Effect of aniline formaldehyde resin on the conjugation length and structure of doped polyaniline: Spectral studies

A DBSA (n‐dodecylbenzene sulfate)‐complexed aniline formaldehyde [AF(DBSA)_1.0] was successfully synthesized with excess aniline (compared with formaldehyde) in the presence of n‐dodecylbenzene sulfonic acid (HDBSA), which was complexed with aniline monomer before polymerization. The resin was carefully characterized with ¹H and ¹³C NMR, electron spectroscopy for chemical analysis, and Fourier transform infrared and was demonstrated to be a polymer in which anilines were all complexed with HDBSA and became anilinium salts. A drastic decrease of the maximum absorption wavelength (ultraviolet–visible spectra) of DBSA‐doped polyaniline [PANI(DBSA)_0.5] was found when AF(DBSA)_1.0 was mixed, and this resulted from the reduced conjugation length. A similar effect on PANI(DBSA)_0.5 was found when free HDBSAs were mixed with PANI(DBSA)_0.5. Visual inspection with an optical microscope revealed that PANI(DBSA)_0.5/AF(DBSA)_1.0 gave uniform morphologies in various compositions, showing possible miscibility for this system. X‐ray diffraction patterns of PANI(DBSA)_0.5/AF(DBSA)_1.0 showed that the layered structure of PANI(DBSA)_0.5 was still present but became shorter in the polyblend because of the presence of AF(DBSA)_1.0. Solid‐state ¹³C NMR spectra revealed that the reduced conjugation length was derived from the interaction of alkyl groups between HDBSA, complexed DBSA, and dopant DBSAs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3116–3125, 2005     

IONIC THERMOPLASTIC ELASTOMERS: A REVIEW

The incorporation of small amount of ionic groups into hydrocarbon polymers results in unique physical properties and these polymers are called ionomers. They are effectively cross-linked through the association of ionic groups, forming multiplets or clusters. These associations are thermally labile to a greater or lesser extent depending on the composition of the ionic domains. In elastomeric ionomers, the thermolabile nature of the ionic domains permits the adequate flow at the processing temperatures, and hence the term ionic thermoplastic elastomers. Polar plasticizers are incorporated into ion-containing polymers in order to reduce the melt viscosity, resulting from the strong ionic associations, and to improve the processability. The introduction of ionic groups into the block copolymers improves their thermal stability and high temperature performance. The presence of ion-ion interactions in different rubber/plastic blends enhances the mechanical compatibility of the otherwise incompatible blends and thereby results in the formation of ionic thermoplastic elastomers, depending on the rubber to plastic ratios. In the absence of ionic groups the blend components are incompatible, as indicated by poor physical properties of the blends. However, the introduction of ionic groups onto the polymer chains causes a dramatic increase in compatibility between the rubbery and the plastic phases, as indicated by the synergism in physical properties. The present paper reviews the ionic thermoplastic elastomers based on elastomeric ionomers, block copolymer ionomers, and ionomeric polyblends.     

Enhancing the electroluminescent efficiency of poly{5‐methoxy‐2‐[(2′‐ethyl‐hexyl)‐oxy]‐p‐phenylenevinylene}/poly(2,3‐diphenyl‐5‐octyl‐p‐phenylenevinylene) polyblends by the introduction of chemical bonding through a thermal treatment

A significant improvement in the electroluminescence (EL) properties was observed for a poly{5‐methoxy‐2‐[(2′‐ethyl‐hexyl)‐oxy]‐p‐phenylenevinylene} (MEH–PPV)/poly(2,3‐diphenyl‐5‐octyl‐p‐phenylenevinylene) (DPO–PPV) blend after a thermal treatment at 200 °C for 2 h in vacuo to furnish the chemical bonding between polymer chains. ¹H NMR spectroscopy and two‐photon excitation microscopy revealed that the chemical bonding turned the immiscible polyblend into a system more like a block copolymer with a vertically segregated morphology. Because both the lowest unoccupied molecular orbital and highest occupied molecular orbital levels of MEH–PPV in the wetting layer were higher than those of DPO–PPV in the upper layer, the heterojunction between the two layers of the polymers fit the category of so‐called type II heterojunctions. As a result, the turn‐on voltage of the polymer light‐emitting diode prepared with the thermally treated polyblend decreased to ～0.6 V, and the EL emission intensities and quantum efficiencies increased to about 4 times those of the untreated polyblend. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 62–69, 2006     

含氢键高分子共混体系的分相动力学研究

经过共聚改性的含羟基聚苯乙烯PS(OH)可以和许多含质子接受基团的聚合物形成氢键而成为互溶体系,本文着重研究这类含氢键共混体系的相分离动力学以及它们的相图。PS(OH)是由苯乙烯与对-六氟异丙醇-α-甲基苯乙烯共聚得到。它与聚甲基丙烯酸丁酯PBMA组成的共混物用温度跃变光散射法研究分相动力学行为。分相初期,符合Cahn-Hilliard-Cook线性理论,共混物具有LCST性质。由于PS(OH)中只含有1.5mol%OH基团,使得共聚物的组成不均匀,以及PS(OH)和PBMA的分子量多分散性,导致共混物的临界共溶点不在亚稳单相极限线(Spinodal curve)和稳定单相极限线(Binodal Curve)的最低点。对于临界组成的共混物在分相后期相区的增长按Siggia模型进行。而非临界组成的共混物按Lifshitz-Slyozov模型进行而且散射光强I(q,t)随散射矢量q的变化出现与q无关的峰,这与金属氧化物的共混物有类似的情况。     

Interaction parameters of crystalline/crystalline polypropylene/poly(butene‐1) blends: Effect of molecular fractionation

Compatibility of crystalline/crystalline polypropylene (PP)/poly(butene‐1) (PB‐1) blends was investigated via the method of equilibrium melting temperature depression followed by determining the polymer–polymer interaction parameter (χ) using the Nishi–Wang equation. The composition variation of the equilibrium melting temperatures of blends (T) was determined with the Hoffman–Weeks plot. The T and its variation with the blend composition depended on the crystallization temperature range. The morphological effect of the blend composition was not a contribution factor for the T depressions of PP and PB‐1 in the blends. The interplay of the dilution effect and molecular fractionation effect of the amorphous component on crystallization of the crystalline component in the blends governed the relation of T with the blend composition. The calculated χ values were negative depending on the blend composition. The negative χ values suggested that PP and PB‐1 in the amorphous region were compatible. The composition variation of the χ values was attributed to the molecular fractionation effect during crystallization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 638–648, 2002; DOI 10.1002/polb.10125