Thermal,dielectric, and mechanical relaxation in poly(benzimidazole)/poly(etherimide) blends

Thermal, dielectric, and mechanical relaxation measurements on miscible blends of polybenzimidazole (PBI) and a polyetherimide (PEI, Ultem 1000) prepared by solution casting from dimethylacetamide (DMAc) reveal a number of structurally related features. Annealing below the glass transition temperature induces an enthalpy relaxation process typical of single-phase glasses of nonequilibrium structure. Dielectric relaxation experiments on samples annealed at ambient conditions reveal two relaxation processes below 400°C. At lower temperatures (50–200°C), the desorption of water is observed. Above 200°C in the first run, a composition-dependent relaxation is seen at the highest frequencies (100 kHz) while a relaxation approximately independent of composition appears in the second run. The latter corresponds to the glass transition of the PEI phase. The glass transition of PBI at this frequency is above the degradation temperature. At lower frequencies a strongly dispersive electrode polarization process masks the high-temperature relaxations. Dynamic mechanical results show similar features with respect to phase separation; the main difference is that the tan δ curves in the first run are complicated by the desorption of residual solvent.     

Thermodynamic properties of poly(2,6-dimethyl-1,4-phenylene ether)

The thermodynamic properties of crystalline and amorphous poly(2,6-dimethyl-1,4-phenylene ether) (PPO

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polymer, General Electric Co.) have been studied calorimetrically between 80 and 570°K. The calculated configurational entropy of this polymer, of similar magnitude to other glass-forming liquids, is consistent with the combination of an unusually high ratio of T_g/T_m, and a low melting entropy.     

Polymer miscibility in capillaries

A thermodynamic analysis predicts an increase in miscibility, relative to that in the bulk state, for a polymer mixture confined in a capillary with a diameter of the order of the size of the polymer coils. This is derived by using both the concepts of growing domains and a consideration of the thickness of polymer–polymer interfaces. The analysis is combined with a Monte Carlo lattice simulation that provides results on such confined systems. Intermixing, described in terms of the number of heterocontacts and the dimensions of the polymer chains in the capillary parallel and perpendicular to the tubular axis, is investigated. The results confirm that demixing in homogeneous mixtures is hindered, whereas intermixing is enhanced, in the capillary relative to that in the unconfined mixture. © 1992 John Wiley & Sons, Inc.     

Para-Xylylenes and analogues by base-induced elimination from 1,4-bis-(dialkylsulfoniomethyl)arene salts in poly(1,4-arylene vinylene) synthesis by the wessling soluble precursor method

para-Xylylenes are generated by treatment of various 1,4-bis(dialkylsulfoniomethyl)arene dihalides with base in water, methanol, and aqueous acetonitrile, as shown by UV-Vis spectroscopy. This procedure allows the monitoring of the transient xylylene monomers that yield polyelectrolyte precursor polymers for poly(arylene vinylene)s, formed by variations of the chemistry developed originally by Wessling and co-workers. Alkoxy, alkyl, and halogen ring substituents on the sulfonium salt precursors do not greatly affect the ability to generate and observe the growth and decay of steady-state concentrations of the para-xylylene intermediates. Use of strong resonance-acceptor substituents—such as cyano or nitro—on the ring reduces production of a strong para-xylylene absorption, possibly due to reluctance of the ylides initially formed from the bis-sulfonium salts to eliminate to the xylylenes. By variation of UV-Vis conditions, it was found that use of 20% aqueous acetonitrile rather than water allowed formation of low to modest molecular weight polyelectrolytes in cyano-substituted cases (M_w = 8000–37,000). Use of UV-Vis test experiments should be useful for screening of bis sulfonium salt precursors that may be expected to give high molecular weight polyelectrolytes—in cases where para-xylylene formation is easy—as well as for finding reaction conditions that will optimize polymer formation. © 1992 John Wiley & Sons, Inc.     

Preparation of poly(phenylene vinylene) from cycloalkylene sulfonium salt monomers and polymers

Two new types of p-xylene bis-sulfonium chloride monomers were prepared from cycloalkylene sulfides. The polymerization characteristics of these monomers to form poly(p-xylene sulfonium chlorides), and the thermal elimination reactions of their polymers to poly(p-phenylene vinylene), were compared with those of two monomers prepared from dialkyl sulfides. The cycloalkylene sulfonium chloride monomer polymerized to higher yields and to higher molecular weight polymers, which showed more efficient elimination reactions.     

