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Stereocomplex crystallization behavior and properties of asymmetric combinations of oppositely configured random copolymers based on chiral 2-hydroxyalkanoic acids


Here, asymmetric combinations of chiral 2-hydroxyalkanoic acid (2HAA)-based random copolymers with monomer compositions of approximately 50/50, which can form stereocomplex (SC) crystallites, are reported. The copolymer combinations were l-configured individually crystallizable poly(l-lactic acid-co-l-2-hydroxybutanoic acid) [P(LLA-co-L-2HB)] (47/53) or poly(l-2-hydroxybutanoic acid-co-l-2-hydroxy-3-methylbutanoic acid) [P(L-2HB-co-L-2H3MB)] (49/51) and d-configured individually noncrystallizable poly(d-lactic acid-co-d-2-hydroxy-3-methylbutanoic acid) [P(DLA-co-D-2H3MB)] (45/55). The interplanar distance values of each SC crystallite agreed well with those expected from the homopolymer SC crystallites. This finding indicated that all four types of monomer units cocrystallized to form SC crystallites. The melting temperature values of the stereocomplexed P(LLA-co-L-2HB)/P(DLA-co-D-2H3MB) and P(L-2HB-co-L-2H3MB)/P(DLA-co-D-2H3MB) blends ranged from 149.3 to 163.6 °C, which were higher than the values observed for the unblended P(LLA-co-L-2HB) (84.8 and 88.7 °C) and P(L-2HB-co-L-2H3MB) (61.6–133.1 °C). This study shows the high SC crystallizability of the asymmetric combination of l- and d-configured chiral 2HAA-based random copolymers even when one of them was individually noncrystallizable. This result strongly suggests that SC crystallization occurred when the common monomer units were incorporated into both l- and d-configured 2HAA-based random copolymers. SC crystallization of new types of asymmetric combinations of l- and d-configured random copolymers is expected to diversify the attainable properties and biodegradation behavior of chiral 2HAA-based polymer materials.

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This research was supported by a research grant from The Hibi Science Foundation and JSPS KAKENHI (Grant Number 16K05912).

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HT: Conceptualization, methodology, supervision, validation, formal analysis, data curation, visualization, original draft preparation, reviewing and editing, project administration, funding acquisition. KO: Resources, investigation, formal analysis, reviewing and editing. YA: Supervision (resources and investigation), reviewing and editing.

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Correspondence to Hideto Tsuji.

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Tsuji, H., Osanai, K. & Arakawa, Y. Stereocomplex crystallization behavior and properties of asymmetric combinations of oppositely configured random copolymers based on chiral 2-hydroxyalkanoic acids. Polym J 54, 1453–1463 (2022).

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