EP1188818B1 - Method for preparing light-coloured alkyl and/or alkenyloligoglycoside mixtures - Google Patents
Method for preparing light-coloured alkyl and/or alkenyloligoglycoside mixtures Download PDFInfo
- Publication number
- EP1188818B1 EP1188818B1 EP01121508A EP01121508A EP1188818B1 EP 1188818 B1 EP1188818 B1 EP 1188818B1 EP 01121508 A EP01121508 A EP 01121508A EP 01121508 A EP01121508 A EP 01121508A EP 1188818 B1 EP1188818 B1 EP 1188818B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- alcohol
- carbon atoms
- mixtures
- alkenyl
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 64
- 125000000217 alkyl group Chemical group 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 32
- 150000002191 fatty alcohols Chemical class 0.000 claims description 44
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004061 bleaching Methods 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000007844 bleaching agent Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 238000004851 dishwashing Methods 0.000 claims description 6
- 229920000151 polyglycol Polymers 0.000 claims description 5
- 239000010695 polyglycol Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 150000001298 alcohols Chemical class 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- -1 arachyl alcohol Chemical compound 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 229960004592 isopropanol Drugs 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 5
- 239000004435 Oxo alcohol Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- DJYWKXYRGAMLRE-QXMHVHEDSA-N (z)-icos-9-en-1-ol Chemical compound CCCCCCCCCC\C=C/CCCCCCCCO DJYWKXYRGAMLRE-QXMHVHEDSA-N 0.000 description 3
- TVPWKOCQOFBNML-SEYXRHQNSA-N (z)-octadec-6-en-1-ol Chemical compound CCCCCCCCCCC\C=C/CCCCCO TVPWKOCQOFBNML-SEYXRHQNSA-N 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 229960001031 glucose Drugs 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-N 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- CFOQKXQWGLAKSK-KTKRTIGZSA-N (13Z)-docosen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCO CFOQKXQWGLAKSK-KTKRTIGZSA-N 0.000 description 2
- IKYKEVDKGZYRMQ-PDBXOOCHSA-N (9Z,12Z,15Z)-octadecatrien-1-ol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCO IKYKEVDKGZYRMQ-PDBXOOCHSA-N 0.000 description 2
- CFOQKXQWGLAKSK-UHFFFAOYSA-N 13-docosen-1-ol Natural products CCCCCCCCC=CCCCCCCCCCCCCO CFOQKXQWGLAKSK-UHFFFAOYSA-N 0.000 description 2
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960000735 docosanol Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- LEAQUNCACNBDEV-KHPPLWFESA-N (Z)-undec-1-en-1-ol Chemical compound CCCCCCCCC\C=C/O LEAQUNCACNBDEV-KHPPLWFESA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000673 dextrose monohydrate Drugs 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
Definitions
- the invention relates to a process for the preparation of light-colored alkyl and / or Alkenyloligoglycosid mixtures and their use in detergents, dishwashing detergents and cleaners.
- Alkyl oligoglucosides are important surfactants because as nonionic compounds they are compatible with a variety of other ingredients but exhibit foam and detergency much more similar to anionic surfactants. Due to their good biodegradability and skin compatibility, they are used in cosmetics and in detergents, dishwashing detergents and cleaning agents. Their preparation is based on glucose and branched, unbranched, and saturated and unsaturated alcohols, which are acetalized in the presence of acidic catalysts. To shift the reaction equilibrium of the alcohol is usually used in considerable excess.
- reaction mixtures with 20 to 50% of alkyl and / or Alkenyloligoglycoside and 50 to 80% alcohol, which has the consequence that the resulting glucosides must then be removed with high technical complexity of unreacted alcohol before they are then water be pasted and bleached.
- the content of water should not be greater than 8% before bleaching, since water is still introduced through the bleaching step. In the context of this process, water must be added during the bleaching process and removed again accordingly.
- the surfactant mixtures of alkyl and / or alkenyl oligoglycosides and ethoxylated nonionic surfactants at least 3.8% water.
- the surfactant mixtures according to the invention are prepared almost free from water, ie with water contents of less than 2% by weight.
- German Patent DE 19543990 discloses liquid, anhydrous precursors for the preparation of detergents, dishwashing detergents and cleaners which consist of alkyl and / or alkenyl oligoglycosides and alkyl polyglycol ethers in a weight ratio of 10:90 and 90:10. There are described at 40 ° C flowable mixtures that can be used in granulation for the production of detergents.
- Non-prepublished German application DE 10019405 (Cognis) describes anhydrous detergent granules containing technical mixtures of alkyl and / or alkenyl oligoglycosides and a maximum of 30% by weight of fatty alcohol. These surfactant mixtures can be mixed or extruded together with detergent additives.
- the object of the invention is to develop a process for producing light-colored alkyl and / or alkenyl oligoglycoside mixtures which avoids the disadvantages mentioned, in particular to prepare mixtures of low water content alkyl and / or alkenyl oligoglycoside mixtures.
- the invention relates to a process for the preparation of surfactant mixtures having a Klett color number of ⁇ 60, the mixtures containing at least alkyl and / or Alkenyloligoglycoside, as rheology-modifying agent fatty alcohols of the formula (I) R 1 -OH (I) wherein R 2 is an aliphatic, linear or branched hydrocarbon radical having 4 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and containing less than 2 wt.% Water. Preference is given to those mixtures which are adjusted at temperatures of 85 to 130 ° C, in particular at 90 to 120 ° C to viscosities of 10 to 1000, preferably 50 to 500 mPas, and then bleached.
- the preparation of the mixture is possible without the addition of water, that is, no water is added to obtain bleachable, pumpable and easy-to-use mixture with favorable rheological properties.
- Particular preference is given to mixtures which contain less than 2% by weight, preferably not more than 1.5% by weight, in particular not more than 0.5% by weight, of water, based on the active substance alkyl and / or alkenyl oligoglycosides.
- This water is mainly introduced via the bleaching agents used and means for pH adjustment.
- the invention includes the recognition that the content of alcohol according to the invention improves the rheological properties of the alkyl and / or alkenyl oligoglycosides. Without being bound by any doctrine, the fatty alcohol content of the invention first enables the bleaching process.
- a process for the preparation of light-colored surfactant mixtures preferably, which is characterized in that the resulting mixtures maximum Contain 1.5% by weight of water.
- alkyl and / or alkenyl oligoglycosides which follow the formula (II), R 2 O- [G] p (II) in which R 2 is a branched and unbranched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.
- R 2 is a branched and unbranched alkyl and / or alkenyl radical having 4 to 22 carbon atoms
- G is a sugar radical having 5 or 6 carbon atoms
- p is a number from 1 to 10.
- They are preferably prepared by reaction of glucose or dextrose monohydrate and fatty alcohol in the presence of catalysts. They can be obtained by relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is here made to the documents EP A1 0301298, WO 90/03977 and to "Alkyl Polyglycosides, Technology, Properties and Applications" (K
- the alkyl and / or alkenyl oligoglycosides can be of aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
- the index number p in the general Formula (II) indicates the degree of oligomerization (DP), i. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10.
- alkyl and / or Alkenyloligoglykoside with a moderate degree of oligomerization p used from 1.1 to 3.0. From an application point of view, such alkyl and / or Alkenyloligoglykoside preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
- the alkyl or alkenyl radical R 2 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
- the alkyl or alkenyl radical R 1 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 18, carbon atoms and also C 12-15 oxo alcohols or the mixtures.
- Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
- Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
- Aliphatic, branched and unbranched, saturated and unsaturated alcohols having a carbon chain length of 2 to 31 are used or mixtures thereof. Particularly preferred are branched alcohols having 11 to 22 carbon atoms and a low boiling and solidification point.
- R 1 can be equated with R 2 according to formula (II).
- These fatty alcohols serve as a rheology modifying agent in the alkyl and / or alkenyl oligoglycoside mixture.
