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@ARTICLE{Go:633016,
author = {Go, Eun Sul and Hong, Eun Ji and Lee, Ji Yeong and Stolar,
Tomislav and Peterson, Gregory I. and Emmerling, Franziska
L. and Kim, Kyoungsoo and Kim, Jeung Gon},
title = {{I}nsights into {M}echanochemical {S}olid-{S}tate
{B}all-{M}illing {R}eaction: {M}onitoring {T}ransition from
{H}eterogeneous to {H}omogeneous {C}onditions},
journal = {JACS Au},
volume = {5},
number = {6},
issn = {2691-3704},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {PUBDB-2025-02342},
pages = {2720 - 2727},
year = {2025},
abstract = {As mechanochemical synthesis has advanced significantly,
there has been intense interest in understanding the
underlying mechanisms of these reactions. Given that many
mechanochemical processes are conducted in the solid-state
without solvation yet sometimes yield faster reactions than
those in solution, we sought to address the following
question: Are mechanochemical reactions homo- or
heterogeneous? To investigate, we employed a model system
involving the mixing and copolymerization of l-lactide (LLA)
and d-lactide (DLA), monitored through powder X-ray
diffraction (PXRD), nuclear magnetic resonance, and
differential scanning calorimetry. In situ and ex situ PXRD
analyses of the mixture of LLA and DLA showed that vibratory
ball milling rapidly transformed the initially heterogeneous
lactide mixture into a homogeneous phase within one min due
to collisions between the balls and the jar. By varying the
milling conditions, we were able to regulate the level of
mixing, which subsequently influenced the copolymerization
outcomes. In the solid-state ball-milling copolymerization
of LLA and DLA in the presence of a catalyst and initiator,
multiblock copolymers of poly(l-lactic acid) and
poly(d-lactic acid) were formed within one min during the
early stage of the reaction, when incomplete mixing of the
monomers led to a process governed by phase heterogeneity.
In contrast, prolonged polymerization promoted conditions
approaching homogeneity, ultimately yielding atactic
poly(lactic acid). This transition from heterogeneous to
homogeneous reactions is a distinctive feature compared to
conventional homogeneous reactions, potentially leading to
mechano-exclusive reaction designs.},
cin = {DOOR ; HAS-User},
ddc = {540},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal: I-20231186
(I-20231186)},
pid = {G:(DE-HGF)POF4-6G3 / G:(DE-H253)I-20231186},
experiment = {EXP:(DE-H253)P-P02.1-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/jacsau.5c00322},
url = {https://bib-pubdb1.desy.de/record/633016},
}