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Article
Consequences of Block Number on the Order-Disorder Transition and Viscoelastic Properties of Linear (AB)n Multiblock Copolymers
Macromolecules (2004)
  • Lifeng Wu, University of Minnesota
  • Eric W. Cochran, University of Minnesota
  • Timothy P. Lodge, University of Minnesota
  • Frank S. Bates, University of Minnesota
Abstract

The effect of block number on the order-disorder transition (ODT) and viscoelastic properties were studied for linear (AB) n multiblock copolymers. A series of symmetric poly(styrene-b-isoprene) n multiblocks ((SI) n, n = 1-10) were synthesized by anionic polymerization, and their order-disorder transition temperatures (T ODT) were located using dynamic mechanical spectroscopy. As n increases, T ODT approaches an asymptotic value, consistent with random phase approximation calculations. A systematic difference between the experimental and theoretical results is attributable to the effects of fluctuations, independent of the number of blocks. Addition of up to 20 vol % of a nonselective solvent depresses T ODT, independent of n. The interaction parameter at the transition, ODT, decreases with polymer volume fraction φ as χ ODT ∼ φ -1.3, consistent with previous reports for diblocks (n = 1). In contrast, the viscoelasticity of (AB) n block copolymers depends strongly on block number. A crossover frequency, ω x, demarcating the transition from block/chain- and domain-dominated relaxation, scales as n- 7.5, which is much stronger than the molecular weight dependence of the longest relaxation time for entangled homopolymers. Coherent lamellar grains were imaged for quenched and annealed (SI) n, n = 1, 6, and 10, by transmission electron microscopy. Ellipsoidal lamellar grains, with aspect ratios of 2-3, were recorded, independent of block number, but the grain size decreased with increasing n. These results establish the criteria for designing multiblock copolymers based on χ, N, n, and concentration.

Publication Date
April, 2004
Publisher Statement
Reprinted with permission from Wu, L., Cochran, E.W., Lodge, T.P., Bates, F.S. Consequences of block number on the order-disorder transition and viscoelastic properties of linear (AB) n multiblock copolymers (2004) Macromolecules, 37 (9), pp. 3360-3368. Copyright 2004 American Chemical Society.
Citation Information
Lifeng Wu, Eric W. Cochran, Timothy P. Lodge and Frank S. Bates. "Consequences of Block Number on the Order-Disorder Transition and Viscoelastic Properties of Linear (AB)n Multiblock Copolymers" Macromolecules Vol. 37 Iss. 9 (2004)
Available at: http://works.bepress.com/eric_cochran/9/