- a method for producing the inventive, light colored surfactant mixtures in which 6 to 30, preferably 8 to 25 and in particular 10 to 15 wt.% Of a rheology-modifying agent are included.
- the information on the weight ratio refer to the active substance content of alkyl and / or alkenyl oligoglycoside.
- the technical synthesis mixtures containing alkyl and / or alkenyl oligoglycosides and alcohol are preferably prepared, the alcohol still free from the reaction, preferably fatty alcohols of the formula (I) from 6 to 30, preferably 8 to 25, in particular 10 to 15 wt.% - Based on the active substance alkyl and / or Alkenyloligoglycosid - included.
- the surfactant mixtures according to the invention by mixing alkyl and / or alkenyl oligoglycosides with alcohols, preferably fatty alcohols of the formula (I).
- the surfactant mixtures according to the invention can also be prepared by mixing with an alcohol other than that used for the synthesis. Preference is given to proceeding when the synthesis alcohol has an intense inherent odor. In this case, the synthesis alcohol is removed by distillation and replaced by a low-odor alcohol.
- rheology-modifying agents used are compounds selected from the group formed by alcohols, alkoxylated alkanols and alkylene oxides.
- saturated and unsaturated, linear and branched alcohols to reduce the viscosity used.
- primary, secondary and tertiary, but also monohydric and dihydric alcohols be used.
- examples of these are ethanol, n-butanol, isopropanol and glycols Ethylene, propylene and butylene base.
- Particularly preferred is the use of ethanol and propylene glycol.
- fatty alcohols of the formula (I), either due to the process already in the Alkyl and / or alkenyl oligoglycoside mixture (see depletion) are included or subsequently the alkyl and / or Alkenyloligoglycosiden be admixed.
- Fatty alcohols of the formula (I) are preferably used as rheology-modifying agent.
- Fatty alcohols are primary alcohols of the formula (I), R 1 OH (I) in which R 1 is an aliphatic, linear or branched hydrocarbon radical having 4 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
- Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
- Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel
- the alkenyl radical R 1 can be derived from primary unsaturated alcohols.
- unsaturated alcohols are undecene-1-ol, laurolein alcohol, myristoleic alcohol, palmitoleic alcohol, petroselide alcohol, oleyl alcohol, elaidyl alcohol, ricinoleic alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidonic alcohol, erucalcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and mixtures thereof and mixtures of unsaturated and saturated fatty alcohols obtained by the processes described in EP 0724 555 B1 .
- mixtures of saturated and unsaturated fatty alcohols on vegetable Base which is essentially, i. at least 10% by weight unsaturated, and iodine numbers of 20 up to 130, preferably 20 to 110, in particular 20 to 85 and a conjugate content of less than 4.5% by weight, preferably 6 wt .-%.
- Guerbet alcohols which are branched at the 2-position with an alkyl group and are usually prepared by base-catalyzed condensation of fatty alcohols.
- An overview on the subject is from AJ O'Lennick and RE Bilbo in Soap Cosm.Chem.Spec. April, 52 (1987).
- Preferred Guerbet alcohols are derived from fatty alcohols having 6 to 22 carbon atoms, such as 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
- Guerbet alcohols which are prepared on the basis of C 6 -C 12 -Fettalkoholmischungen containing caproic alcohol, caprylic alcohol, 2-ethylhexanol, capric alcohol and / or lauryl alcohol.
- a typical fatty alcohol cut suitable as starting material for the preferred Guerbet alcohols contains less than 5% by weight of C 6 , 50 to 60% by weight of C 8 , 35 to 45% by weight of C 10 and less than 2% by weight .-% C 12 .
- Guerbet alcohols of this type are described in greater detail in German Patent DE 4341794 C1 (Henkel), the teaching of which is expressly incorporated.
- branched fatty alcohols the so-called oxo alcohols, having 4 to 20 carbon atoms usually carry 1 to 4 methyl or ethyl groups as branches and after the Oxo process can be produced.
- evaporator types come into consideration, which take into account this fact, but preferably thin-film evaporator, falling film evaporator or short path evaporator and - if necessary - any combination of these components.
- the depletion can then take place in a manner known per se, for example at temperatures in the range from 110 to 220 ° C. and reduced pressures of from 0.1 to 10 mbar.
- the surfactant mixtures according to the invention are additionally with alkoxylated alkanols added.
- alkoxylated alkanols of the formula (III) are further rheology-modifying Medium.
- Typical examples of these are fatty alcohol polyethylene glycol / polypropylene glycol ethers of Formula (III) or Fettalkoholpolypropylenglykol / polyethylene glycol ether of the formula (IV).
- further rheology-modifying agents are fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III) which are optionally end-capped, R 3 O (CH 2 CH 2 O) n [CH 2 (CH 3 ) CHO] m R 4 (III) in which R 3 is an alkyl and / or alkylene radical having 8 to 22 C atoms, R 4 is H or an alkyl radical having 1 to 8 C atoms, n is a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m is 0 or a number from 1 to 10.
- fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) which are optionally end-capped, R 5 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r R 6 (IV) in R 5 is an alkyl and / or alkylene radical having 8 to 22 C atoms, R 6 is H or an alkyl radical having 1 to 8 C atoms, q is a number from 1 to 5 and r is a number from 0 to 15, is used as a rheology modifying agent.
- R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms
- n is a number from 1 to 10
- m is 0
- R 4 is hydrogen
- these are adducts of 1 to 10 moles of ethylene oxide with monofunctional alcohols.
- the above-described alcohols such as fatty alcohols, oxo alcohols and Guerbet alcohols are suitable.
- Such alcohol ethoxylates are those which have a narrow homolog distribution.
- Further suitable representatives of non-terminally capped representatives are those of the formula (III) in which R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, n is a number from 2 to 7, m is a number of 3 to 7 and R 4 is hydrogen.
- R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms
- n is a number from 2 to 7
- m is a number of 3 to 7
- R 4 is hydrogen.
- alkylene oxides as rheology-modifying agent.
- bleaching agents preferably Hydrogen peroxide, in particular in the form of a 30 to 35% aqueous solution used.
- bleaching with organic peracids e.g. -Dodecanedioic.
- it can be bleached with black liquor.
- the pH is added by addition of alkali, preferably sodium hydroxide solution during the bleaching process preferably to values between 6 and 12, in particular 7 to 10 set.
- alkali preferably sodium hydroxide solution
- a sample is drawn. The pH then becomes determined in a 20% solution of the surfactant mixture according to the invention in 15% isopropanol.
- the agents contain 6 to 30% by weight of alcohols, preferably preferably fatty alcohol (based on the active substance alkyl and / or alkenyl oligoglycoside).
- the agents according to the invention may preferably contain bleaches which can be added either as a result of the process or separately.
- Next mixtures are the subject of the application, which are characterized in that they 6 to 30, preferably 8 to 25, in particular 10 to 15 wt.% Fatty alcohol (based on the active substance Alkyl and / or alkenyl oligoglycoside), a viscosity of 10 to 1000, preferably 50 to 500 mPas and a color number ⁇ 60, preferably ⁇ 40, in particular ⁇ 30 according to Klett, measured in one 1% solution of the mixture according to the invention in iso-propyl alcohol.
- Fatty alcohol based on the active substance Alkyl and / or alkenyl oligoglycoside
- a viscosity 10 to 1000, preferably 50 to 500 mPas and a color number ⁇ 60, preferably ⁇ 40, in particular ⁇ 30 according to Klett, measured in one 1% solution of the mixture according to the invention in iso-propyl alcohol.
- anhydrous, light colored alkyl and / or Alkenyloligoglycosid mixtures are obtained, which can be incorporated easily and inexpensively preferably in detergents, dishwashing detergents and cleaning agents, for example by applying to a solid detergent ingredient.
