Macromolecules,
Год журнала:
2024,
Номер
57(20), С. 9546 - 9554
Опубликована: Окт. 8, 2024
Designing
the
next
generation
of
circular
plastics
can
contribute
to
preventing
environmental
pollution
and
loss
embedded
value.
In
light
this,
assessing
thermodynamic
parameters,
i.e.,
polymerization
enthalpy
(ΔHp)
entropy
(ΔSp)
ring-opening
polymerization,
is
becoming
increasingly
important
as
these
directly
connect
chemical
recyclability
polymers.
However,
determining
thermodynamics
currently
requires
synthesis
each
monomer
polymer
structure,
consuming
large
amounts
time
chemicals,
making
it
unfeasible
screen
a
myriad
different
structures
find
polymers
with
optimal
properties
recyclability.
silico
methods
could
mitigate
issues
drastically
increase
rate
at
which
new
recyclable
be
developed.
We
demonstrate
how
collision
frequency
between
reactive
groups
in
monomers,
derived
from
nonreactive
(i.e.,
no
changes)
molecular
dynamics
simulations,
used
for
simultaneous
computation
ΔHp
ΔSp
respective
3.5
kJ
mol–1
6.7
J
K–1
average
deviation
experimental
data.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(19), С. 9609 - 9651
Опубликована: Янв. 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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(24)
Опубликована: Апрель 9, 2024
In
this
paper,
we
proposed
a
heteroatom
substitution
strategy
(HSS)
in
the
δ-valerolactone
(VL)
system
to
modulate
thermodynamics
toward
chemically
recyclable
polyesters.
Three
VL-based
monomers
containing
different
heteroatoms
(M
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(9), С. 7788 - 7798
Опубликована: Фев. 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,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 28, 2025
Abstract
Great
achievements
have
been
made
in
CO
2
/epoxide
copolymerization
and
dialkyl
carbonate/diol
polycondensation;
however,
efficient
preparation
of
high‐molecular‐weight
(>100
kDa)
aliphatic
polycarbonates
with
tunable
properties
recyclability
under
mild
conditions
still
remains
as
a
great
challenge.
Herein,
we
presented
“polycondensation–depolymerization–repolymerization”
strategy
for
structurally
diverse
polycarbonates.
This
involved
step
growth
polycondensation
carbonate
diol
to
low‐molecular‐weight
(0.5−1.9
atmosphere
pressure,
which
are
then
utilized
produce
cyclic
monomers
through
catalytic
depolymerization.
The
ring‐opening
polymerization
led
high
molecular
weight
polymers,
can
be
converted
back
monomer
via
ring‐closing
depolymerization
or
diol/dialkyl
alcoholysis,
enabling
chemical
recycling
dual
closed
loops.
thermal
mechanical
the
widely
adjusted
by
varying
substituent,
polycarbonate
four‐membered
spiro‐cyclic
substituent
shows
recorded
melting
temperature
(217
°C)
strength
within
reported
family.
A(hard)‐B(soft)‐A(hard)
triblock
thermoplastic
elastomers
good
performance
elastic
recovery
were
also
created
sequential
polymerization.
“polycondensation−depolymerization−repolymerization”
provided
powerful
toolbox
developing
high‐performance
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 28, 2025
Abstract
Great
achievements
have
been
made
in
CO
2
/epoxide
copolymerization
and
dialkyl
carbonate/diol
polycondensation;
however,
efficient
preparation
of
high‐molecular‐weight
(>100
kDa)
aliphatic
polycarbonates
with
tunable
properties
recyclability
under
mild
conditions
still
remains
as
a
great
challenge.
Herein,
we
presented
“polycondensation–depolymerization–repolymerization”
strategy
for
structurally
diverse
polycarbonates.
This
involved
step
growth
polycondensation
carbonate
diol
to
low‐molecular‐weight
(0.5−1.9
atmosphere
pressure,
which
are
then
utilized
produce
cyclic
monomers
through
catalytic
depolymerization.
The
ring‐opening
polymerization
led
high
molecular
weight
polymers,
can
be
converted
back
monomer
via
ring‐closing
depolymerization
or
diol/dialkyl
alcoholysis,
enabling
chemical
recycling
dual
closed
loops.
thermal
mechanical
the
widely
adjusted
by
varying
substituent,
polycarbonate
four‐membered
spiro‐cyclic
substituent
shows
recorded
melting
temperature
(217
°C)
strength
within
reported
family.
A(hard)‐B(soft)‐A(hard)
triblock
thermoplastic
elastomers
good
performance
elastic
recovery
were
also
created
sequential
polymerization.
“polycondensation−depolymerization−repolymerization”
provided
powerful
toolbox
developing
high‐performance
Angewandte Chemie,
Год журнала:
2024,
Номер
136(24)
Опубликована: Апрель 9, 2024
Abstract
In
this
paper,
we
proposed
a
heteroatom
substitution
strategy
(HSS)
in
the
δ
‐valerolactone
(VL)
system
to
modulate
thermodynamics
toward
chemically
recyclable
polyesters.
Three
VL‐based
monomers
containing
different
heteroatoms
(M
1
(N),
M
2
(S),
and
3
(O)),
instead
of
C‐5
carbon,
were
designed
synthesized
verify
our
HSS.
All
three
undergo
organocatalytic
living/controlled
ROP
controllable
depolymerization.
Impressively,
resulting
P(M
)
achieved
over
99
%
monomer
recovery
under
both
mild
solution
depolymerization
high
vacuum
pyrolysis
conditions
without
any
side
reactions,
recycled
can
be
polymerized
again
forming
new
polymers.
The
systematic
study
relationship
between
recyclability
shows
that
introducing
does
change
(Δ
H
p
o
,
Δ
S
T
c
values),
thereby
adjusting
polymerizability
depolymerizability.
DFT
calculations
found
introduction
adjusts
ring
strain
by
changing
angular
monomers,
order
their
>M
is
consistent
with
experimentally
obtained
enthalpy
change.
Notably,
one‐pot/one‐step
copolymerization
two
each
enables
synthesis
sequence‐controlled
copolymers
from
gradient
random
block
structures,
simply
switching
temperature.
Polymer Chemistry,
Год журнала:
2024,
Номер
15(24), С. 2502 - 2512
Опубликована: Янв. 1, 2024
Structurally
and
functionally
diverse
poly(thioester)s
were
readily
synthesized
via
ring-opening
copolymerization
of
cyclic
thioanhydrides
episulfides
catalyzed
by
a
bipyridine-bisphenolate
aluminum/onium
pair.
