Surfactant blends for emulsifying and cleaning - Sepawa
Surfactant blends for emulsifying and cleaning - Sepawa
Surfactant blends for emulsifying and cleaning - Sepawa
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<strong>Surfactant</strong> <strong>blends</strong> <strong>for</strong> <strong>emulsifying</strong><strong>and</strong> <strong>cleaning</strong>F. Rittig*, R. Baur, C. Esper, U. Steinbrenner, J. Tropsch, S. ZimdahlBASF SE, 67056 Ludwigshafen, E-EMV/GS-J550
Motivationmotivation• search <strong>for</strong> emulsifiers able to <strong>for</strong>m stable emulsionssolution• surfactant combination with excellent emulsification results(Steinbrenner et al. SEPWA Proceedings 2006, 373)16.05.2008, F. Rittig SEPWA Nordic 2009 2
Evaluation of emulsifiers by the markermethod 1The product (oil) to beemulsified is marked with2 different oil-soluble dyesDetermination ofdroplets of mixedcolor+ blue dyeOilEmulsifierWaterRaw emulsion AGentlemixingHomogenizationto a fine emulsion+ yellow dyeRaw emulsion BMixture 1:11 Thomas Danner, Thesis: „Tropfenkoaleszenz in Emulsionen“,Univ. Karlsruhe, published by GCA, Herdecke 2001Microscopicpicture16.05.2008, F. Rittig SEPWA Nordic 2009 3
Emulsion stabilities with <strong>blends</strong> based onC10 Guerbet alcohol (> 60%)30% sunflower oil, 1% emulsifier, 69% water, storage at 23°C10% of the dropletscoalesced afterblend of (C10-G + longchain alcohol) ethoxilatesmonthweeksdays<strong>blends</strong> of C 10Guerbet with longchain alcohols workwell, much betterthan C 10Guerbetalone.hoursminutesC16C18C12C15C10-G ethoxblend of (C10-G + C12C15alcohol) ethoxilates6 8 10 12 14 16HLB16.05.2008, F. Rittig SEPWA Nordic 2009 4
The "<strong>Surfactant</strong> Team"Coethoxilates of C10 Guerbet + long chainalcoholExamples: C 10 Guerbet + 6 EO Coethethoxilate Long chain alc. + 9 EOHLB ca. 12.5 HLB ca. 12.5 HLB ca. 12.51) wetting(EN 1772, 23°C)0.5 g/l ca. 60 s ca. 60 s > 300 s1.0 g/l ca. 10 s ca. 10 s > 300 s2.0 g/l ca. 5 s ca. 5 s > 300 s2) gel phases in water solid gel at no solid gel solid from 0% to(23°C) 40 w% water (
Can synergistic properties of ethoxilatesof C10 Guerbet alcohol <strong>blends</strong> be utilized <strong>for</strong>laundry detergents ?Agenda• Laundry per<strong>for</strong>mance of surfactant <strong>blends</strong>• Liquid detergents• high active contents• low active contents• fragrance solubilization• Eco-tox• Summary16.05.2008, F. Rittig SEPWA Nordic 2009 6
Can synergistic properties of ethoxilatesof C10 Guerbet alcohol <strong>blends</strong> be utilized <strong>for</strong>laundry detergents ?Agenda• Laundry per<strong>for</strong>mance of surfactant <strong>blends</strong>• Liquid detergents• high active contents• low active contents• fragrance solubilization• Eco-tox• Summary16.05.2008, F. Rittig SEPWA Nordic 2009 7
Screening of synergistic surfactant <strong>blends</strong>Test conditions• In combination with 5% AEO <strong>and</strong> 15% Na-LAS in a zeolite based powder<strong>for</strong>mulation• launder-o-meter tests• water hardness 2.5 mmol/l (4 parts Ca 2+ , 1 part Mg 2+ ,8 parts HCO 3-)• wash time 30 min• wash temperature 30°C <strong>and</strong> 60°C• liquor ratio 1 : 12.5• test swatches <strong>for</strong> screening• wfk10D (pigment/sebum on cotton)• wfk10PF (vegetable oil on cotton)• wfk20D (pigment/sebum on PES/cotton blend)16.05.2008, F. Rittig SEPWA Nordic 2009 8
Screening of synergistic surfactant <strong>blends</strong>Wash tests at 30 °CΔΔ R vs. C13C15 x 7 EO50-5-10-15-20wfk10Dwfk10PFwfk20D• Blends of ethoxilates of C10-Guerbet alcohol <strong>and</strong> long chainalcohols are better than singlecomponents• At certain ratios per<strong>for</strong>mance isequal than system with st<strong>and</strong>ardsurfactants-250 25 50 75 100weight-% C10 alcohol ethoxilate16.05.2008, F. Rittig SEPWA Nordic 2009 9
