Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

Yin, Xuechen; Hewitt, David R.O.; Zheng, Bingqian; Quah, Suan P.; Stanley, Christopher B.; Grubbs, Robert B.; Bhatia, Surita R.

doi:10.1016/j.polymer.2021.123683

Title: Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

Journal Article · Sat May 01 00:00:00 EDT 2021 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2021.123683· OSTI ID:1813236

^[1]; Hewitt, David R.O. ^[1]; Zheng, Bingqian ^[1]; Quah, Suan P. ^[1];

^[2]; Grubbs, Robert B. ^[1];

^[1]

Stony Brook Univ., NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report on the nanoscale assembly of poly(lactic acid)-b-poly(ethylene oxide)-b-poly(lactic acid) (PLA-PEO-PLA) triblock copolymers in water, focusing on the effect of stereochemistry, where the PLA blocks are statistical copolymers of l-lactide and d-lactide with l/d ratios of 100/0, 95/5, 90/10, 85/15, 75/25, and 50/50. Small-angle neutron scattering (SANS) shows a nearly constant d-spacing as concentration varies in triblock systems with l/d ratios of 90/10 and 95/5, which we attribute to inhomogeneity in the structure of these gels, supported by previous USANS and confocal microscopy studies. The SANS data fit well to a core-shell ellipsoid form factor model with a hard-sphere structure factor. Polymeric micelles with l/d ratios from 75/25 to 85/15 displayed very high aggregation numbers, consistent with a strong interaction between PLA chains and the enhanced storage modulus observed in rheological studies of these systems. While the 90/10 and 95/5 samples showed lower aggregation numbers, their SANS profiles shows close spacing between micelles, which may promote a high fraction of intermicellar bridging chains, also consistent with a higher storage modulus. Overall, these results provide insight into the micellar assembly behavior of block copolymers with a crystallizable block, and indicate that tuning stereochemistry of PLA-based block copolymers is an effective means of modifying micellar properties for specific applications.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1813236

Journal Information:: Polymer, Vol. 223, Issue 1; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

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