- This can be done by spray drying but also in a mixer or a fluidized bed, which is dried and granulated at the same time.
- Another object of the application is therefore the use of the surfactant mixtures according to the invention in detergents, dishwashing detergents, formers and cleaners.
- liquid and gel washing, rinsing and cleaning agents can be formulated.
- the surfactant mixtures may still contain bleaches, which then in water-free formulations represent a stable bleaching system which unfolds its bleaching action during the subsequent washing or cleaning process.
- a further advantage of the surfactant mixtures according to the invention containing alkyl and / or alkenyl oligoglycosides and fatty alcohol is that they are less hydrophilic than pure alkyl and / or alkenyl oligoglycosides. Therefore, these mixtures, for example in the form of granules show a lower tendency to clog on storage.
- the following table describes alkyl and / or alkenyl oligoglycoside mixtures with various Fatty alcohol content.
- the inventive examples E1 to E3 are the comparative examples V1 to V2 faced.
- the table shows that the viscosity of the surfactant mixtures according to the invention with increasing fatty alcohol content decreases and the bleaching temperature can be correspondingly lower.
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Description
Die Erfindung betrifft ein Verfahren zur Herstellung von hellfarbigen Alkyl- und/oder Alkenyloligoglycosid-Mischungen und deren Verwendung in Wasch-, Spül- und Reinigungsmitteln.The invention relates to a process for the preparation of light-colored alkyl and / or Alkenyloligoglycosid mixtures and their use in detergents, dishwashing detergents and cleaners.
Alkyloligoglucoside stellen wichtige Tenside dar, da sie als nichtionische Verbindungen mit einer
Vielzahl von weiteren Inhaltsstoffen kompatibel sind, jedoch ein Schaum- und Reinigungsvermögen
zeigen, welches viel mehr dem anionischer Tensiden gleicht. Aufgrund ihrer guten Abbaubarkeit und
Hautverträglichkeit finden sie Einsatz in der Kosmetik und in Wasch-, Spül- und Reinigungsmitteln.
Zu ihrer Herstellung geht man von Glucose und verzweigten, unverzweigten, sowie gesättigten und
ungesättigten Alkoholen aus, die in Gegenwart saurer Katalysatoren acetalisiert werden. Zur
Verlagerung des Reaktionsgleichgewichtes wird der Alkohol in der Regel in erheblichem Überschuß
eingesetzt. Es werden so Reaktionsgemische mit 20 bis 50% Alkyl- und/oder Alkenyloligoglycoside und
50 bis 80% Alkohol erhalten, was zur Folge hat, dass die resultierenden Glucoside anschließend mit
hohem technischen Aufwand von nicht umgesetztem Alkohol befreit werden müssen, ehe sie dann mit
Wasser angepastet und gebleicht werden.Alkyl oligoglucosides are important surfactants because as nonionic compounds they are compatible with a variety of other ingredients but exhibit foam and detergency much more similar to anionic surfactants. Due to their good biodegradability and skin compatibility, they are used in cosmetics and in detergents, dishwashing detergents and cleaning agents.
Their preparation is based on glucose and branched, unbranched, and saturated and unsaturated alcohols, which are acetalized in the presence of acidic catalysts. To shift the reaction equilibrium of the alcohol is usually used in considerable excess. There are thus obtained reaction mixtures with 20 to 50% of alkyl and / or Alkenyloligoglycoside and 50 to 80% alcohol, which has the consequence that the resulting glucosides must then be removed with high technical complexity of unreacted alcohol before they are then water be pasted and bleached.
Eine Bleiche der Alkyl- und/oder Alkenyloligoglycosid ist in der Regel nötig, da sich beim Abdestillieren
des Alkohols dunkle Zersetzungsprodukte bilden. Bisher ist der Bleichvorgang nur unter großem
technischen Aufwand möglich.
Gegenstand der europäischen Anmeldung EP 0 799 884 A2 (Unilever) sind flüssige Tensidmischungen
aus Alkyl- und/oder Alkenyloligoglycoside und ethoxylierten, nichtionischen Tensiden im Gewichtsverhältnis
35:65 und 65:35 und 2 bis 25 % Wasser und ein Verfahren zur Herstellung der Tensidmischungen.
In dem Verfahren wird als Bleichmittel eine 30%ige wässrige Wasserstoffperoxidlösung
bei Temperaturen von 80 bis 100 °C eingesetzt. Der Gehalt an Wasser soll vor der Bleiche nicht größer
als 8 % sein, da noch Wasser durch den Bleichschritt eingebracht wird. Im Rahmen dieses Verfahrens
muß beim Bleichvorgang Wasser zugesetzt und entsprechend wieder entfernt werden. Die Tensidmischungen
aus Alkyl- und/oder Alkenyloligoglycosiden und ethoxylierten, nichtionischen Tensiden
mindestens 3,8 % Wasser. Im Gegensatz dazu werden die erfindungsgemäßen Tensidmischungen
nahezu wasserfrei, d.h. mit Wassergehalten von weniger als 2 Gew.% hergestellt.Bleaching of the alkyl and / or Alkenyloligoglycosid is usually necessary because form when distilling off the alcohol dark decomposition products. So far, the bleaching process is possible only with great technical effort.
The subject of the European application EP 0 799 884 A2 (Unilever) are liquid surfactant mixtures of alkyl and / or alkenyl oligoglycosides and ethoxylated, nonionic surfactants in a weight ratio of 35:65 and 65:35 and 2 to 25% water and a process for the preparation of the surfactant mixtures. In the process, a 30% strength aqueous hydrogen peroxide solution is used at temperatures of 80 to 100 ° C. as bleaching agent. The content of water should not be greater than 8% before bleaching, since water is still introduced through the bleaching step. In the context of this process, water must be added during the bleaching process and removed again accordingly. The surfactant mixtures of alkyl and / or alkenyl oligoglycosides and ethoxylated nonionic surfactants at least 3.8% water. In contrast, the surfactant mixtures according to the invention are prepared almost free from water, ie with water contents of less than 2% by weight.
Aus der deutschen Patentschrift DE 19543990 (Henkel) sind flüssige, wasserfreie Vorprodukte für die Herstellung von Wasch-, Spül- und Reinigungsmitteln bekannt, die aus Alkyl- und/oder Alkenyloligoglycoside und Alkylpolyglycolether im Gewichtsverhältnis 10:90 und 90:10 bestehen. Es werden bei 40°C fließfähige Mischungen beschrieben, die sich bei Granulierverfahren zur Herstellung von Waschmitteln einsetzen lassen.German Patent DE 19543990 (Henkel) discloses liquid, anhydrous precursors for the preparation of detergents, dishwashing detergents and cleaners which consist of alkyl and / or alkenyl oligoglycosides and alkyl polyglycol ethers in a weight ratio of 10:90 and 90:10. There are described at 40 ° C flowable mixtures that can be used in granulation for the production of detergents.
In der nicht vorveröffentlichten deutschen Anmeldung DE 10019405 (Cognis) sind wasserfreie Waschmittelgranulate beschrieben, die technische Mischungen von Alkyl- und/oder Alkenyloligoglycoside und maximal 30 Gew.% Fettalkohol enthalten. Diese Tensidmischungen können zusammen mit Waschmittelzusatzstoffen vermischt oder extrudiert werden. Non-prepublished German application DE 10019405 (Cognis) describes anhydrous detergent granules containing technical mixtures of alkyl and / or alkenyl oligoglycosides and a maximum of 30% by weight of fatty alcohol. These surfactant mixtures can be mixed or extruded together with detergent additives.
Der Erfindung liegt die Aufgabe zugrunde ein Verfahren zur Herstellung hellfarbige Alkyl- und/oder Alkenyloligoglycosid-Mischungen zu entwickeln, das die genannten Nachteile vermeidet, insbesondere Alkyl- und/oder Alkenyloligoglycosid-Mischungen mit niedrigem Wassergehalt herzustellen.The object of the invention is to develop a process for producing light-colored alkyl and / or alkenyl oligoglycoside mixtures which avoids the disadvantages mentioned, in particular to prepare mixtures of low water content alkyl and / or alkenyl oligoglycoside mixtures.
