三聚磺酸盐表面活性剂的合成及物理化学性能

三聚磺酸盐表面活性剂的合成及物理化学性能

JSurfactDeterg(2013)16:665–672DOI10.1007/s11743-013-1442-8

ORIGINALARTICLE

SynthesisandCharacterizationofNovelSurfactants1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)Propanes

MingZhou?JinzhouZhao?XuWangJiaqiangJing?LizhiZhou

?

Received:14October2012/Accepted:2January2013/Publishedonline:13March2013ÓAOCS2013

AbstractAseriesoftrimericsulfonatesurfactants1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propaneswerepreparedbythereactionofglycerintriglycidyletherwithlong-chainalcohols,followedbysulfonationwith1,3-propanesultone.Glycerintriglycidyletherwassynthesizedbythereactionofepichlorohydrinwithglycerin.Thechemicalstructuresofthepreparedcompoundswerecon-?rmedbyFTIR,1HNMRandelementanalysis.Theirsolutionpropertieswerecharacterizedbyuseofthemethodofequilibriumanddynamicsurfacetension,steady-state?uorescencespectroscopyofpyreneand?uorescencequenching.Withtheincreasinglengthofthecarbonchain,thevaluesoftheirCMCinitiallydecreased.Allthesetri-mericsulfonatesurfactantshadgoodwatersolubility.Thesecompoundsweresuperiorinsurfaceactiveproper-tiestothereferencesurfactantSDS.Theef?ciencyofadsorptionatthewater/airinterface(pC20)ofthesesur-factantswasveryhigh.Itisfoundthattheshorterhydro-carbonchainlengthofthetrimericsulfonatesurfactants,thefastertherateofdecreaseofsurfacetension,andthe

biggertheaggregationnumberofthetrimericsulfonatesurfactants.

KeywordsFattyalcoholsÁTrimericsurfactantsÁ1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propanesÁSurface-activepropertiesÁSynthesisÁAggregation

Introduction

Inthelasttwentyyears,therehasbeenanincreasinginterestinanewtypeofsurfactantscalled‘‘gemini’’.Thesesurface-activecompoundshavethecharacteristicofbeingcomposedofadoublehydrophobicchain,doublehydro-philicgroupsandaspacerbetweenthemwhichcanbe?exibleorrigid.Theyhavebettersurface-activepropertiesthanconventionalionicsurfactantsandtheirdynamicsurfacepropertiesdifferdrasticallyfromthoseofsingle-chainspecies[1–6].Geminisurfactantswerefoundtoplayanimportantroleinapplicationstodetergents[7–9].Thedesignandsynthesisofthistypeofcompoundshasrecentlyattractedconsiderableattention.

Geminisurfactantswithtwolong-chainalkylgroupsandtwosulfonateorsulfategroups,whicharederivedfromethyleneglycoldiglycidylether,havegoodwatersolubilityandexcellentsurfaceactivepropertiesinwater.Glycidylcompoundshavebeenwidelyusedasvaluableintermedi-atesforthepreparationofgeminisurfactants[10–13].However,glycerintriglycidyletherasvaluableintermedi-ateforthepreparationof1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propane(Schemes1,2)hasrarelybeenreported[14].

Inthepresentinvestigation,?vemodeltrimericsulfo-natesurfactants1,2,3-tri(2-oxypropylsulfonate-3-alkyl-ether-propoxy)propanes(Scheme2)werepreparedfrom

M.ZhouÁJ.Zhao(&)ÁJ.Jing

StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,SouthwestPetroleumUniversity,Chengdu610500,Sichuan,China

e-mail:zhaojz62@http://wendang.chazidian.comM.Zhou

e-mail:mr.zhouming@http://wendang.chazidian.com

M.ZhouÁX.Wang

SchoolofMaterialScienceandEngineering,SouthwestPetroleumUniversity,Chengdu610500,Sichuan,ChinaL.Zhou

OilandGasEngineeringInstituteofTarimOil?eld,Xinjiang841000,China

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commoningredients,andtheirstructureswerecharacter-izedbyFTIRand1HNMR.TheeffectofthestructureofthealkylgroupsonCMC,cCMC,CMC/C20,pC20,CCMC,ACMC,aggregationnumber,micropolarityanddynamicsurfacetensionwasinvestigated.

