Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(25)
Published: March 23, 2024
Abstract
Although
sulfurated
polymers
promise
unique
properties,
their
controlled
synthesis,
particularly
when
it
comes
to
complex
and
functional
architectures,
remains
challenging.
Here,
we
show
that
the
copolymerization
of
oxetane
phenyl
isothiocyanate
selectively
yields
polythioimidocarbonates
as
a
new
class
sulfur
containing
polymers,
with
narrow
molecular
weight
distributions
(
M
n
=5–80
kg/mol
Đ
≤1.2;
,max
=124
kg/mol)
high
melting
points
up
181
°C.
The
method
tolerates
different
substituent
patterns
on
both
isothiocyanate.
Self‐nucleation
experiments
reveal
π‐stacking
substituents,
presence
unsubstituted
polymer
backbones,
kinetically
linkage
selectivity
are
key
factors
in
maximising
points.
increased
tolerance
macro‐chain
transfer
agents
propagation
allows
synthesis
double
crystalline
amphiphilic
diblock
copolymers,
which
can
be
assembled
into
micellar‐
worm‐like
structures
amorphous
cores
water.
In
contrast,
crystallization
driven
self‐assembly
ethanol
gives
cylindrical
micelles
or
platelets.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(24), P. 14038 - 14083
Published: Nov. 2, 2023
Incorporating
sulfur
(S)
atoms
into
polymer
main
chains
endows
these
materials
with
many
attractive
features,
including
a
high
refractive
index,
mechanical
properties,
electrochemical
and
adhesive
ability
to
heavy
metal
ions.
The
copolymerization
involving
S-containing
monomers
constitutes
facile
method
for
effectively
constructing
polymers
diverse
structures,
readily
tunable
sequences,
topological
structures.
In
this
review,
we
describe
the
recent
advances
in
synthesis
of
via
or
multicomponent
polymerization
techniques
concerning
variety
monomers,
such
as
dithiols,
carbon
disulfide,
carbonyl
sulfide,
cyclic
thioanhydrides,
episulfides
elemental
(S8).
Particularly,
significant
focus
is
paid
precise
control
main-chain
sequence,
stereochemistry,
structure
achieving
high-value
applications.
Advanced Energy Materials,
Journal Year:
2023,
Volume and Issue:
14(3)
Published: Nov. 27, 2023
Abstract
Replacing
liquid
electrolytes
with
solid‐state
polymer
(SPEs)
can
solve
the
safety
hazards
of
Li
metal
batteries
(LMBs)
while
increasing
their
energy
density.
However,
there
has
been
limited
success
so
far
in
preparing
advanced
SPEs
controllable
molecular
structure
and
chemical
composition,
posing
great
obstacles
to
further
promoting
its
application
LMBs.
Recently,
ring‐opening
polymerization
(ROP),
including
cationic
ROP,
anionic
metathesis
polymerization,
become
a
dazzling
new
star
achieving
due
mild
conditions
composition
(molecular
structure,
functional
group),
etc.
Besides,
is
no
small
molecule
released
during
process,
which
means
reduced
interfacial
side
reaction.
Hence,
this
review,
merits
ROP
mechanism
as
well
interfering
factors,
etc
are
evaluated
from
perspective
synthetic
chemistry.
Furthermore,
review
focuses
on
outlining
existing
cases
related
much
possible
summarize
them
different
ring
structures
(from
triple
multivariate
ring)
methods,
hoping
provide
comprehensive
understanding
serve
strategic
guidance
for
designing
high‐performance
SPEs.
Challenges
opportunities
regarding
burgeoning
field
also
discussed
at
end.
JACS Au,
Journal Year:
2023,
Volume and Issue:
3(9), P. 2436 - 2450
Published: Aug. 23, 2023
Over
the
past
couple
of
decades,
polymers
that
depolymerize
end-to-end
upon
cleavage
their
backbone
or
activation
a
terminal
functional
group,
sometimes
referred
to
as
"self-immolative"
polymers,
have
been
attracting
increasing
attention.
They
are
growing
interest
in
context
enhancing
polymer
degradability
but
also
recycling
they
allow
monomers
be
regenerated
controlled
manner
under
mild
conditions.
Furthermore,
highly
promising
for
applications
smart
materials
due
ability
provide
an
amplified
response
specific
signal,
single
sensing
event
is
translated
into
generation
many
small
molecules
through
cascade
reactions.
