Polyurethanes, frontal polymerization

S. Chen, J. Sui, L. Chen, and J. A. PotMAN, Polyurethane-nanosilica hybrid nanocomposites synthesized by frontal polymerization, J. Polym. Sci. Part A - Polym. Chem., 43 (2005), pp. 1670-1680. 

In 2000, we have begun our research on this topic paying particular attention to the possibility of finding new chemical systems able to frontally polymerize and new FP applications. Specifically, we have studied polyurethanes (19, 20), polyester tyrene resins (21), polydicylopentadiene (22) and its BPNs with polyacrylates (23), Furthermore, we were able to prepare films (24) and to apply FP to the consolidation of porous materials (i.e. stones, woods, flaxes, papers), in particular -but not only- those having a historical-artistic interest (24), In this chapter we present a brief overview of these recent findings. 

Chen, S.H., Sui, )., and Chen, L. (2005) Segmented polyurethane synthesized by frontal polymerization. Colloid. 

Frontal polyurethane polymerization [13-15], frontal atom transfer radical polymerization [16], and frontal ring-opening metathesis polymerization (ROMP) [17] all suffer from short pot lives that is, bulk polymerization occurs in less than an hour. In some cases, the only way to avoid even faster bulk polymerization is to cool the reagents. For example, with frontal ring-opening metathesis polymerization of dicyclopentadiene with a Grubbs catalyst, the starting materials had to be frozen to prevent rapid bulk polymerization [17]. 

Most work has been with free-radical systems but other chemistries can be used. Begishev etal. studied frontal anionic polymerization of e-caprolactam [18, 19], and epoxy chemistry has been used as well [20-23]. Mariani ctal. demonstrated frontal ring-opening metathesis polymerization [17]. Fiori et al. produced polyacrylate-poly(dicydopentadiene) networks frontally [24], and Pojman etal. studied epoxy-acrylate binary systems [25]. Polyurethanes have been prepared frontally [13,14, 26]. Frontal atom transfer radical polymerization has been achieved [16] as well as FP with thiol-ene systems [27]. Recent work has been done using FP to prepare microporous polymers [28-30], polyurethane-nanosilica hybrid nanocomposites [31], and segmented polyurethanes [32]. 

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