Liquid crystalline phase behavior of supramolecular of poly(4-vinylpyridine) /3,4,5-tris(dodecyloxy) benzoic acid based on hydrogen-bonding interaction，第十届高分子物理国际研讨会（PP’2012)(2012.6.4~8，成都）-中国聚合物网,论文下载

Liquid crystalline phase behavior of supramolecular of poly(4-vinylpyridine) /3,4,5-tris(dodecyloxy) benzoic acid based on hydrogen-bonding interaction

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分子表征

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第十届高分子物理国际研讨会（PP’2012)(2012.6.4~8，成都）

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Supramolecularliquidcrystallinepolymers(LCPs),whicharebasedonnon-covalentinteractions,suchasionicinteraction,hydrogenbonding,orcoordinationinteraction,havegainedremarkableattentionduringthepastdecades.Recently,wesynthesizedaliquidcrystalsupramolecule,whichiscomposedofpoly(4-vinylpyridine)(P4VP)mainchaingraftedwithnonmesogenicsmallmoleculesof3,4,5-tris(dodecyloxy)benzoicacid(TDBA)throughhydrogen-bonding[denotedasP4VP(TDBA)x,wherexisthemolarratioofTDBAtotherepeatingunitofP4VP].Usingwide-angleX-rayscattering(WAXS),weinvestigatedthecompositiondependenceofthephasestrcutureofP4VP(TDBA)x.SimilartothatobservedforothersupramolecularLCPs,itwasfoundthataddingsmallamountofTDBAcouldinducedensityfluctuationofthemixture,whichcouldbeassignedtoadisorderedphase.Withinthexrangeof0.3to0.6,asmecticstructureofthecomplexwasevidencedbytwoscatteringpeakswiththeq-ratioof1:2(q=4πsinθ/λ).Itisveryinterestingtonotethatfurtherincreasingxwouldleadtoahexagonalcolumnarphase.Therefore,thephasefollowsthesequenceofdisorder-smectic-columnarstructureuponaddingmoreTDBA.Boththesmecticlayerspacingandthediameterofcolumndecreasedwithincreasingx.ThisphasebehaviorimpliedthattheP4VPchainconformationchangedfromcoiltooblateandthentobeingstretchedwhenmoreandmoreTDBAmoleculesaregraftedtothemainchain.Wealsouseddifferentialscanningcalorimetry(DSC)andFT-IRtoexplorethepropertiesofcomplex.DSCresultsshowedthattheglasstransitiontemperatureofP4VP(TDBA)xdecreasedwithincreasingx,whilenootherdistinctthermaltransitionwasfounded.ThehydrogenbondingformationwasconfirmedbyFTIRexperiment.OnthebasisofpeakdeconvolutionofFT-IRspectra,therealcomplexratiox*wasestimated.Itwasfoundthatthecharacteristicdimensionoforderedphaseasafunctionof1/x*satisfieddifferentrelationships.Thed-spacingofsmecticphaseisproportionalto1/x*,whilethediameterofcylindersinhexagonalcolumnarphasefollowedamorecomplicatedrelationship.Therelationshipandthemechanismofphasetransition,whichissimilartoblockcopolymersystem,canbeunderstoodonthebasisofmicrophaseseparationbetweenbackbonesandsidechains.

作者：

Shao-Jie Wang, Shuang Yang, Er- Qiang Chen

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2012-10-31 14:46:30

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