Dies wurde gelöst, durch den erfindungsgemäßen Gehalt an bestimmten rheologiemodifizierenden Mitteln. Dadurch ergeben sich günstige rheologische Eigenschaften der Tensidmischungen und diese sind damit einer direkten Bleiche, ohne großen technischen Aufwand zugänglich, d.h. zum Bleichen müssen keine wässrigen Alkyl- und/oder Alkenyloligoglycosid-Pasten durch Zusatz von Wasser hergestellt werden. Mit dem erfindungsgemäßen Verfahren ist es möglich hellfarbige, hochkonzentrierte Alkylund/oder Alkenyloligoglycosid-haltige Tensidmischungen herzustellen, die sowohl durch ihr Herstellverfahren also auch bei Transport ökonomisch begünstigt sind und dadurch Energie und Kosten sparen.This was solved by the content according to the invention of certain rheology-modifying agents. This results in favorable rheological properties of the surfactant mixtures and these are thus a direct bleach, accessible without great technical effort, ie for bleaching no aqueous alkyl and / or Alkenyloligoglycosid pastes must be prepared by the addition of water. It is possible with the process according to the invention to produce light-colored, highly concentrated alkyl and / or alkenyl oligoglycoside-containing surfactant mixtures which are economically favored both by their preparation process and during transport and thus save energy and costs.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Tensidmischungen mit Farbzahl nach
Klett von <60, wobei die Mischungen mindestens Alkyl- und/oder Alkenyloligoglycoside, als rheologiemodifizierendes
Mittel Fettalkohole der Formel (I) enthalten sind
Die Herstellung der Mischung ist ohne Zusatz von Wasser möglich, d.h. es wird kein Wasser zugesetzt
um bleichbare, pumpfähige und einfach zu verarbeitende Mischung mit günstigen rheologischen
Eigenschaften zu erhalten. Besonders bevorzugt sind Mischungen, die weniger als 2 Gew.%, vorzugsweise
maximal 1,5 Gew.%, insbesondere maximal 0,5 Gew.% Wasser - bezogen auf Aktivsubstanz
Alkyl- und/oder Alkenyloligoglycoside - enthalten. Dieses Wasser wird vor allem über die eingesetzten
Bleichmittel und Mittel zur pH-Wert-Einstellung eingebracht.
Die Erfindung schließt die Erkenntnis ein, dass der erfindungsgemäße Gehalt an Alkohol die rheologischen
Eigenschaften der Alkyl- und/oder Alkenyloligoglycoside verbessert. Ohne an eine Lehre gebunden
zu sein, ermöglicht der erfindungsgemäße Fettalkoholgehalt erst den Bleichvorgang.
Unter dem Begriff hellfarbig sind Farbzahlen nach Klett < 60, vorzugsweise < 40, insbesondere <30 zu
verstehen gemessen in einer 1 %igen Lösung der erfindungsgemäßen Mischung in iso-Propylalkohol.The preparation of the mixture is possible without the addition of water, that is, no water is added to obtain bleachable, pumpable and easy-to-use mixture with favorable rheological properties. Particular preference is given to mixtures which contain less than 2% by weight, preferably not more than 1.5% by weight, in particular not more than 0.5% by weight, of water, based on the active substance alkyl and / or alkenyl oligoglycosides. This water is mainly introduced via the bleaching agents used and means for pH adjustment.
The invention includes the recognition that the content of alcohol according to the invention improves the rheological properties of the alkyl and / or alkenyl oligoglycosides. Without being bound by any doctrine, the fatty alcohol content of the invention first enables the bleaching process.
The term light-colored color numbers after Klett <60, preferably <40, in particular <30 to be understood measured in a 1% solution of the mixture according to the invention in iso-propyl alcohol.
In einer weiteren Ausführungsform ist ein Verfahren zur Herstellung von hellfarbigen Tensidmischungen bevorzugt, welches dadurch gekennzeichnet ist, dass die daraus hervorgehenden Mischungen maximal 1,5 Gew.% Wasser enthalten.In a further embodiment, a process for the preparation of light-colored surfactant mixtures preferably, which is characterized in that the resulting mixtures maximum Contain 1.5% by weight of water.
Zur Herstellung der erfindungsgemäßen Mischungen werden bevorzugt Alkyl- und/oder Alkenyloligoglycoside
eingesetzt, die der Formel (II) folgen,
Dabei können sie nach einschlägigen Verfahren der präparativen organischen Chemie erhalten werden.
Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP A1 0301298, WO 90/03977
und auf "Alkyl Polyglycosides, Technology, Properties and Applications" (K. Hill, VCH 1997)
verwiesen.For the preparation of the mixtures according to the invention it is preferred to use alkyl and / or alkenyl oligoglycosides which follow the formula (II),
They can be obtained by relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is here made to the documents EP A1 0301298, WO 90/03977 and to "Alkyl Polyglycosides, Technology, Properties and Applications" (K. Hill, VCH 1997).
Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyl oligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (II) gibt den Oligomerisierungsgrad (DP), d.h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkylund/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt.The alkyl and / or alkenyl oligoglycosides can be of aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general Formula (II) indicates the degree of oligomerization (DP), i. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in a given compound is always integer and here, above all, can assume the values p = 1 to 6, the value p is for a certain one Alkyloligoglycoside an analytically determined arithmetic size, which is usually a fractional number represents. Preferably, alkyl and / or Alkenyloligoglykoside with a moderate degree of oligomerization p used from 1.1 to 3.0. From an application point of view, such alkyl and / or Alkenyloligoglykoside preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
Der Alkyl- bzw. Alkenylrest R2 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können, sowie Alkyloligoglucoside auf Basis technischer C9-11-Oxoalkohole (DP = 1 bis 3) oder deren Mischungen. Der Alkyl- bzw. Alkenylrest R1 kann sich femer auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ableiten sowie von C12-15-Oxoalkoholen oder der Mischungen. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.The alkyl or alkenyl radical R 2 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C 8 -C 10 (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C 8 -C 18 coconut fatty alcohol and in a proportion of less than 6% by weight C 12 - Alcohol can be contaminated, as well as alkyl oligoglucosides based on technical C 9-11 oxo alcohols (DP = 1 to 3) or mixtures thereof. The alkyl or alkenyl radical R 1 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 18, carbon atoms and also C 12-15 oxo alcohols or the mixtures. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
Zur Herstellung der erfindungsgemäßen Tensidmischungen können aliphatische, verzweigte und unverzweigte, gesättigte und ungesättige Alkohole mit einer Kohlenstoffkettenlänge von 2 bis 31 eingesetzt werden oder deren Mischungen. Besonders bevorzugt sind verzweigte Alkohole mit 11 bis 22 Kohlenstoffatomen und einem niedrigen Siede- und Erstarrungspunkt.Aliphatic, branched and unbranched, saturated and unsaturated alcohols having a carbon chain length of 2 to 31 are used or mixtures thereof. Particularly preferred are branched alcohols having 11 to 22 carbon atoms and a low boiling and solidification point.
Bevorzugt werden Fettalkohol der Formel R1OH (I) eingesetzt, wobei R1 mit R2 gemäß Formel (II) gleichgesetzt werden kann. Diese Fettalkohole dienen in der Alkyl- und/oder Alkenyloligoglycosid-Mischung als rheologiemodifizierendes Mittel. Preference is given to using fatty alcohols of the formula R 1 OH (I), where R 1 can be equated with R 2 according to formula (II). These fatty alcohols serve as a rheology modifying agent in the alkyl and / or alkenyl oligoglycoside mixture.
