Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15428 - 15437
Опубликована: Май 25, 2024
Chemical
recycling
to
monomers
(CRM)
offers
a
promising
closed-loop
approach
transition
from
current
linear
plastic
economy
toward
more
sustainable
circular
paradigm.
Typically,
this
has
focused
on
modulating
the
ceiling
temperature
(Tc)
of
monomers.
Despite
considerable
advancements,
polymers
with
low
Tc
often
face
challenges
such
as
inadequate
thermal
stability,
exemplified
by
poly(γ-butyrolactone)
(PGBL)
decomposition
∼200
°C.
In
contrast,
floor
(Tf)-regulated
polymers,
particularly
those
synthesized
via
ring-opening
polymerization
(ROP)
macrolactones,
inherently
exhibit
enhanced
thermodynamic
stability
increases.
However,
development
Tf
regulated
chemically
recyclable
remains
relatively
underexplored.
context,
judicious
design
and
efficient
synthesis
biobased
macrocyclic
diester
monomer
(HOD),
we
developed
type
-regulated
poly(ketal-ester)
(PHOD).
First,
entropy-driven
ROP
HOD
generated
high-molar
mass
PHOD
exceptional
Td,5%
reaching
up
353
Notably,
it
maintains
high
345
°C
even
without
removing
catalyst.
This
contrasts
markedly
PGBL,
which
spontaneously
depolymerizes
back
above
its
in
presence
Second,
displays
outstanding
chemical
recyclability
at
room
within
just
1
min
tBuOK.
Finally,
copolymerization
pentadecanolide
(PDL)
high-performance
copolymers
(PHOD-co-PPDL)
tunable
mechanical
properties
both
components.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Июнь 2, 2023
The
development
of
chemically
recyclable
polymers
serves
as
an
attractive
approach
to
address
the
global
plastic
pollution
crisis.
Monomer
design
principle
is
key
achieving
chemical
recycling
monomer.
Herein,
we
provide
a
systematic
investigation
evaluate
range
substitution
effects
and
structure-property
relationships
in
ɛ-caprolactone
(CL)
system.
Thermodynamic
recyclability
studies
reveal
that
substituent
size
position
could
regulate
their
ceiling
temperatures
(Tc).
Impressively,
M4
equipped
with
tert-butyl
group
displays
Tc
241
°C.
A
series
spirocyclic
acetal-functionalized
CLs
prepared
by
facile
two-step
reaction
undergo
efficient
ring-opening
polymerization
subsequent
depolymerization.
resulting
demonstrate
various
thermal
properties
transformation
mechanical
performance
from
brittleness
ductility.
Notably,
toughness
ductility
P(M13)
comparable
commodity
isotactic
polypropylene.
This
comprehensive
study
aimed
guideline
future
monomer
towards
polymers.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Фев. 4, 2023
The
green
revolution
in
plastics
should
be
accelerated
due
to
growing
sustainability
concerns.
Here,
we
develop
a
series
of
chemically
recyclable
polymers
from
the
first
reported
cascade
polymerization
H2
O,
COS,
and
diacrylates.
In
addition
abundant
feedstocks,
method
is
efficient
air-tolerant,
uses
common
organic
bases
as
catalysts,
yields
with
high
molecular
weights
under
mild
conditions.
Such
polymers,
structurally
like
polyethylene
low-density
in-chain
polar
groups,
manifest
impressive
toughness
ductility
comparable
high-density
polyethylene.
ester
group
acts
breaking
point,
enabling
these
undergo
chemical
recycling
through
two
loops.
structures
properties
also
have
an
immeasurably
expanded
range
owing
versatility
our
method.
readily
available
raw
materials,
facile
synthesis,
performance
make
promising
prospects
sustainable
materials
practice.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(14)
Опубликована: Фев. 9, 2023
Abstract
This
contribution
reports
the
efficient
conversion
of
γ‐valerolactone
and
its
derivatives,
abundant
but
unexplored
renewable
feedstocks,
into
sustainable
degradable
polythioesters
via
establishment
first
isomerization‐driven
ring‐opening
polymerizations
(IROPs)
corresponding
thionolactone
intermediates.
The
key
to
this
success
relies
on
development
a
new
simple
robust
[Et
3
O]
+
[B(C
6
F
5
)
4
]
−
cationic
initiator
which
possesses
high
activity,
exclusive
selectivity,
living
nature,
broad
scope
thionolactones.
A
complete
inversion
configuration
during
IROP
enantiopure
γ‐thionovalerolactone
is
also
disclosed,
affording
isotactic
semicrystalline
(
T
m
=87.0
°C)
with
mechanical
property
compared
well
representative
commodity
polyolefins.
formation
highly
crystalline
supramolecular
stereocomplex
enhanced
thermal
=117.6
has
been
revealed.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15428 - 15437
Опубликована: Май 25, 2024
Chemical
recycling
to
monomers
(CRM)
offers
a
promising
closed-loop
approach
transition
from
current
linear
plastic
economy
toward
more
sustainable
circular
paradigm.
Typically,
this
has
focused
on
modulating
the
ceiling
temperature
(Tc)
of
monomers.
Despite
considerable
advancements,
polymers
with
low
Tc
often
face
challenges
such
as
inadequate
thermal
stability,
exemplified
by
poly(γ-butyrolactone)
(PGBL)
decomposition
∼200
°C.
In
contrast,
floor
(Tf)-regulated
polymers,
particularly
those
synthesized
via
ring-opening
polymerization
(ROP)
macrolactones,
inherently
exhibit
enhanced
thermodynamic
stability
increases.
However,
development
Tf
regulated
chemically
recyclable
remains
relatively
underexplored.
context,
judicious
design
and
efficient
synthesis
biobased
macrocyclic
diester
monomer
(HOD),
we
developed
type
-regulated
poly(ketal-ester)
(PHOD).
First,
entropy-driven
ROP
HOD
generated
high-molar
mass
PHOD
exceptional
Td,5%
reaching
up
353
Notably,
it
maintains
high
345
°C
even
without
removing
catalyst.
This
contrasts
markedly
PGBL,
which
spontaneously
depolymerizes
back
above
its
in
presence
Second,
displays
outstanding
chemical
recyclability
at
room
within
just
1
min
tBuOK.
Finally,
copolymerization
pentadecanolide
(PDL)
high-performance
copolymers
(PHOD-co-PPDL)
tunable
mechanical
properties
both
components.