ExperimentalMaterials

Octyl,decyl,dodecyl,tetradecylandhexadecylalcoholswerepurchasedfromKelongLtd.,Chengdu,China.Epi-chlorohydrin,tetrabutylammoniumbromide(TBAB:CH3CH2CH2CH2)4N?-HSO4-),sodiumhydroxide,tetra-hydrofuran(THF),1,3-propanesultone,potassium,sodiumhydride,dichloromethane,glycerol,anhydrousmagnesiumsulfateandsodiumdodecylsulfate(SDS:C12H25SO3Na)werepurchasedfromChangzhengLtd.,Chengdu,China.Silicagelforcolumnchromatography(60–120mesh)waspurchasedfromHuideyiLtd.,Beijing,China.Allthechemicalswereofreagentgradeanduseddirectlywithoutfurtherpuri?cation.Distilledwaterwaspreparedinour

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laboratoryby1810-Bquartzautomaticdualdistilledwaterutensil.Methods

1

H-nuclearMagneticResonance(NMR)spectrawererecordedonaBruker(Wissembourg,France)AR9400spectrometer(400MHz)withCDCl3solvent.Infrared(IR)spectrawereobtainedonaFTIR-8400Sspectrometer(ShimadzuCorporation,Japan)withaliquid?lmbetweenKBrdiscs.ElementanalysesweredeterminedbyaCostechECS4010CHNSOanalyzer,Italy.Synthesis

Fivemodel1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propanesweresynthesizedthroughthreestepsbyfollowingScheme3.

ATypicalProcedurefortheSynthesisofGlycerolTriglycidylEther

Glyceroltriglycidyletherwaspreparedunderphase-trans-fercatalyticconditionsreportedpreviously[11].Accordingtothereactionprinciple,glyceroltriglycidyletherwaspreparedbythesuccessivetreatmentofamixtureof0.8molepichlorohydrinand0.1molglycerol(8:1molarratio)in40mL0.8mol/LNaOHaqueoussolutionat50°Cfor10hwith0.1molartetrabutylammoniumhydrogensulfateasthephase-transfercatalyst,followedbytheadditionof50mL4mol/LNaOHaqueoussolutionatroomtemperaturefor20h.Reactionproductswere?lteredtoremovethesolidsgeneratedinthesystem,The?ltratewasthenaddedintothedichloromethane,washedwithsaturatedsalttopH=7,glyceroltriglycidyletherwasobtainedbydistillationunderreducedpressure(70–86%yield).ATypicalProcedurefortheSynthesisof1,2,3-tri(2-hydroxy-3-alkylether-propoxy)Propane

1,2,3-tri(2-hydroxy-3-alkylether-propoxy)propanes(R=C8H17,C10H21,C12H25,C14H29,C16H33)wereobtainedbytheringopeningreactionofglyceroltriglycidyletherwithlong-chainfattyalcoholsinthepresenceofpotassiumat60°Cfor8h.Themolarratioofglyceroltriglycidylethertolong-chainfattyalcoholsandpotassiumwas1:8:2.Theorganiclayerwasdriedwithanhydrousmagnesiumsulfate,andthendistilledtoremovethesolventmethylenechlo-ride.Finally,puri?cationof1,2,3-tri(2-hydroxy-3-alky-lether-propyl)propanewascarriedoutbysilicagelcolumn

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chromatographywithahexane:ethanol(2:1,v/v)eluent

(71–75%yield).

