The thermal activation
of cellulose by initial glycosidic bond
cleavage determines the overall rate of conversion to organic products
for energy applications. Here, the kinetics of ether scission by transglycosylation
of β-1,4-glycosidic bonds was measured using the “pulse-heated
analysis of solid reactions” (PHASR) method from 400 to 500
°C. Levoglucosan (LGA) formation from cellulose was temporally
resolved over the full extent of conversion, which was interpreted
via a coupled reactant–product evolution model to determine
an apparent barrier of LGA formation of 27.9 kcal mol–1. In parallel, LGA formation from the glucose monomer of cellobiosan
was measured at temperatures between 380 and 430 °C by isotopically
labeling the 13C1 carbon; an apparent activation
energy of LGA formation was measured as 26.9 ± 1.9 kcal mol–1. The unusually low activation barrier for LGA formation
at lower temperature is in agreement with previous PHASR studies for
cellulose breakdown and is indicative of catalytic rather than thermal
C–O bond activation. A catalytic mechanism was proposed wherein
vicinal hydroxyl groups from neighboring cellulose sheets promote
transglycosidic C–O bond activation. First-principle density
functional theory (DFT) calculations showed that these vicinal hydroxyl
groups cooperatively act to create an environment that (a) stabilizes
charged transition states and (b) aids in proton transfer, thus leading
to reduced activation barriers for transglycosylation. Models incorporating
intrasheet H bonding of cellulose were also used to establish their
influence on kinetics. The calculated apparent barrier (29.5 kcal
mol–1) agreed well with the experimental apparent
activation energy (26.9 ± 1.9 kcal mol–1) and
establishes the dominant mode for cellulose activation and subsequent
levoglucosan formation at lower temperatures (<467 °C) as
site-specific, vicinal hydroxyl-catalyzed transglycosylation.
Isosorbide
is a rigid, sugar-derived building block that has shown
promise in high-performance materials, albeit with a lack of available
controlled polymerization methods. To this end, we provide mechanistic
insights into the cationic and quasi-zwitterionic ring-opening polymerization
(ROP) of an annulated isosorbide derivative (1,4:2,5:3,6-trianhydro-d-mannitol, 5). Ring-opening selectivity of this
tricyclic ether was achieved, and the polymerization is selectively
directed toward different macromolecular architectures, allowing for
formation of either linear or cyclic polymers. Notably, straightforward
recycling of unreacted monomer can be accomplished via sublimation.
This work provides the first platform for tailored polymer architectures
from isosorbide via ROP.
We
report the rapid, one-pot synthesis of functional polycarbonates
derived from renewable alcohols (i.e., glucose tetraacetate, acetyl
isosorbide, lauryl alcohol, and ethanol) and a cyclic carbonate bearing
an imidazolecarboxylate. This tandem functionalization/ring-opening
polymerization strategy can be performed on multigram scale and eliminates
the need for rigorous purification and specialized equipment. A wide
range of glass transition temperatures (T
g) was accessible from these renewable pendant groups (>75 °C T
g window). We also synthesized several statistical
copolycarbonates to show the thermal properties can be tailored with
this tandem method. Additionally, we demonstrate a circular polymer
economy via chemical recycling to a cyclic carbonate precursor. This
work may facilitate development of sustainable polycarbonates with
tailored properties that work toward eliminating plastic waste streams.
We report the facile synthesis and characterization of 1,6-α linked functional stereoregular polysaccharides from biomass-derived levoglucosan via cationic ring-opening polymerization (cROP). Levoglucosan is a bicyclic acetal with rich hydroxyl functionality,...
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