Poly(ethylene terephthalate) copolymers containing 5‐nitroisophthalic units. I. Synthesis and characterization

Poly(ethylene terephthalate‐co‐5‐nitroisophthalate) copolymers, abbreviated as PETNI, were synthesized via a two‐step melt copolycondensation of bis(2‐hydroxyethyl) terephthalate and bis(2‐hydroxyethyl) 5‐nitroisophthalate mixtures with molar ratios of these two comonomers varying from 95/5 to 50/50. Polymerization reactions were carried out at temperatures between 200 and 270 °C in the presence of tetrabutyl titanate as a catalyst. The copolyesters were characterized by solution viscosity, GPC, FTIR, and NMR spectroscopy. They were found to be random copolymers and to have a comonomer composition in accordance with that used in the corresponding feed. The copolyesters became less crystalline and showed a steady decay in the melting temperature as the content in 5‐nitroisophthalic units increased. They all showed glass‐transition temperatures superior to that of PET with the maximum value at 85 °C being observed for the 50/50 composition. PETNI copolyesters appeared stable up to 300 °C and thermal degradation was found to occur in two well‐differentiated steps. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1934–1942, 2000     

Poly(ester amide)s derived from L‐tartaric acid and amino alcohols. II. Aregic polymers

A series of aregic poly(ester amide)s (a‐PEAT6) with ester/amide ratios (a : b) varying from 1 : 19 to 1 : 2 were prepared with L ‐tartaric acid, 6‐aminohexanol, and 1,6 hexanediamine as the starting materials. Polycondensation in a solution of the diamine with mixtures of pentachlorophenyl‐activated di‐O‐methyl‐L ‐tartaric and 6‐aminohexyl‐di‐O‐methyl‐L ‐tartaric acids led to a‐PEAT6(a : b), with the a : b ratio determined by the composition of the feed. The newly synthesized poly(ester amide)s were characterized by elemental analysis, size exclusion chromatography, and IR and NMR spectroscopy. They had number‐average molecular weights between 25,000 and 45,000 and were highly crystalline, showing melting temperatures ranging from 100 to 230 °C and glass‐transition temperatures oscillating between 50 and 100 °C. The thermal degradation of a‐PEAT6(a : b) began above 200 °C and concluded with a final weight loss between 60 and 90% of the initial mass. The process evolved with the formation of cyclic tartarimide units and extensive main‐chain scissions. The degradation mechanism is discussed in relation to the chemical composition and microstructure of the polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2687–2696, 2000     

Poly(ethylene terephthalate) copolymers containing nitroterephthalic units. I. Synthesis and characterization

The synthesis, microstructure, and thermal behavior of a series of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units are described. These novel copolyesters were synthesized by transesterification followed by melt copolycondensation of dimethyl terephthalate and dimethyl nitroterephthalate mixtures with ethylene glycol. The molar ratio of the two comonomers in the feed varied from 95/5 to 25/75. Furthermore, PET and poly(ethylene nitroterephthalate) homopolymers were synthesized with the same method and comparatively studied. Copolyester compositions were practically the same as in the feed, and weight‐average molecular weights ranged from 10,000 to 60,000. The two monomeric units were randomly distributed along the polymer chain, and the experimentally determined average sequence lengths were in accordance with ideal copolycondensation statistics. Melting temperatures and enthalpies of the copolyesters decreased with increasing content in nitroterephthalic units, and they all showed a single glass‐transition temperature superior to that of PET. They appeared to be stable up to 300 °C, and thermal degradation occurred in two well‐differentiated steps. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3761–3770, 2000     

Site-selective multi-emitter gold-silver metallopolymers: A novel class of self-assembled materials

New luminescent heterometallopolymers [(Au-C₆F₅)_m(AgOSO₂CF₃)_n (PVP)] with different Au:Ag molar ratios were synthesized. The luminescent emissions of these polymers are strongly dependent on the temperature, excitation wavelengths, and the Au(I):Ag(I) molar ratio. The incorporation of a precise amount of Ag(I) atoms in the backbone of [(Au-C₆F₅)_m(PVP)] metallopolymer allows a controlled tuning of the emission energy in the green-blue range.