From
chemistry
perspective,
depolymerization
relies
on
principles
self-immolative
linkers
and
ceiling
temperature
(Tc).
In
this
article,
we
will
introduce
key
chemical
concepts
foundations
field
then
our
perspective
recent
exciting
developments.
For
example,
over
few
years,
new
depolymerizable
backbones,
including
polyacetals,
polydisulfides,
polyesters,
polythioesters,
polyalkenamers,
developed,
while
modern
approaches
conventional
backbones
such
polymethacrylates
introduced.
Progress
has
made
topological
evolution
systems,
introduction
fully
block
copolymers,
hyperbranched
networks.
precision
sequence-defined
oligomers
synthesized
studied
data
storage
encryption.
Finally,
perspectives
future
opportunities
challenges
discussed.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(9), P. 7788 - 7798
Published: Feb. 20, 2025
It
remains
a
long-standing
challenge
for
chemical
recycling
of
polyhydroxyalkanoates
(PHAs)
to
propiolactone-based
monomers
due
the
high
ring
strain
and
many
inevitable
side
reactions.
In
this
contribution,
novel
α-spiro-cyclohexyl-propiolactone
(SHPL)
has
been
designed
with
reactivity
toward
ring-opening
polymerization
even
at
catalyst
loading
<1
ppm.
The
resulting
poly(3-hydroxy-2-spiro-cyclohexylpropionate)
(P3HSHP)
exhibited
thermal
stability
Td
364
°C
Tm
272
°C.
Meanwhile,
it
could
be
depolymerized
back
SHPL
in
86%
yield
without
decarboxylation
or
elimination
products.
Notably,
exploited
construct
high-performance
thermoplastic
elastomers
(TPEs)
via
one-pot
copolymerization
ε-caprolactone
(CL).
Particularly,
gradient
P(CL2000-grad-SHPL500)
showcased
an
ultimate
tensile
strength
58.8
±
4.0
MPa,
stretchability
1959
53%,
record
toughness
600
MJ/m3,
elastic
recovery
(>90%).
This
superior
performance
advance
development
new
sustainable
TPEs.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(9)
Published: Jan. 5, 2024
Abstract
Polythioesters
are
important
sustainable
polymers
with
broad
applications.
The
ring‐opening
polymerization
(ROP)
of
S
‐Carboxyanhydrides
(SCAs)
can
afford
polythioesters
functional
groups
that
typically
difficult
to
prepare
by
ROP
thiolactones.
Typical
methods
involving
organocatalysts,
like
dimethylaminopyridine
(DMAP)
and
triethylamine
(Et
3
N),
have
been
plagued
uncontrolled
polymerization,
including
epimerization
for
most
SCAs
resulting
in
the
loss
isotacticity.
Here,
we
report
use
salen
aluminum
catalysts
selective
various
without
epimerization,
affording
functionalized
polythioester
high
molecular
weight
up
37.6
kDa
highest
P
m
value
0.99.
Notably,
TlaSCA
(SCA
prepared
from
thiolactic
acid)
generates
first
example
a
isotactic
crystalline
poly(thiolactic
acid),
which
exhibited
distinct
T
152.6
°C.
Effective
ligand
tailoring
governs
binding
affinity
between
sulfide
chain‐end
metal
center,
thereby
maintaining
activity
organometallic
reducing
occurrence
reactions.
ACS Macro Letters,
Journal Year:
2025,
Volume and Issue:
unknown, P. 377 - 384
Published: March 8, 2025
The
effective
management
of
plastic
waste
is
critical
for
environmental
sustainability.
This
work
explores
the
use
carbocation
catalysts
recycling
common
polyesters
and
polycarbonates
through
alcoholysis.
We
demonstrate
complete
depolymerization
end-of-life
materials
investigate
relationship
between
catalytic
reactivity
structural
features
compounds,
including
cations
their
counteranions.
Carbocations
function
as
Lewis
acids,
facilitating
interaction
with
carbonyls
in
polymer
chains.
Moreover,
our
approach
enables
hierarchical
degradation
polyester
blends.
research
not
only
elucidates
role
carbocations
alcoholysis
these
polymers,
but
also
establishes
a
metal-free
process
efficient
plastics.