Intercalation ofn-alkylamines into α-titanium phosphate from aqueous solutions

The intercalation reactions betweenn-alkylamines and -titanium phosphate in aqueous media have been investigated. The compounds with the maximum intercalation have the formula -Ti(HOPO₃)₂ · 2 C _n H _2n+1 NH₂ · H₂O (n=1–10). Defined crystalline phases with lower amine content are described, the general formula being -Ti(HOPO₃)₂ · _m C _n H _2n+1 NH₂ ·pH₂O (m=1.0 1.3, 1.5, 1.7). Whenm=1.0 then-alkylamines form a monomolecular layer. Whenm>1.0 the layer is bimolecular. The inclination angle and the packing density of then-alkylamines in the interlayer space is determined.     

Miscibility of Some Polycarbonates with Polyvinyl Chloride and Chlorinated Polyvinyl Chloride

The phase behavior of several polycarbonate homopolymers and copolymers blended with PVC and chlorinated PVCs (CPVCs) has been investigated. Tetrachlorobisphenol-A polycarbonate (TCPC) is miscible in all proportions with PVC and CPVCs containing up to70.2 wt% chlorine. CPVCs having chlorine contents greater than 70.2% (by weight) are immiscible with TCPC. Tetrabromobisphenol-A polycarbonate (TBPC) exhibits phase mixing with PVC and CPVCs; however, the high T_g of this polycarbonate (260°C) prevents adequate investigation of equilibrium phase behavior. Bisphenol-A polycarbonate (BPC), tetramethylbisphenol-A polycarbonate (TMPC), and hexafluorobisphenol-A polycarbonate (HFPC) form two-phase mixtures with the vinyl polymers. Microstructural differences in the CPVCs due to chlorination method (solution chlorination vs. slurry chlorination) have no effect on the miscibility results. Miscibility was observed in several copolycarbonate/CPVC blends and was found to be dependent on copolymer composition. Using a binary interaction, mean-field theory, segmental interaction parameters were estimated for repeat unit interactions. Based on the estimated interaction parameters, miscibility in these blends is primarily the result of intramolecular repulsive effects, rather than strong intermolecular attractive forces.This revised version was published online in November 2005 with corrections to the Cover Date.     

Microwave properties of low-density polyacetylene

The results of an initial study of the microwave properties of low-density foamlike (CH)_x are reported for intermediate dopant levels. The electrical conductivity and dielectric constant are obtained at microwave frequencies, and the results are analyzed in terms of effective medium theory. The possibility of utilizing the doped foamlike (CH)_x as an efficient microwave absorber is discussed.     

Poly[(2‐alkoxy‐5‐methyl‐1,3‐phenylene vinylene)‐alt‐(phenylene vinylene)] derivatives with different contents of cis‐ and trans‐olefins: The effect of the olefin bond geometry and conjugation length on luminescence

Poly[(2‐alkyloxy‐5‐methyl‐1,3‐phenylenevinylene)‐alt‐(1,3‐phenylenevinylene)]s ( 8 ) and poly[(2‐alkyloxy‐5‐methyl‐1,3‐phenylenevinylene)‐alt‐(1,4‐phenylenevinylene)]s ( 10 ) were synthesized by the Wittig reaction to provide materials containing 45–62% cis‐vinylene bonds. The optical characteristics of 8 and 10 were compared with those of their respective isomers, 3 and 4 , the cis‐vinylene contents of which were significantly lower (9–16%). Although a greater fraction of cis‐CH?CH linkages caused the absorption maximum (λ_max) of 8 and 10 to be slightly blueshifted (by ～3–6 nm) from that of 3 and 4 , the impact of the vinylene bond geometry appeared to be negligible on their fluorescence spectra. The fluorescence quantum efficiencies of 8 and 10 were estimated to be approximately 0.25 and 0.72, respectively. Both 8 (λ_max ≈ 445 or 462 nm) and 10 (λ_max ≈ 480 or 506 nm) were electroluminescent, showing effective color tuning by the controlled insertion of m‐phenylene moieties. The external electroluminescence quantum efficiencies were determined to be 4.26 × 10^?3% for 8 and 0.63% for 10 . The cis/trans‐vinylene bond ratio had a great impact on the electroluminescence device performance of 8 but a much smaller impact on the performance of 10 . © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 303–316, 2004