Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(17), P. 2035 - 2042
Published: April 30, 2024
Comprehensive
Summary
Copolymerization
as
an
efficient
strategy
can
provide
opportunity
to
create
new
closed‐loop
recyclable
polymeric
materials
with
tailored
properties
that
are
generally
inaccessible
the
individual
homopolymers.
In
this
contribution,
bulk
ring‐opening
copolymerization
of
bio‐renewable
δ‐caprolactone
and
trans
‐hexahydro‐(4,5)‐benzofuranone
was
achieved
produce
copolyesters
by
using
organobase/urea
binary
catalyst
at
room
temperature.
The
obtained
exhibited
composition‐dependent
thermal
properties.
Remarkably,
were
able
depolymerize
back
recover
corresponding
monomers
under
mild
conditions.
suitable
compositions
be
directly
used
pressure‐sensitive
adhesives
(PSAs)
possessed
comparable
peel
strength
commercially
available
PSA
scotch
tapes.
When
mixed
plasticizers,
as‐prepared
PSAs
desirable
adhesive
failure
removable
post‐it
note.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(19), P. 9609 - 9651
Published: Jan. 1, 2024
We
present
the
state-of-the-art
of
circular
polymers
based
on
monomer
and
polymer
design
reversible
ring-opening
addition
polymerization
reactions
without
involvement
other
reactants.
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(30)
Published: May 10, 2024
Abstract
Ring‐opening
polymerization
(ROP)
offers
a
striking
solution
to
solve
problems
encountered
in
step‐growth
condensation
polymerization,
including
precise
control
over
molecular
weight,
weight
distribution,
and
topology.
This
has
inspired
our
interest
ROP
of
cycloalkanes
with
an
ultimate
goal
rethink
polyolefins,
which
clearly
poses
number
challenges.
Practicality
is
actually
limited
by
their
low
polymerizability
elusive
mechanisms
arise
from
significantly
varied
ring
size
non‐polar
C−C
bonds
monomers.
In
this
work,
using
Lewis
acid/Brønsted
base/C(
sp
3
)‐H
initiator
system
previously
developed
laboratory,
we
focus
on
cyclobutanes
explore
the
positional
electronic
effects
substituents
ring,
namely
electron
push‐pull
effect,
promoting
controlled
afford
densely
functionalized
poly(cyclobutanes),
as
well
catalytic
degradation
obtained
polymers
for
upcycling.
More
importantly,
experiments
DFT
calculations
unveil
considerable
population
Lewis‐acid‐induced
thermostabilized
1,4‐zwitterions,
distinguish
cyclopropanes
others.
All
these
findings
would
shed
light
synthesis
saturated
all‐carbon
main‐chain
polymers,
small
molecule
transformations
cyclobutanes.
Fundamental Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 1, 2024
The
development
of
modern
society
is
closely
related
to
polymer
materials.
However,
the
improper
disposal
wastes
not
only
squanders
resources
but
also
intensifies
environmental
issues,
despite
that
energy
recovery,
physical
recycling
and
chemical
pathways
have
been
developed
tackle
recycle
reuse
polymers.
Among
them,
considered
as
most
pivotal
solution,
it
can
depolymerize
back
monomers,
which
then
repolymerize
into
Recently,
remarkable
progress
has
made
in
chemically
recyclable
polymers
through
monomer
design
shift
"polymerization-depolymerization"
equilibrium
realize
selective
depolymerization
achieve
closed-loop.
This
article
reviews
closed-loop
such
polyesters,
polycarbonates,
sulfur-containing
polymers,
vinyl
monomer-based
well
other
types
Moreover,
challenges
prospects
this
field
are
discussed.
Polymer Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
The
recent
advancements
in
the
synthesis
of
sustainable
polyesters
mediated
by
base/(thio)urea
binary
catalysts
are
discussed,
focusing
on
catalytic
mechanism,
activity
and
selectivity
as
well
current
challenges
future
directions.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 22, 2025
Degradable
chalcogenide
polyesters,
e.g.,
polythioesters
(PTEs),
typically
exhibit
improved
thermal,
mechanical,
and
optical
properties.
Anionic
ring-opening
polymerization
(ROP)
of
thionolactones,
an
intrinsically
promising
yet
underexplored
approach
to
accessing
PTEs,
however,
is
still
limited
by:
intolerance
metal
catalysts,
inadequate
control
over
chain
growth,
the
absence
aromatic
system.
Monomer
design-boosted
mechanistic
studies
may
address
above
challenges.
Here,
we
present
a
new
highly
reactive
thionolactone
synthesized
from
1,1'-binaphthyl-2,2'-diol
(BINOL).
Our
investigations
into
kinetics
thermodynamics
have
underscored
importance
rapid
initiation,
eventually
leading
discovery
tetrabutylammonium
2-naphthyl-thiocarboxylate
as
distinctive
initiator
that
enables
genuinely
controlled
living
thionolactones.
Ultimately,
atropisomerism
inherent
in
BINOL
has
resulted
creation
axially
chiral
PTE
materials
with
tailored
molecular
weights,
enantiomeric
compositions,
topologies.
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 22, 2025
Abstract
Degradable
chalcogenide
polyesters,
e.g.,
polythioesters
(PTEs),
typically
exhibit
improved
thermal,
mechanical,
and
optical
properties.
Anionic
ring‐opening
polymerization
(ROP)
of
thionolactones,
an
intrinsically
promising
yet
underexplored
approach
to
accessing
PTEs,
however,
is
still
limited
by:
intolerance
metal
catalysts,
inadequate
control
over
chain
growth,
the
absence
aromatic
system.
Monomer
design‐boosted
mechanistic
studies
may
address
above
challenges.
Here,
we
present
a
new
highly
reactive
thionolactone
synthesized
from
1,1′‐binaphthyl‐2,2′‐diol
(BINOL).
Our
investigations
into
kinetics
thermodynamics
have
underscored
importance
rapid
initiation,
eventually
leading
discovery
tetrabutylammonium
2‐naphthyl‐thiocarboxylate
as
distinctive
initiator
that
enables
genuinely
controlled
living
thionolactones.
Ultimately,
atropisomerism
inherent
in
BINOL
has
resulted
creation
axially
chiral
PTE
materials
with
tailored
molecular
weights,
enantiomeric
compositions,
topologies.