In einer weiteren bevorzugten Ausführungsform ist ein Verfahren zur Herstellung der erfindungsgemäßen, hellfarbigen Tensidmischungen bevorzugt, bei dem 6 bis 30, vorzugsweise 8 bis 25 und insbesondere 10 bis 15 Gew.% eines rheologiemodifizierenden Mittels enthalten sind. Die Angaben zum Gewichtsverhältnis beziehen sich auf den Aktivsubstanzgehalt an Alkyl- und/oder Alkenyloligoglycosid.In a further preferred embodiment, a method for producing the inventive, light colored surfactant mixtures in which 6 to 30, preferably 8 to 25 and in particular 10 to 15 wt.% Of a rheology-modifying agent are included. The information on the weight ratio refer to the active substance content of alkyl and / or alkenyl oligoglycoside.
Im Sinne des erfindungsgemäßen Verfahrens werden bevorzugt die technischen Synthesegemische,
enthaltend Alkyl- und/oder Alkenyloligoglycoside und Alkohol hergestellt, die durch die Reaktionsführung
noch freien Alkohol, vorzugsweise Fettalkohole der Formel (I) von 6 bis 30, vorzugsweise 8 bis 25,
insbesondere 10 bis 15 Gew.% - bezogen auf Aktivsubstanz Alkyl- und/oder Alkenyloligoglycosid - enthalten.
Es ist aber auch möglich die erfindungsgemäßen Tensidmischungen durch Vermischen von
Alkyl- und/oder Alkenyloligoglycosiden mit Alkoholen, vorzugsweise Fettalkoholen der Formel (I), herzustellen.
Die erfindungsgemäßen Tensidmischungen können auch durch Vermischen mit einem anderen als den
zur Synthese eingesetzten Alkohol hergestellt werden. Bevorzugt wird so verfahren, wenn der Synthesealkohol
einen intensiven Eigengeruch aufweist. In diesem Fall wird der Synthesealkohol destillativ
entfernt und durch einen geruchsarmen Alkohol ersetzt.In the context of the process according to the invention, the technical synthesis mixtures containing alkyl and / or alkenyl oligoglycosides and alcohol are preferably prepared, the alcohol still free from the reaction, preferably fatty alcohols of the formula (I) from 6 to 30, preferably 8 to 25, in particular 10 to 15 wt.% - Based on the active substance alkyl and / or Alkenyloligoglycosid - included. However, it is also possible to prepare the surfactant mixtures according to the invention by mixing alkyl and / or alkenyl oligoglycosides with alcohols, preferably fatty alcohols of the formula (I).
The surfactant mixtures according to the invention can also be prepared by mixing with an alcohol other than that used for the synthesis. Preference is given to proceeding when the synthesis alcohol has an intense inherent odor. In this case, the synthesis alcohol is removed by distillation and replaced by a low-odor alcohol.
Als weitere rheologiemodifizierende Mittel werden Verbindungen eingesetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von Alkoholen, alkoxylierten Alkanolen und Alkylenoxiden.Other rheology-modifying agents used are compounds selected from the group formed by alcohols, alkoxylated alkanols and alkylene oxides.
Es werden gesättigte und ungesättigte, lineare und verzweigte Alkohole zur Senkung der Viskosität eingesetzt. Vorzugsweise können primäre, sekundäre und tertiäre, aber auch ein- und zweiwertige Alkohole eingesetzt werden. Beispiele hierfür sind Ethanol, n-Butanol, iso-Propanol und Glycole auf Ethylen-, Propylen- und Butylen-Basis. Besonders bevorzugt ist der Einsatz von Ethanol und Propylenglycol.There are saturated and unsaturated, linear and branched alcohols to reduce the viscosity used. Preferably, primary, secondary and tertiary, but also monohydric and dihydric alcohols be used. Examples of these are ethanol, n-butanol, isopropanol and glycols Ethylene, propylene and butylene base. Particularly preferred is the use of ethanol and propylene glycol.
Weiterhin sind Fettalkohole der Formel (I), die entweder verfahrensbedingt schon in der Alkyl- und/oder Alkenyloligoglycosid-Mischung (siehe Abreicherung) enthalten sind oder nachträglich den Alkyl- und/oder Alkenyloligoglycosiden zugemischt werden. Furthermore, fatty alcohols of the formula (I), either due to the process already in the Alkyl and / or alkenyl oligoglycoside mixture (see depletion) are included or subsequently the alkyl and / or Alkenyloligoglycosiden be admixed.
Es werden Fettalkohole der Formel (I) bevorzugt als rheologiemodifizierendes Mittel eingesetzt. Unter
Fettalkoholen sind primäre Alkohole der Formel (I) zu verstehen,
Der Alkenylrest R1 kann sich von primären ungesättigten Alkoholen ableiten. Typische Beispiele ungesättigter Alkohole sind Undecen-1-ol, Lauroleinalkohol, Myristoleinalkohol, Palmitoleinalkohol, Petroselaidinalkohol, Oleylalkohol, Elaidylalkohol, Ricinolalkohol, Linoleylalkohol, Linolenylalkohol, Gadoleylalkohol, Arachidonalkohol, Erucaalkohol, Brassidylalkohol, Palmoleylalkohol, Petroselinylalkohol, Arachylalkohol, sowie deren Mischungen und Gemischen aus ungesättigten und gesättigten Fettalkohlen, die durch die in der EP 0724 555 B1 beschriebenen Verfahren erhalten wurden.The alkenyl radical R 1 can be derived from primary unsaturated alcohols. Typical examples of unsaturated alcohols are undecene-1-ol, laurolein alcohol, myristoleic alcohol, palmitoleic alcohol, petroselide alcohol, oleyl alcohol, elaidyl alcohol, ricinoleic alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidonic alcohol, erucalcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and mixtures thereof and mixtures of unsaturated and saturated fatty alcohols obtained by the processes described in EP 0724 555 B1 .
Weiterhin bevorzugt sind Mischungen aus gesättigten und ungesättigten Fettalkoholen auf pflanzlicher Basis, die im Wesentlichen, d.h. mindestens zu 10 Gew.-% ungesättigt sind, und Jodzahlen von 20 bis 130, vorzugsweise 20 bis 110, insbesondere 20 bis 85 und einen Konjugengehalt kleiner 4,5 Gew.-%, vorzugsweise 6 Gew.-% aufweisen.Further preferred are mixtures of saturated and unsaturated fatty alcohols on vegetable Base, which is essentially, i. at least 10% by weight unsaturated, and iodine numbers of 20 up to 130, preferably 20 to 110, in particular 20 to 85 and a conjugate content of less than 4.5% by weight, preferably 6 wt .-%.
