Synthesis, structure, and properties of rigid‐rod polymers with special emphasis on poly(p‐phenylene benzobisoxazole) (PBO) and poly(p‐phenylene benzobisthiazole) (PBZT) have been reviewed. Recent studies on chemical modifications and molecular simulations have also been given. After nearly 20 years of research and development, PBO fiber was commercialized in the late 1990s. However, due to processing difficulties, the concept of the so called molecular composites has not been successful. Development of the high compressive strength M5 and dihydroxy‐PBI fibers clearly suggest that there is potential for further developing properties of this class of materials. Opto‐electronic properties have also been reviewed.Synthesis of PBZT.magnified imageSynthesis of PBZT.

Poly(ethylene terephthalate) (PET) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS) was prepared by melt‐mixing and in situ polymerization methods. The melt‐mixed composite showed phase separation while the in situ polymerized composite did not, based on SEM characterization. During melt mixing, the reaction between the epoxy groups of POSS and hydroxyl groups of PET occurred, based on DSC results. DSC results on the in situ polymerization product showed formation of a lower‐melting component compared with PET. The tensile strength and modulus of the melt‐mixed composite fiber decreased compared with those properties of PET, whereas those of the in situ polymerized composite showed slightly higher values than PET despite the relatively small amounts (1 wt%) of POSS used. Dynamic mechanical analysis results showed an increase in storage modulus for the in situ polymerized composite of POSS and PET compared with PET over the temperature range of 40 °C to 140 °C. Copyright © 2004 Society of Chemical Industry

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The crystal structures of nylon‐6 and nylon‐6/clay fibers were investigated on annealing and drawing. Annealing increased the γ‐crystalline form of both fibers, as indicated by the DSC curves, and its effect was dominant in nylon‐6/clay fiber. On drawing, the γ‐crystalline form was easily converted into the α form in nylon‐6, whereas it was still observed at a relatively high spin‐draw ratio in nylon‐6/clay fiber. However, although the α‐crystal form was dominant in nylon‐6, the γ‐crystal form was dominant in nylon‐6/clay with annealing and drawing, on the basis of the XRD data. The fast crystallization rate of nylon‐6/clay compared with pure nylon‐6 was confirmed, on the basis of the Avrami exponent. The initial modulus of nylon‐6/clay fiber was 30 % higher than the neat nylon‐6 fiber. The reinforcing effect of clay on the dynamic storage modulus was observed. Copyright © 2004 Society of Chemical Industry

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