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Cholesteric Liquid-Crystal Copolyester, Poly[oxycarbonyl- 1,4-phenylene- oxy - 1,4 terephthaloyl- oxy- 1,4-phenylenecarbonyloxy (1,2-dodecane)] [C34H36O8]n, Synthesized from Racemic Materials: Kinetics, Structure and Optical Characterization.
|Autor:||Pérez Méndez, Mercedes ; Sanguino Otero, Javier|
|Palabras clave:||Cholesteric LC-polymer, crystal modelling, kinetics, optical activity|
|Fecha de publicación:||jul-2015|
|Citación:||International journal of engineering research and applications 5( 7 Part. 2): 48-62 (2015)|
|Resumen:||The cholesteric liquid-crystal poly[oxycarbonyl-1,4-phenylene-oxy-1,4 terephthaloyl-oxy-1,4-phenylenecarbonyloxy(1,2-dodecane)] [C34H36O8]n, named PTOBDME, synthesized by polycondensation reaction from equimolar quantities of TOBC and the racemic mixture of glycol (R-S-1,2 dodecanediol), exhibits unexpected optical activity and chiral morphology. The structure of racemic-PTOBDME, under different polymerization kinetics conditions, is analyzed by conventional NMR techniques and compared with those of polymer enantiomers R-PTOBDME and S-PTOBDME obtained starting R(+)1,2 and S(-)1,2-dodecanediol respectively. Molecular models based on the NMR signals intensities are proposed. The optical activity of racemic-PTOBDME is evaluated by measuring the ORD values during kinetics study, and compared to the chiral polymers. Each enantiomeric polymer seems to present the same stereoregular head-tail, isotactic structure than the racemic, which we explain by the higher reactivity of the primary hydroxyl than the secondary one in the glycol through polycondensation. For each enantiomer, two independent sets of signals were observed by NMR, explained as two diastereomeric helical conformers: gg and gt, related with two possible staggered conformations, along the copolymer backbone. Chirality in racemic-PTOBDME is proposed to be due to the kinetic resolution of a preferable helical diastereomer, such as Sgt, with respect to the possible four forms, while the R/S ratio of asymmetric carbon atoms remained 50:50. Chiral amplification is observed in R-PTOBDME and S-PTOBDME due to a helical screw sense excess. Optimum yield was obtained for racemic PTOBDME, after 120 minutes polycondensated and decanted in toluene for 24 hours. Two weeks later a second fraction precipitated from the toluene mother liquor with 67.6% chiral excess. After eight months and two weeks a third fraction precipitated with 85.2% chiral excess.|
|Aparece en las colecciones:||(ICTP) Artículos|
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|IJERA_Cholesteric Liquid-Crystal Copolyester, PTOBDME_(C34H36O8)n_Synthesized from Racemic Materials_Kinetics_Structure and Optical Characterization..pdf||Artículo principal||3,62 MB||Adobe PDF|