ATypicalProcedureforthePreparationof1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)PropanesThetargetcompounds1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propanes(R=C8H17,C10H21,C12H25,C14H29,C16H33)weresynthesizedbysulfonationofcorresponding1,2,3-tri(2-hydroxy-3-alkylether-pro-poxy)propanewith1,3-propanesultoneandsodiumhydrideindryTHFat60°Cfor12h.Themolarratioof1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propyl)pro-panestoTHF,1,3-propanesultoneandsodiumhydridewas1:20:8:6.Methanolwasaddedtotheproductstoremoveunreactedsodiumhydride,distilledtoremoveTHF,andthentheremainingsolutionwasdissolvedinann-butanolandwatersolution(molarratio3:1).Theorganicphasewasdriedwithanhydrousmagnesiumsulfate,anddistilledtoremovethebutanol.Finally,puri?cationof1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propaneswascarriedoutaswhitewaxyproductbysilicagelcolumnchromatographywithahexane:ethanol(2:1,v/v)eluent(72–80%yield).

FTIR,1HNMRandElementAnalysis

Thestructureof1,2,3-tri(2-oxypropylsulfonate-3-alky-lether-propoxy)propaneswascon?rmedbyitsFTIR,NMRandelementanalysis.NMRandelementanalysisisshowedinTable1.TheFTIR,1HNMRandelementanalysisshowthatthesyntheticproductsaretargetproducts.

Measurements

EquilibriumSurfaceTension

Thesurfacetensionsofsurfactantsweremeasuredwitha

¨ssCorporation,Germany)bytheK100tensiometer(Kru

Wilhelmyplatetechniqueat20°C.Aseriesofmeasure-mentstoobtainequilibriumsurfacetensionweretakenuntilthechangeinsurfacetensionwaslessthan0.05mNm-1for10min.Thesurfacetensionofeachsurfactantisanaveragedvalueofthreemeasurementsonlywhenthedeviationofthreemeasurementvalueswaslessthan1%.Thecriticalmicelleconcentration(CMC)andsurfacetensionattheCMC(cCMC)weredeterminedfromthebreakpointofthesurfacetensionandlogarithmofconcentrationcurve.ThesolutionsofthetrimericsulfonatesurfactantswithconcentrationsabovetheCMCreachedequilibriumwithin1h,whereasthosebelowtheCMCreachedequilibriumwithinseveralhours.Theadsorptionamountofsurfactant(C)(inmolm-2)fortrimericsulfo-natesurfactantscanbecalculatedbyapplyingthefollow-ingGibbsadsorptionisothermequation[15],C¼À

1dcð1Þ

wherecistheequilibriumsurfacetensioninmNm-1,Cisthesaturationadsorbedamountinmol/1,000m2,Risthegasconstant(8.314Jmol-1K-1),Tistheabsolutetemperature,Cisthesurfactantconcentration,and(dc/dlnC)istheslopeinthesurfacetensionisothermwhentheconcentrationisneartheCMC.Thevalueofn(thenumberofspeciesattheinterfacewhoseconcentration

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Table1Preparationandpropertiesof1,2,3-tri(2-oxypropylsulfonation-3-alkylether-propoxy)propaneRC8H17C10H21C12H25C14H29C16H33

Yield(%)8076787274

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HNMR(CDCl3)(d)Anal.found(calc.)

C,49.98(49.91);S,8.79(8.87);H,8.20(8.22);O,26.48(26.62)

C,52.51(52.49);S,8.11(8.23)H,8.53(8.66);O,25.87(25.94)

C,54.72(54.56);S,7.68(7.83)H,9.04(9.12);O,22.46(23.04)

C,59.65(59.15);S,7.42(7.51)H,9.95(9.78);O,22.32(22.54)

C,64.21(63.40);S,7.23(7.35)H,10.64(10.49);O,21.83(22.05)

0.81–0.88(m,9H,1.18–1.51(m,36H),1.93–2.18(m,6H,2.86–3.13(m,6H,3.16–3.81(m,32H)0.81–0.88(m,9H,1.15–1.55(m,48H),1.88–2.19(m,6H,2.89–3.15(m,6H,3.11–3.91(m,32H)0.81–0.88(m,9H,1.17–1.59(m,60H),1.82–2.33(m,6H,2.78–3.06(m,6H,3.22–3.85(m,32H)0.81–0.88(m,9H,1.20–1.68(m,72H),1.88–2.28(m,6H,2.72–3.10(m,6H,3.25–3.92(m,32H)0.81–0.90(m,9H,1.28–1.61(m,84H),1.95–2.24(m,6H,2.83–3.03(m,6H,3.30–3.89(m,32H)

