二氧化硅粒子的表面化学修饰_方法_原理及应用_陈凯玲

1、25120131PROGRESSINCHEMISTRYVol．25No．1Jan．20132012620129*Correspondingauthore-mailzhaoyunhui@tju．edu．cnyuanxy@tju．edu．cn———、**300072、、-、。。。O613.72TB332A1005-281X201301-0095-10ChemicalModificationofSilicaMethodMechanismandApplicationChenKailingZhaoYunhui*YuanXiaoyan*SchoolofMaterialsScienceandEngineeringTianjinKeyLaboratoryofCompositeandFunctionalMaterialsTianjinUniversityTianjin300072ChinaAbstractSilicaisoneofthemostimportantinorganicmaterialsandhasbeendrawingagrowingnumberofattentionsinthefield。

2、oforganic/inorganiccompositematerials．Inthispaperresearchprogressonmethodsandmechanismsofchemicalmodificationaswellasapplicationsofmodifiedsilicaparticlesarereviewedindetail．Mechanismsofcouplingmethodsurfacegraftingmethods“graftingfrom”and“graftingonto”includedandone-stepmethodarediscussedalongwiththecommentsonkeypointsandadvantagesofthesemethods．Themethodsof“graftingfrom”basedonconventionalfreeradicalpolymerizationatomtransferradicalpolymerizationandreversibleaddition-fragmentationchaintransfer。

3、polymerizationarediscussedwhereas“graftingon”basedonring-openingadditionreaction“clickchemistry”andesterificationreactionaredescribed．Generallyendowingsilicasurfacewithfunctionalgroupsforfurtherreactionbysilanecouplingagentsisessentialandsilanecouplingagentsandtheirmodificationmechanismsareintroducedfirstly．Inadditionone-stepmethodisalsodiscussedhere．Atthesametimesignificancesofsurfacemodificationwhichareimprovementondispersibilityendowingsilicawithfunctionalityandimprovementoncompatibilityaresu。

4、mmarized．Thedispersibilityofsurfacemodifiedsilicaparticlesinorganicsolventsororganicmatrixisimproved．Themodifiedsilicaparticlesarefunctionedbythegroupsorpolymerswhicharegraftedontheirsurfaces．Theadhesiveforcesbetweenorganicphaseandinorganicphaseareenhancedsincethemodifiedsilicaparticlesaredispersedwellintheorganicmatrix．Andthemodifiedsilicaparticlesareexpectedapplicationsinfabricatingnewmaterials．Keywordssilicachemicalmodificationcouplingmethodsurfacegraftingmethodone-stepmethod·96·25Contents1In。

5、troduction2Methodsandmechanismsofchemicalmodification2.1Couplingmethod2.2Surfacegraftingmethod2.3One-stepmethod3Significanceofsurfacemodification3.1Improvementondispersibility3.2Endowingsilicawithfunctionality3.3Improvementoncompatibility3.4Othersignificances4Conclusionsandoutlook1SiO21。-sol-gelSiO223PS“”4SiO2。SiO256。、。SiO2、。SiO27。、、。SiO2。3、。SiO2。SiO2SiO2。22.1postsynthesisgraftingmethod8co-condensationmethod9。SiO2SiO2SiO2SiO2。SiO2TEOSSiO2。Sun10SiO2pH。。SiO211。1SiO2Scheme1Mechanismformodificationo。

6、fSiO2bysilanecouplingagentsSiO212YCH2nSiX3n=0—3X、X1———、·97·Y、Y“”YSiO2。SiO21。XSi—OHSi—OHSiO2Si—OHSi—O—SiXSiO2Si—OHSi—O—Si1314。SiO2。2.2SiO2SiO2。SiO2-2、34、1516179、V18、Y19。Matyjaszewski20ATRPSiO2SiO2。rch＞rc“”polymer-likeh＜rc“”hard-sphere-like。hrchh。“”。2.2.1SiO2graftingfrom721。SiO2“”22。SiO21SiO2FRP2SiO2ATRP3SiO2-RAFT。———MPSSiO2SiO2。Wang8MPSSiO2MMASDSKPSMMASiO2IRPMMASiO2TEM-SiO2PMMA30nm。PMMASiO2NR。Kang9TEOSSiO2MPSMPSSiO2。N-VCz、DVBAIBN-distillation-precipitationpolymerizationSiO2PVKTEM-SiO2PVK14—19nm。。。