Screening of synergistic surfactant <strong>blends</strong>Wash tests at 60 °CΔΔ R vs. C13C15 x 7 EO50-5-10-15-20wfk10Dwfk10PFwfk20D• Blends of ethoxilates of C10-Guerbet alcohol <strong>and</strong> long chainalcohols are better than singlecomponents• At certain ratios per<strong>for</strong>mance is inthe range of the system withst<strong>and</strong>ard surfactants-250 25 50 75 100 More detailed studies are requiredweight-% C10 alcohol ethoxilate16.05.2008, F. Rittig SEPWA Nordic 2009 10
Special coethoxilatesProduct <strong>and</strong> per<strong>for</strong>mance data• fixed alcohol composition (types <strong>and</strong> ratio)• ethoxilation according to cloud point of benchmark• full scale tests (washing machine) in powder <strong>and</strong> liquid detergentsPhysical data M5 ST5 M7 ST7Alcohol G-C 10+C 13/15G-C 10+C 13/15Hydrophilic part 5 EO 7 EOCloud points (EN 1890, Method E,BDG)59-63 °C 60-64 °C 73-76 °C 75 °CFoaming 2g/l EN 12728 110 ml 110 ml 300 ml 280 mlWetting @ 23°C (1g/l EN1772) 20 s 100 s 20 s 30 sWetting @ 70°C (1g/l EN1772) 35 s 160 s 30 s 30 sM = Coethoxilates, ST = benchmark (e.g. Lutensol AO)16.05.2008, F. Rittig SEPWA Nordic 2009 11
Can synergistic properties of ethoxilatesof C10 Guerbet alcohol <strong>blends</strong> be utilized <strong>for</strong>laundry detergents?Agenda• Laundry per<strong>for</strong>mance test of surfactant <strong>blends</strong>• Liquid detergents• high active contents• low active contents• fragrance solubilization• Eco-tox• Summary16.05.2008, F. Rittig SEPWA Nordic 2009 12
Formulations with high contents of WASLaundry wash test 40°C<strong>for</strong>mulationFAS 10nonionic surfactant 153025ST 7M 7soap 10MPG 620citric acid 3B(OH) 3 1.5Δ remission15Ethanol 210percarbonate 15Savinase Ultra 16 L 25neutralized with ethanol aminewaterbalance0general soil (w fk 20D,EMPA general 101; 141/2; PCS4)stainbleachableenzymaticbleachable soil (EMPA enzymatical stain (EMPA114; BC-1; BC-2; PCS 3) 112; 116; CS 1; CS-10;stain CS-8; AS-10; Stain PC-5; CS-28)16.05.2008, F. Rittig SEPWA Nordic 2009 13
Different viscosity profile of coethoxilatesin dilution with water1000000100000• Lower viscosities observed whencoethoxilated samples are dilutedwith watervisc /m Pas100001000100101M 7 ST 70 20 40 60 80 100conc. surfactant (%)• Advantages• Faster dilution in water• In liquid dosing systems,e.g. in I&I laundry(all concentrations possible)• During manufacturingprocesses• Special liquid detergent typesneed more detailed investigations16.05.2008, F. Rittig SEPWA Nordic 2009 14
“super concentrates” with high contents ofwashing active substances (WAS)C C D DWAS (LAS + soap + AEO) 41 41 51.5 51.5LAS (Lutensit A-LBS) 7.9 7.9 7.4 7.4soap (Edenor K12-18) 11 11 14.6 14.6ST 7 22 26.6M 7 22 26.61,2-propylene glycol 8.8 6 9 6ethanol 2 2 2 2pH 8.7 8.7 8.7 8.7viscosity (Sp 2, 60rpm)/mPas200 160phaseseparated140ST 7 M 7Formulation DConcentrations in active matter16.05.2008, F. Rittig SEPWA Nordic 2009 15
“highly viscous super concentrates” with highcontents of washing active substances (WAS)FormulationDFormulationEFormulationFWAS (LAS + soap + AEO) 51.5 51.5 51.5LAS (Lutensit A-LBS) 7.4 7.4 7.4soap (Edenor K12-18) 14.6 14.6 14.6M 7 26.6 26.6 26.61,2-propylene glycol 6 6 6ethanol 2 2 2Sokalan AT120 0.9 1.5pH 8.7 8.7 8.7viscosity (Sp 2, 60rpm)/mPas140 500 1100Concentrations in active matter16.05.2008, F. Rittig SEPWA Nordic 2009 16