Außerdem bevorzugt sind Guerbetalkohole, die in 2-Stellung mit einer Alkylgruppe verzweigt sind und üblicherweise durch basenkatalysierte Kondensation von Fettalkoholen herstellt werden. Eine Übersicht zu dem Thema ist von A. J. O'Lennick und R. E. Bilbo in Soap Cosm.Chem.Spec. April, 52 (1987) erschienen. Bevorzugte Guerbetalkohole leiten sich von Fettalkoholen mit 6 bis 22 Kohlenstoffatomen ab, wie z.B. 2-Ethylhexanol, 2-Butyloctanol, 2-Hexyldecanol und/oder 2-Octyldodecanol. Insbesondere bevorzugt sind Guerbetalkohole, die auf Basis von C6-C12-Fettalkoholmischungen hergestellt werden, enthaltend Capronalkohol, Caprylalkohol, 2-Ethylhexanol, Caprinalkohol und/oder Laurylalkohol. Ein typischer Fettalkoholschnitt, der als Ausgangsstoff für die bevorzugten Guerbetalkohole in Frage kommt, enthält weniger als 5 Gew.-% C6, 50 bis 60 Gew.-% C8, 35 bis 45 Gew.-% C10 und weniger als 2 Gew.-% C12. Guerbetalkohole dieser Art sind in der Deutschen Patentschrift DE 4341794 C1 (Henkel) näher beschrieben, deren Lehre ausdrücklich miteinbezogen wird.Also preferred are Guerbet alcohols which are branched at the 2-position with an alkyl group and are usually prepared by base-catalyzed condensation of fatty alcohols. An overview on the subject is from AJ O'Lennick and RE Bilbo in Soap Cosm.Chem.Spec. April, 52 (1987). Preferred Guerbet alcohols are derived from fatty alcohols having 6 to 22 carbon atoms, such as 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol. Particularly preferred are Guerbet alcohols, which are prepared on the basis of C 6 -C 12 -Fettalkoholmischungen containing caproic alcohol, caprylic alcohol, 2-ethylhexanol, capric alcohol and / or lauryl alcohol. A typical fatty alcohol cut suitable as starting material for the preferred Guerbet alcohols contains less than 5% by weight of C 6 , 50 to 60% by weight of C 8 , 35 to 45% by weight of C 10 and less than 2% by weight .-% C 12 . Guerbet alcohols of this type are described in greater detail in German Patent DE 4341794 C1 (Henkel), the teaching of which is expressly incorporated.
Weiterhin bevorzugt sind verzweigte Fettalkohole, die sogenannten Oxo-Alkohole, mit 4 bis 20 Kohlenstoffatomen die meist 1 bis 4 Methyl- bzw. Ethylgruppen als Verzweigungen tragen und nach dem Oxoprozeß hergestellt werden.Further preferred are branched fatty alcohols, the so-called oxo alcohols, having 4 to 20 carbon atoms usually carry 1 to 4 methyl or ethyl groups as branches and after the Oxo process can be produced.
Bisher wurden niedrige Fettalkoholgehalte in den Alkyl- und/oder Alkenyloligoglycosid-Mischungen angestrebt.
Um dies zu erreichen, muß mit hohem Energieeinsatz verdampft werden, das aus ökonomischen
Gründen negativ für das Verfahren zu bewerten ist. Des weiteren muß man berücksichtigen,
dass die Glykoside temperaturempfindlich sind, also eine schonende und damit technisch aufwendige
Abtrennung erforderlich wäre. Somit zeigen höhere Fettalkoholgehalte einen ökonomischen Vorteil.
Die Abreicherung auf den erfindungsgemäßen Gehalt an Alkoholen ist aus technischer Sicht unter Berücksichtigung
der bekannt geringen Temperaturbelastbarkeit von Zuckertensiden (Gefahr der Karamelisierung)
durchzuführen. Dazu kommen alle Verdampfertypen in Betracht, die diesem Umstand Rechnung
tragen, vorzugsweise jedoch Dünnschichtverdampfer, Fallfilmverdampfer oder Kurzwegverdampfer
sowie - falls erforderlich - beliebige Kombinationen dieser Bauteile. Die Abreicherung kann dann in
an sich bekannter Weise beispielsweise bei Temperaturen im Bereich von 110 bis 220 °C und verminderten
Drücken von 0,1 bis 10 mbar erfolgen.So far, low fatty alcohol contents have been sought in the alkyl and / or Alkenyloligoglycosid mixtures. To achieve this, it must be evaporated with a high energy input, which is negative for economic reasons to evaluate the process. Furthermore, one must take into account that the glycosides are sensitive to temperature, so a gentle and thus technically complex separation would be required. Thus, higher fatty alcohol contents show an economic advantage.
The depletion of the content of alcohols according to the invention is carried out from a technical point of view, taking into account the known low temperature resistance of sugar surfactants (risk of caramelization). For this purpose, all evaporator types come into consideration, which take into account this fact, but preferably thin-film evaporator, falling film evaporator or short path evaporator and - if necessary - any combination of these components. The depletion can then take place in a manner known per se, for example at temperatures in the range from 110 to 220 ° C. and reduced pressures of from 0.1 to 10 mbar.
In einer bevorzugten Ausführungsform werden die erfindungsgemäßen Tensidmischungen zusätzlich mit alkoxylierten Alkanolen versetzt. In a preferred embodiment, the surfactant mixtures according to the invention are additionally with alkoxylated alkanols added.
Bevorzugt ist der Einsatz von alkoxylierten Alkanolen der Formel (III) als weitere rheologiemodifizierendes Mittel. Typische Beispiele hierfür sind Fettalkoholpolyethylenglykol/polypropylenglykolether der Formel (III) bzw. Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (IV).Preference is given to the use of alkoxylated alkanols of the formula (III) as further rheology-modifying Medium. Typical examples of these are fatty alcohol polyethylene glycol / polypropylene glycol ethers of Formula (III) or Fettalkoholpolypropylenglykol / polyethylene glycol ether of the formula (IV).
In einer bevorzugten Ausführungsform werden als weitere rheologiemodifizierendes Mittel Fettalkoholpolyethylenglykol/polypropylenglykolether
der Formel (III), die gegebenenfalls endgruppenverschlossen
sind,
Ebenso bevorzugt werden Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (IV), die
gegebenenfalls endgruppenverschlossen sind,
Einer bevorzugten Ausführungsform entsprechend werden im erfindungsgemäßen Verfahren Fettalkoholpolyethylenglykol/polypropylenglykolether der Formel (III), in der R3 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Atomen, n für eine Zahl von 1 bis 10, und m für 0 und R4 für Wasserstoff steht eingesetzt. Es handelt sich hierbei um Anlagerungsprodukte von 1 bis 10 Mol Ethylenoxid an monofunktionelle Alkohole. Als Alkohole sind die oben beschriebenen Alkohole wie Fettalkohole, Oxoalkohole und Guerbetalkohole geeignet. According to a preferred embodiment, in the process according to the invention, fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III) in which R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, n is a number from 1 to 10, and m is 0 and R 4 is hydrogen. These are adducts of 1 to 10 moles of ethylene oxide with monofunctional alcohols. As alcohols, the above-described alcohols such as fatty alcohols, oxo alcohols and Guerbet alcohols are suitable.
Auch geeignet sind von solchen Alkoholethoxylaten solche, die eine eingeengte Homologenverteilung
aufweisen.
Weitere geeignete Vertreter von nichtendgruppenverschlossenen Vertretern sind solche der Formel
(III), in der R3 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16
C-Atomen, n für eine Zahl von 2 bis 7, m für eine Zahl von 3 bis 7 und R4 für Wasserstoff steht. Es
handelt sich hierbei um Anlagerungsprodukte von zunächst mit 2 bis 7 Mol Ethylenoxid und dann mit 3
bis 7 Mol Propylenoxid alkoxylierten monofunktionellen Alkohole der schon beschriebenen Art.Also suitable of such alcohol ethoxylates are those which have a narrow homolog distribution.
Further suitable representatives of non-terminally capped representatives are those of the formula (III) in which R 3 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, n is a number from 2 to 7, m is a number of 3 to 7 and R 4 is hydrogen. These are addition products of initially with 2 to 7 moles of ethylene oxide and then with 3 to 7 moles of propylene oxide alkoxylated monofunctional alcohols of the type already described.
Weiterhin bevorzugt sind Alkylenoxide als Rheologie-modifizierendes Mittel. Vorzugsweise werden Polyglycolether und Polyglycole auf Ethylen-, Propylen- und Butylen-Basis. Besonders bevorzugt sind 1,2-Propylenglycol und 1,3-Propandiol, sowie deren Ethyl- und Butylether.Further preferred are alkylene oxides as rheology-modifying agent. Preferably Polyglycol ethers and polyglycols based on ethylene, propylene and butylene. Particularly preferred 1,2-propylene glycol and 1,3-propanediol, and their ethyl and butyl ethers.
