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A series of symmetric poly(methyl methacrylate-stat-styrene)-block-polylactide (P(MMA-s-S)-b-PLA) diblock terpolymers with nearly constant molar masses yet varying block interaction parameters were synthesized as a model system to probe the extent and utility of composition fluctuations in the disordered state. A combination of differential scanning calorimetry, dynamic mechanical analysis, and small-angle X-ray scattering revealed that a broad range of segregation strengths ranging from what we ascribe to essentially a mean-field disordered to a fluctuating disordered to an ordered system could be readily obtained by tuning the molar fraction of styrene in these diblocks. The P(MMA-s-S)-b-PLA diblocks were annealed above their order-disorder transition temperatures (TODT) and rapidly quenched to low temperatures to trap the disordered state via vitrification, as confirmed by scanning electron microscopy. Small-angle X-ray scattering and N2 sorption analysis post-removal of PLA demonstrated that a transition from a very weakly structured, mean-field-like melt to a bicontinuous fluctuating disordered state occurred with increasing segregation strength. This work demonstrates that the extent of microphase segregation as well as the domain continuity of the disordered block polymer melt can be tuned using both synthetic design and thermal stimuli, guiding the design of disordered block polymers with targeted nanostructures that have potential technological utility.
Bibliographical noteFunding Information:
The authors thank Prof. Frank Bates for careful reading of the manuscript and insightful comments. Altasorb generously donated lactide monomer. Funding for this work was provided by the National Science Foundation (DMR-1609459). The Hitachi SU8320 SEM was provided by NSF MRI DMR1229263. Parts of this work were carried out in the Characterization Facility, UMN, which receives partial support from NSF through the MRSEC program. Portions of this work were performed at the DuPont–Northwestern–Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the APS, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data were collected using an instrument funded by the NSF under Award Number 0960140.
© 2020 American Chemical Society.
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