Gradient copolymers with broad glass transition temperature regions: Design of purely interphase compositions for damping applications

• Published in: Journal of polymer science. Part B, Polymer physics Vol. 46; no. 1; pp. 48 - 58
• Main Authors: Mok, Michelle M, Kim, Jungki, Torkelson, John M
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 2008; Wiley
• Subjects: addition polymerization; Applied sciences; block copolymers; Copolymerization; Exact sciences and technology; glass transition; mechanical properties; nanoheterogeneity; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; structure-property relations; Styrene(hydroxy) copolymer; block copolymers; copolymerization; Nitroxyl; Styrene derivative copolymer; Experimental study; Butyl acrylate copolymer; mechanical properties; nanoheterogeneity; Glass transition; Random copolymer; structure-property relations; Dynamic mechanical properties; Preparation; addition polymerization; Gradient copolymer; Radical copolymerization; Block copolymer; Comparative study; Styrene copolymer
• ISSN: 0887-6266; 1099-0488
• DOI: 10.1002/polb.21341

Gradient copolymers with gradients in composition along the chain lengths are synthesized by controlled radical polymerization, and their damping behaviors are compared to those of random and block copolymers. The effect of comonomer incompatibility is studied by comparing behaviors of strongly segregating styrene/4-hydroxystyrene (S/HS) and moderately segregating styrene/n-butyl acrylate (S/nBA) copolymers. The effect of composition gradient steepness is studied by designing "constant" or "increasing" gradients via the comonomer addition rate during semibatch polymerization. Dynamic mechanical analysis (DMA) is used to compare the temperature dependences of the storage modulus (E'), loss modulus (E"), and tan δ of the materials. A glass transition breadth (ΔTg) is defined by a temperature range over which E' decreases from 10⁹ Pa to 10⁸ Pa. The gradient copolymer ΔTgs are at least four times larger than the random copolymer ΔTgs. The S/nBA gradient copolymers show strong effects of gradient steepness on ΔTg, with ΔTg being much larger for the increasing gradient than for the constant gradient. DMA data are compared to predictions by Hashimoto et al. for tapered block copolymers in the limit where the taper extends across the entire chain. The shapes of their calculated temperature dependences of E' and E" correspond well to the gradient copolymers with large ΔTg values, providing strong support for symmetric gradient copolymers forming nanoscale, ordered domains with sinusoidal composition profiles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 48-58, 2008