In einer weiteren Ausführungsform werden im erfindungsgemäßen Verfahren Bleichmittel, vorzugsweise Wasserstoffperoxid, insbesondere in Form einer 30 bis 35 %ige wässrige Lösung, eingesetzt. Außerdem bevorzugt ist das Bleichen mit organischen Persäuren, wie z.B. Dodecandipersäure. Weiterhin kann mit Chlobleichlauge gebleicht werden.In a further embodiment, bleaching agents, preferably Hydrogen peroxide, in particular in the form of a 30 to 35% aqueous solution used. Also preferred is bleaching with organic peracids, e.g. -Dodecanedioic. Furthermore, it can be bleached with black liquor.
In einer weiteren Ausführungsform wird durch Zusatz von Alkali, vorzugsweise Natronlauge der pH-Wert während des Bleichvorganges vorzugsweise auf Werte zwischen 6 und 12, insbesondere 7 bis 10 eingestellt. Zur indirekten Bestimmung des pH-Wertes wird eine Probe gezogen. Der pH-Wert wird dann in einer 20 %igen Lösung der erfindungsgemäßen Tensidmischung in 15%igem iso-Propanol bestimmt.In a further embodiment, the pH is added by addition of alkali, preferably sodium hydroxide solution during the bleaching process preferably to values between 6 and 12, in particular 7 to 10 set. For indirect determination of the pH, a sample is drawn. The pH then becomes determined in a 20% solution of the surfactant mixture according to the invention in 15% isopropanol.
Ein weiterer Gegenstand der Erfindung sind Mittel, enthaltend Alkyl- und/oder Alkenyloligoglycoside,
rheologiemodifizierende Mittel und maximal 1,5, vorzugsweise 1,0 und insbesondere 0,5 Gew.%
Wasser.
In einer weiteren Ausführungsform ist bevorzugt, dass die Mittel 6 bis 30 Gew.% Alkohole,
vorzugsweise bevorzugt Fettalkohol (bezogen auf Aktivsubstanz Alkyl- und/oder Alkenyloligoglycosid)
enthalten. Vorzugsweise können die erfindungsgemäßen Mittel Bleichmittel enthalten, die entweder
verfahrensbedingt oder separat zugesetzt werden können.
Bevorzugt sind außerdem Mittel, die Viskositäten von 10 bis 1000 mPas bei Temperaturen von 85 bis
130, vorzugsweise 90 bis 120°C aufweisen. Another object of the invention are agents containing alkyl and / or Alkenyloligoglycoside, rheology-modifying agent and at most 1.5, preferably 1.0 and in particular 0.5 wt.% Water.
In a further embodiment it is preferred that the agents contain 6 to 30% by weight of alcohols, preferably preferably fatty alcohol (based on the active substance alkyl and / or alkenyl oligoglycoside). The agents according to the invention may preferably contain bleaches which can be added either as a result of the process or separately.
Also preferred are agents which have viscosities of 10 to 1000 mPas at temperatures of 85 to 130, preferably 90 to 120 ° C.
Weiter sind Mischungen Gegenstand der Anmeldung, die dadurch gekennzeichnet sind, dass sie 6 bis 30, vorzugsweise 8 bis 25, insbesondere 10 bis 15 Gew.% Fettalkohol (bezogen auf Aktivsubstanz Alkyl- und/oder Alkenyloligoglycosid) enthalten, eine Viskosität von 10 bis 1000, vorzugsweise 50 bis 500 mPas und eine Farbzahl <60, vorzugsweise <40, insbesondere <30 nach Klett, gemessen in einer 1 %igen Lösung der erfindungsgemäßen Mischung in iso-Propylalkohol, aufweisen.Next mixtures are the subject of the application, which are characterized in that they 6 to 30, preferably 8 to 25, in particular 10 to 15 wt.% Fatty alcohol (based on the active substance Alkyl and / or alkenyl oligoglycoside), a viscosity of 10 to 1000, preferably 50 to 500 mPas and a color number <60, preferably <40, in particular <30 according to Klett, measured in one 1% solution of the mixture according to the invention in iso-propyl alcohol.
Durch das erfindungsgemäße Verfahren werden hochkonzentrierte, wasserfreie, hellfarbige Alkylund/oder
Alkenyloligoglycosid-Mischungen erhalten, die sich problemlos und kostengünstig bevorzugt in
Wasch-, Spül- und Reinigungsmittel einarbeiten lassen, beispielsweise durch das Aufbringen auf einen
festen Waschmittelinhaltsstoff. Dies kann durch Sprühtrocknung erfolgen aber auch in einem Mischer
oder einer Wirbelschicht, wobei gleichzeitig getrocknet und granuliert wird.
Ein weiterer Gegenstand der Anmeldung ist also die Verwendung der erfindungsgemäßen Tensidmischungen
in Wasch-, Spül-, Format- und Reinigungsmitteln. Bevorzugt lassen sich flüssige und gelförmige
Wasch-, Spül- und Reinigungsmittel formulieren. Aufarbeitungsbedingt können die Tensidmischungen
noch Bleichmittel enthalten, die dann in wasserfreien Rezepturen ein stabiles Bleichsystem
darstellen, das beim späteren Wasch- bzw. Reinigungsvorgang seine Bleichwirkung entfaltet. Mit dem
erfindungsgemäßen Verfahren ist jedoch selbstverständlich möglich, bleichmittelfreie Tensidmischungen
herzustellen.
Weiterhin ergibt sich als großer Vorteil der erfindungsgemäßen Tensidmischungen, dass diese wasserfrei,
d.h. mit einem Wassergehalt von weniger als 2 Gew.%, zu Fertigprodukten konfektioniert werden
können. In diese Produkte ist aufgrund der Wasserfreiheit auch im Neutralbereich eine Stabilisierung
zur Verhinderung der Verkeimung nicht nötig.
Ein weiterer Vorteil der erfindungsgemäßen Tensidmischungen enthaltend Alkyl- und/oder Alkenyloligoglycoside
und Fettalkohol ist, dass diese weniger wasseranziehend als reine Alkyl- und/oder Alkenyloligoglycoside
sind. Deshalb zeigen diese Mischungen z.B. in Form von Granulaten bei Lagerung eine
geringere Verklumpungsneigung. By the method according to the invention highly concentrated, anhydrous, light colored alkyl and / or Alkenyloligoglycosid mixtures are obtained, which can be incorporated easily and inexpensively preferably in detergents, dishwashing detergents and cleaning agents, for example by applying to a solid detergent ingredient. This can be done by spray drying but also in a mixer or a fluidized bed, which is dried and granulated at the same time.
Another object of the application is therefore the use of the surfactant mixtures according to the invention in detergents, dishwashing detergents, formers and cleaners. Preferably, liquid and gel washing, rinsing and cleaning agents can be formulated. As a result of workup, the surfactant mixtures may still contain bleaches, which then in water-free formulations represent a stable bleaching system which unfolds its bleaching action during the subsequent washing or cleaning process. However, it is of course possible with the process according to the invention to prepare bleach-free surfactant mixtures.
Furthermore, it is a great advantage of the surfactant mixtures according to the invention that they can be prepared anhydrous, ie with a water content of less than 2% by weight, to form finished products. Due to the freedom from water, stabilization to prevent microbial contamination is not necessary in these products, even in the neutral range.
A further advantage of the surfactant mixtures according to the invention containing alkyl and / or alkenyl oligoglycosides and fatty alcohol is that they are less hydrophilic than pure alkyl and / or alkenyl oligoglycosides. Therefore, these mixtures, for example in the form of granules show a lower tendency to clog on storage.
Die folgende Tabelle beschreibt Alkyl- und/oder Alkenyloligoglycosid-Mischungen mit verschiedenen Fettalkoholgehalten. Die erfindungsgemäßen Beispiele E1 bis E3 sind den Vergleichsbeispielen V1 bis V2 gegenübergestellt.The following table describes alkyl and / or alkenyl oligoglycoside mixtures with various Fatty alcohol content. The inventive examples E1 to E3 are the comparative examples V1 to V2 faced.