Decrease of viscosity in regular <strong>for</strong>mulaswith low WAS200180Washing active substance(Nonionic+LAS+soap)14.25% 19% 23.75%visc./mPas16014012010080pH8.28.69.0ST 7LAS (Lutensit ALBS)* 7.5% 10% 12.5%Soap (Edenor K12-18)* 1.5% 2% 2.5%AEO 5.25% 7% 8.75%EtOH 2.82% 3.76% 4.7%NaCitrate 0.75% 1% 1.25%water to 100 to 100 to 1006040200M 7*viscosities measured with Sp 62, 60 rpm0% 10% 20% 30%WAS different viscosity profile16.05.2008, F. Rittig SEPWA Nordic 2009 17
Options to readjust viscosityin regular liquid detergentsI. Reduce solventsII.Check if thickeners are an option16.05.2008, F. Rittig SEPWA Nordic 2009 18
Option IAdjusting viscosity by solvent reductionST 7H 2O 43.9 43.9Na 2SO 41.9 1.9NaCl 0.1 0.1HP56 0.2 0.2Glycerin 1.2 1.2EtOH 1.7 1.7MPG 7.2 7.2Triethylenglycolmonobutylether 1.5 1.5AEO 16.4 16.4Soap 6.1 6.1SAS 11.6 11.6pH 8 8Viscosity (mPas) 112 65Appearance opaque opaqueCold cloud point
Option IAdjusting viscosity by solvent reductionST 7 M7 M 7H 2O 43.9 43.9 53.5Na 2SO 41.9 1.9 1.9NaCl 0.1 0.1 0.1HP56 0.2 0.2 0.2Glycerin 1.2 1.2 0EtOH 1.7 1.7 0MPG 7.2 7.2 2Triethylenglycolmonobutylether 1.5 1.5 0AEO 16.4 16.4 16.4Soap 6.1 6.1 6.1SAS 11.6 11.6 11,6pH 8 8 8Viscosity (mPas) 112 65 126Appearance opaque opaque opaqueCold cloud point
Option IIAdjusting viscosity by thickenere.g. II/A II/BLAS Lutensit A-LBS 10 10Soap Edenor K12-18 2 2KOH pH = 8.6M 7 0 7ST 7 7 0EtOH 2 2MPG 1.2 1.2NaCitrate 1 1KOH pH = 8.6NaClViscosity/mPas 177 70Concentrations in active matter16.05.2008, F. Rittig SEPWA Nordic 2009 21
Option IIAdjusting viscosity by thickenere.g. II/A II/B III/C III/DLAS Lutensit A-LBS 10 10 10 10Soap Edenor K12-18 2 2 2 2KOH pH = 8.6M 7 0 7 7 7ST 7 7 0 0 0EtOH 2 2 2 2.5MPG 1.2 1.2 1.2 1.2NaCitrate 1 1 1 1NaClSokalan AT120 0.26 0.58Viscosity/mPas 177 70 160 355Concentrations in active matter16.05.2008, F. Rittig SEPWA Nordic 2009 22
Make use of superior emulsification propertiesMethod• 1 g <strong>Surfactant</strong>• 0.1 to 0.5 g Perfume (orangeterpene)• Mix it• Balance with water (100 g)• Stir <strong>for</strong> 5 min at given speed• Check samples after 24 h1 g ST0.5 g orange terpene1 g M X0.1 g orange terpene1 g M X0.2 g orange terpene1 g M X0.4 g orange terpenecloudy Slightly cloudy clear1 g M X0.5 g orange terpenePhaseseparated16.05.2008, F. Rittig SEPWA Nordic 2009 23
Make use of superior emulsification propertiesMethodOrange terpene0.1 g 0.2 g 0.3 g 0.4 g 0.5 g1 g ST0.5 g orange terpene1 g M X0.1 g orange terpene1 g M X0.2 g orange terpene1 g M X0.4 g orange terpene1 g M X0.5 g orange terpeneST 7M XCloudyclear2 phaseslightly cloudyST 7M XST 7M XLillial0.1 g 0.2 g 0.3 g 0.4 g 0.5 gIsoamylsalicylateST 7M 7ST 7M 7C11 aldehyde0.1 g 0.2 g 0.3 g 0.4 g 0.5 gGlobalide16.05.2008, F. Rittig SEPWA Nordic 2009 24
Eco-tox properties & labelingAquatic invertebrates:Daphniamagna/EC50(48h)Aquatic plants:M 7 ST 71-10 mg/l 0.1-1 mg/l1- 10 mg/l 0.1-1 mg/lScenedesmussubspictus/EC50 (72h)Labeling Xn, R22, R41 Xn, N, R22, R41, R50Transport No hazardous material Class 916.05.2008, F. Rittig SEPWA Nordic 2009 25
Summary<strong>Surfactant</strong> <strong>blends</strong> <strong>and</strong> coethoxilates with C10-Guerbet alcohols show• Synergistic effects in• emulsification (triglycerides)• laundry detergentsΔ remission3025201510monthweeksdayshoursminutesC16C18C12C15C10-G ethox6 8 10 12 14 16200180160HLBEMPA 101 WFK 10D WFK 20D Triolein Olive oil average• Different viscosity profiles vs. st<strong>and</strong>ards50visc./mPas140120100806040208.28.69.0• Improved solubilization of fragrances00% 10% 20% 30%WAS/%• Sustainable eco-tox profile16.05.2008, F. Rittig SEPWA Nordic 2009 26
Per<strong>for</strong>mance profilelabelingLaundryper<strong>for</strong>mance laundryEmulsificationemulsification (triglycerides) (triglycerdynamicsemulsification Emulsification(p(paraffin)wettingcmclow foamLutensol MC12C15 ethoxylatesThank you!16.05.2008, F. Rittig SEPWA Nordic 2009 27
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