ma048327y_si_001.pdf (438.9 kB)
Tailored Phase Transitions via Mixed-Mesogen Liquid Crystalline Polymers with Silicon-Based Spacers
journal contribution
posted on 2005-05-17, 00:00 authored by Ingrid A. Rousseau, Haihu Qin, Patrick T. MatherControl over thermotropic phase behavior in low-Tg main-chain liquid crystalline polymers
(LCPs) is desired for a variety of applications, including soft actuation when cross-linked. Here, we describe
the synthesis of new silicon-based main-chain LCPs, including homopolymers, blends, and copolymers,
with tunable clearing temperatures as governed by their chemical composition. Two mesogenic groups,
namely, 1,4-bis[4-(4-pentenyloxy)benzoyl]hydroquinone (M1) and 2-tert-butyl-1,4-bis[4-(4-pentenyloxy)benzoyl]hydroquinone (M2), were polymerized with various silicon-based flexible spacers, specifically,
1,4-bis(dimethylsilyl)benzene (S1), 1,1,3,3,5,5-hexamethyltrisiloxane (S2), and hydride-terminated poly(dimethylsiloxane) (DP = 8) (S3) spacers, following routine hydrosilation reaction techniques. These
mesogens and flexible spacers were chosen so that both copolymerization and blending of homopolymers
would allow for potential tailoring of phase behavior. Indeed, despite their similar chemical structure,
the clearing transition temperatures of M1 and M2 differ dramatically (ΔTNI = 140 °C), while the silicon-based spacers offer accessibility to a large range of molecular flexibility. High-molecular-weight LCPs
were successfully prepared using Pt-catalyzed addition polymerization. Interestingly, the polymers
exhibited wide liquid crystalline windows with relatively high degree of order (smectic phases) except for
the S1-based blends, which, in addition to a smectic phase, also displayed a narrow nematic phase. As
expected, a drastic decrease of the glass transition temperature arose on polymerizing with longer, more
flexible spacers, from about 56 to −17 °C. Finally, in comparing the two approaches to phase behavior
tailoring, namely, blending vs copolymerization, the former led to apparently immiscible systems with
constant isotropization temperatures, while the latter yielded homogeneous, single-phased materials with
tunable isotropization temperatures dictated by the M1/M2 ratio of the copolymers.