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

Schmitt, Adam K.; Mahanthappa, Mahesh K.

doi:10.1021/acs.macromol.7b01452

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

Journal Article · Thu Aug 31 00:00:00 EDT 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.7b01452· OSTI ID:1409091

Schmitt, Adam K. ^[1]; ^[2]

Univ. of Wisconsin, Madison, WI (United States)
Univ. of Wisconsin, Madison, WI (United States); Univ. of Minnesota, Minneapolis, MN (United States)

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 (M_n = 4.5–17.7 kg/mol; Ð = M_w/M_n = 1.72–1.88) and narrow dispersity L end blocks (M_n = 0.6–15.3 kg/mol; Ð = 1.10–1.21) with volume fractions 0.26 ≤ $$f$$_B ≤ 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 $$χ$$N ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction $$χ$$N ≥ 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, in contrast, 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: E.I. DuPont de Nemours & Co.; National Science Foundation (NSF); Northwestern University; The Dow Chemical Company; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1409091

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 17 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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