TheFTIRspectrumintherange3,000–700cm-1of1,2,3-tri(2-oxypropylsulfonate-3-dodecylether-propoxy)propaneswasasfollows.Theabsorptionpeakat2,933.25cm-1correspondstothe–CH3asymmetricstretchingvibration.Thespectrumbandat2,851.15cm-1contributestothesymmetricstretchingvibrationpeakof–CH2.Further,thespectrumalsohasapeakat1,461.75cm-1contributingtothedeformationvibrationof–CH2–,1,212.90cm-1,thestretchingvibrationoftheetherbond(C–O–C).Peaksat1,199.42,1,121.23and1,034.56cm-1correspondtothesymmetricalandasymmetricalpeaksof–SO3-,719.35cm-1,thevibrationpeakoflong-chain–CH2–

changeswiththesurfactantconcentration)istakenas2foranequimolarratioofsurfactantanionandcounteractionatinterfaceintheabsenceofextraelectrolyte.Inordertoextracttheminimumsurfaceareaoccupiedbyasurfactantmolecule,ACMC(nm2),attheair–waterinterfacewhenthesurfaceadsorptionwassaturated,Eq.(2)wasused,ACMC

1

¼À

NCCMC

ð2Þ

lnðI0=IÞ¼½Q??=½ðCÀCMCÞ=N??ð3Þ

whereI0andIarethe?uorescenceintensitieswithoutandwithquencher,respectively,and[Q]istheconcentrationofquencher.

DynamicSurfaceTension

¨ssThedynamicsurfacetensionwasmeasuredusingaKru

bubblepressuretensiometerBP2,amethodwhichinvolvesmeasuringthemaximumpressurenecessarytoblowabubbleinaliquidfromthetopofacapillary.Themea-surementswereconductedwitheffectivesurfaceagesfrom1mstoseveralseconds.

whereNisAvogadro’snumber.WhenCCMCisinmolcm-2,ACMCisinnm2.Steady-StateFluorescence

The?uorescencemeasurementswereperformedusingaSENS-9000?uorescencespectrophotometer.Thespectrawererecordedbetween185and900nmwiththeexcitationwavelengthat350nm,wheretheconcentrationofpyrenewas1910-5molL-1foreachsolution.The?uorescenceintensityratioofthe?rst(373nm)tothethird(384nm)vibronicpeaks,I1/I3,dependsontheenvironmentofthepyrenemolecules[16,17].TheenvironmentofthepyreneismorehydrophobicwhentheI1/I3ratiodecreases.TheI1/I3ratioisin?uencednotonlybythesolventpolaritybutalsobytheaggregationnumberandcorecavity[18].FluorescenceQuenching

Themicelleaggregationnumberswereobtainedbythequenchingmethod,withpyreneasthe?uorescenceprobeandcetylpyridiniumchlorideasthequencherofthepyrene?uorescence.Pyrenewasexcitedat350nmanditsemissionrecordedat384nm.Theprobeconcentrationinthesurfac-tantsolutionwas1910-5molL-1.Theaggregationnumber(N)canbecalculatedfromtheequation[19,20],

ResultsandDiscussionEquilibriumSurfaceTension

TheCMCvaluesandsurfacetensionattheCMC(cCMC)oftrimericsulfonatesurfactantswithnof8,10,12,14and16weredeterminedusingWilhelmytensiometry.TheresultsofthesemeasurementsareshowedinTable2.TheseresultsindicatethattheCMCvaluesoftrimericsulfonatesurfac-tantsareaboutoneortwoordersofmagnitudelowerthanthoseofthecorrespondingmonomericsurfactants,whichsuggeststhatthetrimericsulfonatesurfactantsmakeiteasytoformmicellesinthebulksolution.TheCMCofthecon-ventionalionicsurfactantisknowntodecreasewithincreasingnumberofcarbonatomsinthehydrophobicgroups.Inthiswork,theCMCoftrimericsulfonatesurfac-tantdecreasefrom3.16910-4to1.80910-6molL-1whenincreasingthecarbonatomofhydrocarbonchainfrom8to16,whichissimilartothosecommonsurfactantsina

