Macromolecules
Macromolecules
5 years ago

Order and Disorder in High χ/Low N, Broad Dispersity ABA Triblock Polymers

Order and Disorder in High χ/Low N, Broad Dispersity ABA Triblock Polymers
Mahesh K. Mahanthappa, Adam K. Schmitt
Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (Mn = 4.5–17.7 kg/mol; Đ = Mw/Mn = 1.72–1.88) and narrow dispersity L end blocks (Mn = 0.6–15.3 kg/mol; Đ = 1.10–1.21) with volume fractions 0.26 ≤ fB ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength χN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction χN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low χ/high N ABA triblocks, the present study indicates that broad B block dispersity in related high χ/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.

Publisher URL: http://dx.doi.org/10.1021/acs.macromol.7b01452

DOI: 10.1021/acs.macromol.7b01452

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