7、、。Matyjaszewski23ATRPRAFTSiO2。Werne242519992001ATRPSiO2PSPMMA。SiO2ATRPSiO2ATRPSiO2。Park26SiO22-CPCSiO2—ClATRPSSAPOEMSiO22a。IR、UV、XXRDXXPS·98·25POEMPSSASiO2。TGAPSSAPOEM5wt%8wt%。POEM27。PSSA。PSSASiO2。SEMPSSAPOEMSiO2SiO2。ATRP-ARGETATRP28Fe3+Fe2+。Du29APTESSiO22-—BrSiO2。Fe2+CVcATRPMMASiO22b。IRPMMASiO2TEM-SiO2。2ATRPSiO2aSiO2-g-POEMSiO2-g-PSSA26bSiO2-g-PMMA29Scheme2SyntheticroutesofaSiO2-g-POEMandSiO2-g-PSSA26bSiO2-g-PMMA29byATRPATRP、SiO2“”SiO2。ATRP。RAFTSiO2———SiO2RAFT。RAFT30。RAFTSiO2R-R-groupapproachZ-。

8、Z-groupapproach3。RRAFTZ-。R-Z-。R-“”31。Z-。32。Ohno33RAFTEHT4aSiO2SiO2“”PS“”。PS1.3×105PDI1.15TGA0.2—0.5/nm2。TEM-。CLSM1———、·99·3RAFTR-Z-31Scheme3StructureofRAFTagentandmechanismsofpolymerizationviaZ-groupapproachandR-groupapproach31。SiO2PMMA、PBAPNIPAM。Zhu34———CMPTSSiO2。RAFTBCBD4bSiO2SiO2-BCBD4c4-4-VP。IR、UVXPSRAFTBCBDP4VPSiO2。TEM-SiO2。P4VPP4VPAu、Ag/。RAFT、。SiO2。4RAFTaEHT33bBCBD35cBCBDSiO234Scheme4SynthesisofRAFTagentsaEHT33bBCBD35andcreactionbetweenBCBDandSiO234RAFT。·100·252.2.2736“Graftingonto”。ring-o。

9、peningadditionreactionSiO2。He18CDBRAFT-b--b-PMMA-b-PGMA-b-PtBMA5a。PGMASiO2Si—OH120℃TEAPMMA-b-PGMA-b-PtBMASiO2V“”。PtBMATFAPMAAPMMA-g-SiO2-g-PMAA。PMMAPMAA。5abV18Scheme5aSyntheticrouteoftriblockcopolymersandbmodificationofsilicananoparticleswith“V-shaped”mixedpolymerbrushandthesubsequentself-assemblyatoil-waterinterface18clickchemistry“”37SiO2。Fried38Cu+-SiO2。。Kang9-PNIPAMSiO2“PNIPAM”0.1/nm2。Kar39SiO2Si—OHAzPTES1∶1SiO23/nm2。PLLSiO2pH=7、Cu+-6。TGAPLL1.02/nm21.1/nm2。“graftingfrom”“graftingonto”“”“graf。

10、tingonto”。6PLLSiO239Scheme6ProcedureofgraftingPLLchainsontosurfaceofSiO2byclickchemistry39esterificationreactionSiO2。。FengSiO2PEG40PS41。SiO21———、·101·7PEGSiO240Scheme7ProcedureofgraftingPEGchainsontothesurfaceofSiO2byesterificationreaction40PEG7。SiO223-GPTMSSiO2100℃2hSiO2-CH2OHSiO2-CH2OHPEGPEG-COOHNN'-DCC、4--p-DPTSPEGSiO240。IRESCAPEGSiO2PEG55wt%。TEM-DLS。SiO2PEGSiO2PEGSiO2“”。SiO2。Hwang42PEGMEIPTESPEGMEPEGME-IPTES-SiO2PEGME-IPTESPEGSiO2。2.2.3SiO2743。SiO2Si—OHSi—O—Si。-。SiO27。44。SiO245、43。43SiO2TGASi。