表面修饰纳米氧化锌的制备及其在化妆品和橡胶中的应用

IZnOZnOZnOZnOZnO1(TEOS)DEDMSZnOZnO4nmZnOZnOZnOZnOZnOZnOW/OUVAUVBOMCZnOUVA2ZnOZnOZnOZnOZnOZnOZnOW/OUVAZnO3ZnOIIZnOZnOZnOZnOZnO4ZnO/ZnOZnOZnOZnOIIIABSTRACTAsanewmulti-functionalfinechemicalproduct,ZnOnanoparticlehaspromisingapplicationinmanyfields.However,similartootherkindsofnanoparticles,ZnOnanoparticlealsotendstoagglomerate,whichconsiderablylimitsitsapplicationinindustry.Toovercomethatbottleneck,wehavetriedtomodifythesurfaceofZnOnanoparticlewithvariousmethodstoimproveitsdispersibilityinorganicsolutions.Theperformanceofsurface-modifiedZnOnanoparticlehasalsobeeninvestigatedinrelationtoitspracticeinindustry.Themaincontentsandresultsareasfollows.1Tetraethylorthosilicate(TEOS)anddimethyldiethoxysilane(DEDMS)wereusedascoprecursorstoprepareorganicallymodifiedsilica(ormosil)viasol-gelprocess.ResultantormosilwasthencoatedontothesurfaceofZnOnanoparticletoformormosilmodifiedZnOnanoparticlewithacappinglayerthicknessofabout4nm.Themodificationmechanismwasdiscussed,andthepropertiesoformosilmodifiedZnOnanoparticlewereinvestigated.Resultsindicatethatormosil-cappedZnOnanoparticleshowshydrophobicityandgoodcompatibilitywithorganicphases,aswellaseffectivelydecreasedphotocatalyticactivityandalmostunchangedultraviolet(UV)-shieldingability.SurfacemodificationwithormisilincreasesthestabilityofZnOnanoparticleandhindersmigrationofZnOnanoparticletowaterphaseinpreparationofsunscreenformulation.Water-oil(W/O)emulsionformulatedwithormosil-cappedZnOnanoparticlehasexcellentshieldingabilityagainstUVinregionA(UVA).Besides,ormosil-cappedZnOnanoparticleandoctylmethoxycinnamate(OMC)showsasynergisticeffectinimprovingthesun-protectionfactor(SPF)oftheemulsion.Correspondinghybridsurface-cappedZnOcouldfindpromisingapplicationinsunscreencosmeticsasakindofUVA-shieldingadditive.2Ormosil-cappedZnOnanoparticlewaspreparedviainsitumodificationroute,whereormosilwasdirectlymodifiedonthesurfaceofprecursor(zinccarbonateIVhydroxide(ZCH)ofZnOnanoparticle,andheat-treatmentoftheprecursorandsurface-cappednanoparticlewassimultaneouslyaccomplishedinonesinglestep.Thepropertiesofresultantflake-likeZnOnanoparticlewereinvestigated.Resultsshowthattheflake-likeZnOnanoparticlepossessesgoodstabilityandcompatibilitywithorganicphases.Besides,theW/Oemulsionformulatedwiththeflake-likeZnOnanoparticlehasgoodprotectionagainstUVA.3ZnOnanoparticlewassurfacemodifiedviaamechanochemicalroute,forwhichafluidizedbedjetmillwasperformed.Grindingandsurfacemodificationwithstearicacid(SA)ofZnOnanoparticlewererealizedsimultaneouslybyrevampingthejetmill.ThepropertiesofresultantSA-cappedZnOnanoparticlewereinvestigated.ResultsindicatethattheagglomerationofSA-modifiedZnOnanoparticleisreducedsignificantlyascomparedwiththatofunmodifiedZnOnanoparticle.Besides,ZnOnanoparticlesurface-modifiedwithstearicacidhassignificantlyimoroveddispersibilityandstabilityinorganicmedia.4SurfacemodifiedZnOnanoparticlepreparedviamechanochemicalroutewasusedasanactivatorinnaturalrubber,styrene-butadienerubberandbutadienerubber/naturalrubberblend.Thepropertiesofresultantrubberswereinvestigated.Resultsshowthat,ascomparedwithunmodifiedZnOnanoparticle,SA-moidifiedZnOnanoparticlehasbetteraffinitytorubberandimproveddispersioninrubber.AtivationofrubberswithSA-moidifiedZnOnanoparticleresultsinincreasedsafetyofprocessingandimprovedperformanceaswell.Moreover,evenwhenSA-cappedZnOwasintroducedintotherubbermatrixatalowereddosage,resultantrubbersstillpossessedgreatlyimprovedcuringactivityandmechanicalproperties.Keywords:ZnOnanoparticle,Surfacemodification,Organicallymodifiedsilica,Mechanochemistry,Sunscreencosmetics,Rubber111ZnOZnOZnOZnO1.1[1]ZnOZnOZnOZnO1ZnOZnOZnO2ZnO3ZnOZnO1.1.11[2,3]ZnOZnOZnOZnO2ZnOZnOZnO[4,5]2[6]ZnOZnO400~600ZnOZnO3[7-9]ZnOZnOZnOZnOCO2H2OZnO13SO24ZnO[10,11]ZnO[12]5[13,14]ZnO0.25~0.5%ZnOZnO35~50%6TiO2ZnOZnO[15]ZnOZnO[16,17]ZnO[18,19]4ZnO1.1.2ZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnO1[20]15220OstwaldMechanochemistry[21-23]162[24][25]ZnOZnO[26]ZnO2ZnOZnO173EI-shall[27]ZnO1.1.32001[28]ZnO[29]ZnO/ZnOZnOZnOZnO[30]ZnO8ZnO17~30%[31]ZnOZnOZnO1.21.2.1200~400nmUVC200~290nmUVB290~320nmUVA320~400nmUVAUVA-II320~340nmUVA-I340~400nmUVCUVBUVAD3[32][33,34]UVBUVBUVA95%UVA[35]UVA[36]UVA19UVAUVA[37-40]UVA[41]ZnOUVAFoodandDrugAdmistraton,FDAUVAZnO3.2eVZnORayleigh[42]ZnOUVAUVBZnO1.2.2ZnOZnOZnO1.1[43]ZnO3.2eV380nme-h+10ZnOZnOZnO1.1.Fig.1.1SchemeillustratingthephotochemicaleventsthatoccurwhenZnOisphotoactivatedbytheabsorptionofUVradiation.ZnO[44][45]ZnOAl3+Co3+[46]ZnOZnOZnO111ZnOZn2+Zn2+Zn2+W/OO/WZnOZnO[47]ZnOpHpH8.5pH67ZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnOZnO[48]ZnOZnOZnOZnO1.2.31ZnO[49-54][46,55]Zn2+12ZnOZnOZnO[56]Zn2+ZnO2ZnOZnO[57]ZnOZnO[58]ZnOZnOZnOZnOHong[59,60]PMMAZnOZnOZnOMitchnich[61]ZnOZnOGrasset[62]ZnOZnOMa[63]KH570ZnOZnO1131.2.4/[64]OrganincallyModifiedSilicaOrganicallyModifiedSilicatesORMOSIL[65-68]Si―O―SiTEOSTMOSR4-xSi(OR')x,Rx13CH3C2H4C2H5C6H5(CH2)3NH2(CH2)3SH[69]Si―O―Si14ZnOZnO1.3ZnOZnOZnOZnO[70]1.3.11ZnOSBRNRBRNBRZnOZnOZnO5ZnO2~31152ZnOZnO45ZnOZnOZnCl2ZnOZnOZnO43ZnOZnOZnOZnOl050ZnO30~50%ZnOZnOZnO1.3.2ZnOZnO16ZnOZnOZnOZnOZ