Chemistry of Materials

Polyimide Nanofoams from Aliphatic Polyester-Based Copolymers

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High-temperature polymeric foams were prepared using compositionally asymmetric microphase-separated block copolymers where the major component is thermally stable and the minor component is thermally labile. Upon thermal treatment, the dispersed phase undergoes thermolysis leaving pores the size and shape of which are dictated by the initial copolymer morphology. The driving force behind the survey of aliphatic polyesters as possible labile blocks stems from their quantitative degradation into low-boiling, polar degradation products. Poly(lactones), as a general class of materials, degrade by a backbiting process producing, primarily, monomer and cyclic oligomers. A ring-opening synthetic route to poly-(lactones) affords oligomers of predictable molecular weight, narrow molecular weight distribution, and controlled end-group functionality. Block copolymers were prepared using monofunctional caprolactone and valerolactone oligomers and a high-Tg polyimide. Microphase separation was observed in all cases, and the lactone blocks did not crystallize. Thermal decomposition of the caprolactone block was accomplished by heating the copolymer to 370°C for 5 h. Significant density reductions were found with pore sizes in the 60-70 Å range.