立体复合聚乳酸及其纳米复合物的制备与性能研究-preparation and properties of stereo composite polylactic acid and its nanocomposites.docxVIP

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立体复合聚乳酸及其纳米复合物的制备与性能研究-preparation and properties of stereo composite polylactic acid and its nanocomposites.docx

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立体复合聚乳酸及其纳米复合物的制备与性能研究-preparation and properties of stereo composite polylactic acid and its nanocomposites

PREPARATIONANDSTUDYONPROPERTIESOFSTEREOCOMPLEXPLAANDITSNANOCOMPOSITESAbstractPoly(L-lacticacid)s(PLLA)andPoly(D-lacticacid)s(PDLA)withdifferentmolecularweights(Mw,rangedbetween0.6×104and12.0×104)weresynthesizedviameltandsolidstatepolycondensation.Aseriesblends(L/D1~L/D5)werepreparedbysolution-mixingequalmassofPLLAandPDLA,inwhichcompletestereocomplexationoccurbetweenL-andD-chainsformingstereocomplexPLA(sc-PLA).Theeffectofmolecularweightsonthethermalstability,crystallizationkinetics,andspherulitemorphologywereanalyzedwiththehelpofdifferentialscanningcalorimetry(DSC),polarizingopticalmicroscope(POM),thermogravimetricanalyzer(TGA)Inaddition,sc-PLA/SiO2compositeswerefabricatedwithdifferentSiO2loadingsbydirectlyaddingSiO2dispersionsolutionintopolymersandin-situpolymerizationinthepresenceofacidicsilicasol.ThedispersionmorphologyofSiO2,crystallizationbehavior,thermalproperties,rheologicalpropertyanddegradationpropertyofthecompositeswereinvestigatedbymeansoftransmissionelectronmicroscope(TEM),DSC,TGAandrotaryrheometer.TheresultsindicatedthatthecrystallizationabilityofL/Dblendsenhancedgreatlybecauseofcompletestereocomplexation.Thetemperatureofmeltcrystallizaiton(Tmc)ofL/D5wasupto180℃,by60℃higherthanthatofL/D1.Inaddition,theinitialtemperatureofdegradationinsampleswithhigherMw(L/D4andL/D5)increasedby40℃comparedwithsampleswithlowerMw(L/D1~3).ThecrystallinityimprovedduetothenucleationofSiO2insc-PLA/SiO2composites.Specifically,Xcincreasedfrom30.1%to49.2%at1wt%loading.Comparedwithpuresc-PLA,thermalstabilityofsc-PLA/SiO2improvedobviouslyandtheinitialtemperatureofdegradationincreasedbyca.50℃withadding5wt%ofSiO2.Betterdispersionstatehappenedinthemethodofin-situadditionofSiO2.ThermalstabilitygreatlyimprovedwhenthecontentofSiO2was1.0-1.5wt%.Theinitialtemperatureofdegradationwas50℃higherthanthethatofcrude.RheologicalresultsshowedthatcompositesexhibitedVsolid-likebehaviorwithappearanceofnon-terminaleffectinlowfrequency,indicatingtheformationofnetstructurebetweenSiO2andPLAchains.Inaddition