Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis and liquid crystalline properties of new amide‐modified poly(1,4‐cyclohexanedimethylene terephthalate)

New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006     

Lightly crosslinked,mesomorphic networks obtained through the reaction of dimeric,liquid‐crystalline epoxy–imine monomers and heptanedioic acid

We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006     

Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate

The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO₄ (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO₄, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006     

Synthesis and luminescence characteristics of conjugated dendrimers with 2,4,6‐triaryl‐1,3,5‐triazine periphery

We have synthesized conjugated dendrimer with triazine peripheries, and their luminescence properties were investigated. The dendrimers consist of dendritic triazine wedges for electron transport, distyrylbenzene core as an emitting moiety, and t‐butyl peripheral groups for good processing properties. The dendrimers have LUMO values of about ?2.7 eV possibly because of the triazine moiety with high electron affinity. Photoluminescence study indicates that energy transfer occurs from the triazine wedges to the stilbene bridge, and finally to the core chromophore units due to a cascade decrease of bandgap from the peripheral wedge to core moiety. Therefore, the emission wavelength was determined by the structure of the core unit. The energy transfer efficiency of distyrylbenzene‐cored dendrimers was about 75 and 55% for Trz‐1GD‐DSB and Trz‐2GD‐DSB, respectively. A preliminary electroluminescence property also was investigated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 254–263, 2006     

Stimuli‐responsive polymers. VIII. Polyesters and poly(ester amides) containing azobenzene and chiral binaphthylene segments: Highly adaptive materials endowed with light‐, heat‐, and solvent‐regulated optical rotatory power

Azobenzene‐modified polyesters and poly(ester amide)s fitted with chiral, atropisomeric binaphthylene segments were prepared by a series of low‐temperature polycondensation reactions carried out in polar solvent media. When compared with their polyaramide counterparts studied earlier, these materials had significantly improved solubility behaviors and were readily dissolved by a wide range of organic solvents. In solution, each of these constructs underwent photoinduced oscillations in optical rotatory power when subjected to multiple UV‐light/visible‐light illumination cycles that drove trans?cis isomerization reactions along their polymer chains. Light‐regulated chiroptical perturbations were dependent on polymer backbone structures and were further modulated by well‐coordinated temperature fluctuations and by the nature of the solvent medium employed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 207–218, 2006     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

Postmodification of poly(9‐alkyl‐9H‐carbazole‐2,7‐diyl)s as a route to new main‐chain‐functionalized carbazole polymers

The postmodification of poly[9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P1 ) upon its reaction with N‐bromosuccinimide affords exclusive and full bromination of the 3,6‐positions of the carbazole repeat units to yield poly[3,6‐dibromo‐9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P2 ). Brominated polymer P2 can be used as a precursor for further functionalization at the 3,6‐positions with the desired functional group to afford other useful polymers. Polymer P2 has hence been reacted with copper(I) cyanide to afford poly[3,6‐dicyano‐9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P3 ). Full substitution of the bromide groups with nitrile‐functional groups has been achieved. The preparation and structural characterization of polymers P2 and P3 are presented together with studies on their electronic conjugation and photoluminescence properties. Cyclic voltammetry studies on polymer P3 indicate that the new polymer is easier to reduce (n‐dope) but more difficult to oxidize than its unsubstituted counterpart ( P1 ) as a result of the introduction of the electron‐withdrawing nitrile‐functional groups at the 3,6‐positions on the carbazole repeat units on the polymer chains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3336–3342, 2006     

Poly(ortho‐phenylene ethynylene)s: Synthetic accessibility and optical properties

Poly(ortho‐phenylene ethynylene)s (PoPEs) have been synthesized via an in situ activation/coupling AB′ polycondensation protocol. The resulting polymers have been characterized by several analytical methods and are shown to have no structural defects. Although the Sonogashira–Hagihara polycondensation reaction is less efficient than for the preparation of the corresponding meta‐ and para‐linked polymers, presumably because of steric hindrance caused by the ortho substituents, the process can be accelerated by the use of microwave irradiation. Optical spectroscopy indicates solvent‐dependent conformational changes between extended transoid and helical cisoid conformations, providing the first experimental evidence for solvophobically driven folding of the PoPE backbone. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1619–1627, 2006     

Template atom transfer radical polymerization of a diaminopyrimidine‐derivatized monomer in the presence of a uracil‐containing polymer

Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006