Synthesis And Characterization Of Hydrogen Bonded Main Chain Liquid Crystalline Polymers

Author : Wenyi Huang
Publisher :
ISBN 13 :
Total Pages : 236 pages
Book Rating : 4.:/5 (115 download)

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Download or read book Synthesis, Characterization, and Rheology of Functional and Heterocyclic Liquid Crystalline Polymers written by Wenyi Huang and published by . This book was released on 2006 with total page 236 pages. Available in PDF, EPUB and Kindle. Book excerpt: Three segmented main-chain thermotropic liquid crystalline polymers (TLCPs) functionalized with nitrogen-containing heterocyclic groups were synthesized; namely PyHQ12 having pendent pyridyl group, PABP having side-chain azopyridyl group with flexible spacer, and PTBP containing side-chain terpyridine group with flexible spacer. The principles of specific interactions were applied to prepare supramolecular structures and organoclay or clay nanocomposites based on these functional TLCPs. Three combined main-chain/side-chain liquid-crystalline polymers (MCSCLCPs) were prepared via hydrogen bonding or ionic interactions based on PyHQ12 and PABP. The presence of hydrogen bonds in self-assembled PyHQ12-7CNCOOH and PABP-AA, and the presence of ionic interactions in self-assembled PABP-TSA, which exist above their respective clearing temperatures, were confirmed using Fourier transform infrared (FTIR) spectroscopy, the thermal transitions in each MCSCLCP were determined using differential scanning calorimetry (DSC), and the mesophase structures of each self-assembled MCSCLCP were characterized using polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). PyHQ12 was observed to be very effective in exfoliating organoclay (Cloisite 30B) aggregates, because of the formation of hydrogen bonds, as determined by in situ FTIR spectroscopy, between the pendent pyridyl group in PyHQ12 and the hydroxyl groups in the surfactant MT2EtOH residing at the surface of Cloisite 30B. Thus, functionality in TLCP is necessary to obtain highly dispersed organoclay nanocomposites, but at the same time there is a possibility to lose some degree of liquid crystallinity in the TLCP, due to the proximity of the pendent pyridyl group to the mesogenic main-chain backbone. Thus, another functional TLCP, PABP having side-chain azopyridyl group with flexible spacer, was synthesized. It has been found that the liquid crystallinity of PABP in the organoclay nanocomposites was more or less intact and yet organoclay (Cloisite 30B) aggregates were very well dispersed, which was attributed to the fact that the pyridyl group in the side-chain azopyridine of PABP is located sufficiently far away from the mesogenic main chain. The rheological properties of functional TLCP/organoclay nanocomposites were also investigated. A unique polymer/ruthenium complex [RuII(PTBP)(6TPy)](PF6)2 based on PTBP was used to prepare natural clay (Montmorillonite, MMT) nanocomposite. X-ray diffraction and transmission electron microscopy indicate that MMT has a high degree of exfoliation in the matrix of PTBP/ruthenium complex. UV-vis spectroscopy and FTIR spectroscopy show that the driving force for exfoliating MMT in PTBP/ruthenium complex is attributable to the Coulombic interactions between the positively charged ruthenium center in the side chain of the polymer and the negatively charged clay surfaces.