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Table2Surfacechemicalpropertiesof1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy)propane(20°C)AlkylchainC8H17C10H21C12H25C14H29C16H33SDS

CMC(910-4molL-1)3.1600.8000.3300.0400.01882.00

cCMC(mNm-1)29.526.823.324.826.232.5

pC204.645.526.056.747.022.50

CMC/C2013.7926.4937.0321.9818.842.60

106CCMC(molm-2)2.452.302.722.472.343.16

669

ACMC,nm2(molecule-1)0.6780.7220.6110.6720.7100.526

homologouscompound,asmayresultfromtheconformationofthesurfactantsatinterfaceorthecurlingofthethreehydrophobicchainsduringdissolution.Theformationofthemicelleisthejointresultofthehydrophobiceffectandintermolecularforcebetweensurfactants.Inviewoftheconformationoftrimericsulfonatesurfactants,threehydrophobicchainsarenotparallelduetothepresenceofseveraloxygenatomsinetherbonds.

Trimericsulfonatesurfactantsexhibitedclearsolutionsanddisplayedasharpbreakinthesurfacetensionversusconcentration(onalogscale)curvesanda?nalplateauindicatingawell-de?nedCMCandsurfacetensionattheCMC(cCMC),asshowedinFig.1.Thesurfacetensiondecreaseswithincreasingconcentrationandthenclearlyreachesabreakpoint.ItcanbeseenfromFig.1thatwhenthelengthofhydrophobicchainincreases,theCMCofthesurfactantsdecrease.

Figure2showstherelationshipbetweenthelogarithmofCMCandthetotalcarbonnumberinthehydrophobicgroupsfortrimericsulfonatesurfactantswiththechainlengthof8–16;theplotoftrimericsulfonatesurfactantsshowsalineardecrease.Ingeneral,therelationshipbetweentheCMCandthenumberofcarbonatomsninthehydrophobicchainforhomologousstraight–chainionicsurfactantscanbewritteninthefollowingform[21,25],whereAandBareconstants.logCMC¼AÀBn

ð4Þ

ThelinearrelationshipsbetweenlogCMCandnfortri-mericsulfonatesurfactantsandCnH2n?1SO3NadeducedfromFig.2areasfollows:

Trimericsulfonatesurfactants:logCMC¼2:8296À0:0965nðR2¼0:982ÞCnH2n?1SO3Na:

logCMC¼6:5868À0:3103nðR2¼0:9923Þ

Fromtheslopeofthestraightline,thevaluesofBaredeterminedtobe0.0965forthetrimericsulfonatesurfac-tant.ThevalueofBoftrimericsulfonatesurfactantsissmallerthanthatoftheconventionalsurfactantsSDS(0.3038);itindicatesthatthedecreaseintheCMCwithan

Fig.1Surfacetensionversuslogarithmoftheaqueousmolarconcentration(logC)ofsynthesized1,2,3-tri(2-oxypropylsulfo-nate-3-alkylether-propoxy)propane:(circles)n=8,(multiplicationsigns)10,(triangles)12,(squares)14,(diamonds)

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increaseofchainlengthforthetrimericsulfonatesurfac-tantsissmallerthaninthecaseofmonomericsurfactants.Thistrendisconsistentwiththedataoncarboxylategeminisurfactants[22]andquaternaryammoniumtypetrimericsurfactants[23].Thus,itisclari?edthattheeffectofthechainlengthontheCMCfortrimericsulfonatesurfactantsissmallerincomparisonwithmonomericsurfactants.

ThesurfacetensionsattheCMCoftrimericsulfonatesurfactantswithnof8–16arelowerthanthoseofthemonomericsurfactants.Thisshowsthatthegeminisur-factantsadsorbstronglyattheair/waterinterface,andorientthemselvestocauseeffectivesurface

activities.

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