to 50, preferably 5 to 30 wt .-%, based on the Means that may be included.
Das folgende Beispiel soll den Gegenstand der Erfindung näher erläutern.The following example is intended to illustrate the subject matter of the invention explain.
Nach beendeter Reaktion wurde das Reaktionsprodukt noch zwei Stunden im Dampfbad nachhydrolisiert, der pH-Wert wurde dabei mit einigen Tropfen NaOH auf etwa 9 gehalten.After the reaction ended, the reaction product became two more Hydrolyzed for hours in the steam bath, the pH was thereby kept at about 9 with a few drops of NaOH.
Handelsüblicher Erucaalkohol wurde bei einer Temperatur von 80°C aufgeschmolzen. Der aufgeschmolzene Erucaalkohol wurde in einen Labor-Conti-Fallfilmreaktor (Reaktorabmessungen: 110 cm Länge, Innendurchmesser: 0,6 cm) mit vorgeschaltetem Oleumver dampfer wurde unter Verwendung eines Stickstoffstromes von ca. 750 l/h mit einem Produktstrom von 10 g/min eingeführt (Das Mo lekulargewicht wurde dabei aus der OH-Zahl des Ausgangsproduk tes bestimmt). Gleichzeitig wurde 65 gew.-%iges Oleum mit einer Rate von 1,05 Moläquivalenten pro funktioneller Gruppe in den Verdampfer gepumpt. Das dort entstehende Schwefeltrioxid wurde mit einem Stickstoffstrom von 250 l/h aus dem Verdampfer ausgetrieben und ebenfalls in den Reaktor überführt. Der Reak tor wurde dabei mit Wasser (30°C) temperiert. Der entstehende Schwefelsäurehalbester wurde am Reaktorausgang entgast und in einem Becherglas unter kontinuierlicher Zugabe und unter Eis kühlung und kräftigem Rühren mit 25 gew.-%iger Natronlauge neu tralisiert.Commercial erucalcohol was made at a temperature of Melted 80 ° C. The melted eruca alcohol was in a Labor-Conti falling film reactor (reactor dimensions: 110 cm Length, inner diameter: 0.6 cm) with upstream oleum converter steamer was used using a nitrogen flow of approx. 750 l / h introduced with a product flow of 10 g / min (Mon. The molecular weight was calculated from the OH number of the starting product tes determined). At the same time 65 wt .-% oleum with a Rate of 1.05 molar equivalents per functional group in the Evaporator pumped. The sulfur trioxide produced there was with a nitrogen flow of 250 l / h from the evaporator expelled and also transferred to the reactor. The reak gate was tempered with water (30 ° C). The emerging Sulfuric acid half-ester was degassed at the reactor outlet and in a beaker with continuous addition and under ice cooling and vigorous stirring with 25% by weight sodium hydroxide solution tralized.
Die Kenndaten der so erhaltenen Tensidpasten wurden nach den Einheitsmethoden der DGF bestimmt. Zwecks weiterer analytischer Untersuchungen wurden die Tensidpasten im Vakuum gefrierge trocknet. The characteristic data of the surfactant pastes obtained in this way were determined according to Standard methods of the DGF determined. For the purpose of further analytical Investigations were freezing the surfactant pastes in vacuum dries.
Trockenrückstand (TR): 37,3 Gew.-%
Unsulfierte Anteile (US): 0,6 Gew.-%
Sulfiergrad (S°): 98,4%
Natriumsulfat: 1,7 Gew.-%
Organisch gebundener Schwefel: 4,3 Gew.-% (entspricht 2,1 Mol
S pro Mol Mono-sulfat-mono-sulfonat).Dry residue (TR): 37.3% by weight
Unsulfated parts (US): 0.6% by weight
Degree of sulfonation (S °): 98.4%
Sodium sulfate: 1.7% by weight
Organically bound sulfur: 4.3% by weight (corresponds to 2.1 moles of S per mole of monosulfate monosulfonate).
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19502194A DE19502194A1 (en) | 1995-01-25 | 1995-01-25 | Prepn. of eruca alcohol mono:sulphate mono:sulphonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19502194A DE19502194A1 (en) | 1995-01-25 | 1995-01-25 | Prepn. of eruca alcohol mono:sulphate mono:sulphonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19502194A1 true DE19502194A1 (en) | 1996-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19502194A Withdrawn DE19502194A1 (en) | 1995-01-25 | 1995-01-25 | Prepn. of eruca alcohol mono:sulphate mono:sulphonate |
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| Country | Link |
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| DE (1) | DE19502194A1 (en) |
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1995
- 1995-01-25 DE DE19502194A patent/DE19502194A1/en not_active Withdrawn
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