Eingesetzt werden:
Der Tabelle ist zu entnehmen, dass die Viskosität der erfindungsgemäßen Tensidmischungen mit steigendem Fettalkoholgehalt abnimmt und die Bleichtemperatur entsprechend niedriger sein kann.The table shows that the viscosity of the surfactant mixtures according to the invention with increasing fatty alcohol content decreases and the bleaching temperature can be correspondingly lower.
Claims (13)
- A process for the production of surfactant mixtures with Klett colour values of <60, the mixtures which containbeing adjusted to viscosities of 10 to 1,000 mPas at temperatures of 85 to 130°C and then bleached at those temperatures, characterized in that fatty alcohols corresponding to formula (I):a. alkyl and/or alkenyl oligoglycosides,b. rheology modifiers andc. less than 2% by weight water,
- A process for the production of light-coloured surfactant mixtures as claimed in claim 1, characterized in that the resulting mixtures contain at most 1.5% by weight water.
- A process as claimed in claim 1 and/or 2, characterized in that alkyl and/or alkenyl oligoglycosides corresponding to formula (II):
are used. - A process as claimed in any of claims 1 to 3, characterized in that the surfactant mixtures contain 6 to 30, preferably 8 to 25 and more particularly 10 to 15% by weight, based on alkyl and/or alkenyl oligoglycoside active substance, of the rheology modifier.
- A process as claimed in any of claims 1 to 4, characterized in that fatty alcohol polyethylene glycol/polypropylene glycol ethers corresponding to formula (III):
are used as an additional rheology modifier. - A process as claimed in any of claims 1 to 5, characterized in that fatty alcohol polypropylene glycol/polyethylene glycol ethers corresponding to formula (IV):
are used as an additional rheology modifier. - A process as claimed in any of claims 1 to 6, characterized in that alkylene oxides, such as polyglycol ethers and polyglycols, are used as an additional rheology modifier.
- A process as claimed in any of claims 1 to 7, characterized in that the bleaching step is carried out with hydrogen peroxide, chlorine bleaching liquors or organic per acids.
- Compositions with Klett colour values of <60 containing alkyl and/or alkenyl oligoglycosides, characterized in that they contain as rheology modifier fatty alcohols corresponding to formula (I):
- Compositions as claimed in claim 9, characterized in that they contain 6 to 30% by weight fatty alcohol, based on alkyl and/or alkenyl oligoglycoside active substance.
- Compositions as claimed in claim 9 and/or 10, characterized in that they contain bleaching agents.
- Compositions as claimed in any of claims 9 to 11, characterized in that they have viscosities of 10 to 1,000 mPas at temperatures of 85 to 130°C.
- The use of the compositions claimed in any of claims 9 to 12 in laundry detergents, dishwashing detergents and cleaners.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10046250 | 2000-09-19 | ||
| DE10046250A DE10046250A1 (en) | 2000-09-19 | 2000-09-19 | Process for the preparation of light-colored alkyl and / or alkenyl oligoglycoside mixtures and their use in washing, rinsing and cleaning agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1188818A1 EP1188818A1 (en) | 2002-03-20 |
| EP1188818B1 true EP1188818B1 (en) | 2004-02-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01121508A Expired - Lifetime EP1188818B1 (en) | 2000-09-19 | 2001-09-08 | Method for preparing light-coloured alkyl and/or alkenyloligoglycoside mixtures |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6903066B2 (en) |
| EP (1) | EP1188818B1 (en) |
| DE (2) | DE10046250A1 (en) |
| ES (1) | ES2215829T3 (en) |
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| DE10046250A1 (en) * | 2000-09-19 | 2002-03-28 | Cognis Deutschland Gmbh | Process for the preparation of light-colored alkyl and / or alkenyl oligoglycoside mixtures and their use in washing, rinsing and cleaning agents |
| EP2336280A1 (en) * | 2009-12-05 | 2011-06-22 | Cognis IP Management GmbH | Use of branched alkyl (oligo)gycosides in cleaning agents |
| GB2541930A (en) * | 2015-09-04 | 2017-03-08 | Cosmetic Warriors Ltd | Composition |
| ES2776635T3 (en) | 2015-10-07 | 2020-07-31 | Elementis Specialties Inc | Wetting and defoaming agent |
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|---|---|---|---|---|
| DE3723826A1 (en) | 1987-07-18 | 1989-01-26 | Henkel Kgaa | METHOD FOR PRODUCING ALKYL GLYCOSIDES |
| DE3833780A1 (en) | 1988-10-05 | 1990-04-12 | Henkel Kgaa | METHOD FOR THE DIRECT PRODUCTION OF ALKYL GLYCOSIDES |
| US5576425A (en) | 1988-10-05 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for the direct production of alkyl glycosides |
| US5362861A (en) * | 1992-07-15 | 1994-11-08 | Henkel Corporation | Continuous bleaching of alkylpolyglycosides |
| DE4317089A1 (en) * | 1993-05-21 | 1994-11-24 | Henkel Kgaa | Nonionic emulsifiers |
| US5478930A (en) * | 1993-09-20 | 1995-12-26 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing light colored alkyl polyglucosides with partially sulfated fatty alcohol catalysts |
| DE4335781C2 (en) | 1993-10-20 | 1998-02-19 | Henkel Kgaa | Vegetable-based fatty alcohols and process for their preparation |
| DE4423641C1 (en) * | 1994-07-06 | 1995-09-07 | Henkel Kgaa | Prodn. of bright-coloured surfactants |
| DE19534371C1 (en) * | 1995-09-15 | 1997-02-20 | Henkel Kgaa | Process for the production of water and dust-free sugar surfactant granules |
| US5866530A (en) | 1995-11-25 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications |
| DE19543990C2 (en) * | 1995-11-25 | 2000-07-20 | Cognis Deutschland Gmbh | Liquid primary products for washing, rinsing and cleaning agents |
| GB9606913D0 (en) * | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
| AU3238600A (en) * | 1999-02-22 | 2000-09-14 | Cognis Corporation | Low viscosity high active blends of alkyl polyglycosides and alcohol ethoxylates |
| DE10019405A1 (en) | 2000-04-19 | 2001-10-25 | Cognis Deutschland Gmbh | Dry detergent granulate production comprises reducing fatty alcohol content in technical mixture of alkyl and/or alkenyl-oligoglycosides and mixing resultant melt with detergent additives in mixer or extruder |
| DE10046250A1 (en) * | 2000-09-19 | 2002-03-28 | Cognis Deutschland Gmbh | Process for the preparation of light-colored alkyl and / or alkenyl oligoglycoside mixtures and their use in washing, rinsing and cleaning agents |
| DE10046251A1 (en) * | 2000-09-19 | 2002-03-28 | Cognis Deutschland Gmbh | Detergents and cleaning agents based on alkyl and / or alkenyl oligoglycosides and fatty alcohols |
-
2000
- 2000-09-19 DE DE10046250A patent/DE10046250A1/en not_active Withdrawn
-
2001
- 2001-09-08 DE DE50101495T patent/DE50101495D1/en not_active Expired - Lifetime
- 2001-09-08 EP EP01121508A patent/EP1188818B1/en not_active Expired - Lifetime
- 2001-09-08 ES ES01121508T patent/ES2215829T3/en not_active Expired - Lifetime
- 2001-09-19 US US09/956,414 patent/US6903066B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1188818A1 (en) | 2002-03-20 |
| ES2215829T3 (en) | 2004-10-16 |
| DE50101495D1 (en) | 2004-03-25 |
| DE10046250A1 (en) | 2002-03-28 |
| US20020123453A1 (en) | 2002-09-05 |
| US6903066B2 (en) | 2005-06-07 |
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