Chemistry of Materials,
Год журнала:
2025,
Номер
37(3), С. 1297 - 1305
Опубликована: Янв. 30, 2025
Though
possessing
advantages
of
durability
and
exceptional
performances
profit
from
cross-linked
structure,
it
is
challenging
to
recycle
reuse
thermoset
polymers.
Here,
reprocessability
in
industrially
relevant
polyurethane
polyurea
thermosets
unveiled.
Unlike
prior
methods,
this
strategy
does
not
require
the
complicated
design
monomer
structures
suitable
for
a
variety
systems.
With
enaminoneamide
structure
inserted,
PU
possesses
reprocessing
performance
without
affecting
mechanical
properties.
Upon
thermal
treatment,
polymer
network
dissociates
into
isocyanate
enaminone,
allowing
materials
be
recycled.
The
reclaimed
multiple
generations
demonstrates
long-term
materials.
This
work
offers
convenient
approach
make
widely
used
isocyanate-based
networks
recyclable
via
involving
systems
consuming
Furthermore,
stability
product
β-diketone
isocyanate,
sensibility
water
prevented
during
synthesis,
enhancing
properties
polymer.
Given
poised
widespread
adoption,
may
an
important
advance
lifecycle
ACS Sustainable Chemistry & Engineering,
Год журнала:
2022,
Номер
10(25), С. 8228 - 8238
Опубликована: Июнь 13, 2022
The
chemical
recycling
of
plastic
wastes
into
value-added
products
is
an
attractive
strategy
to
reduce
the
consumption
fossil
fuels
and
pollution.
We
report
here
facile
upcycling
poly(3-hydroxybutyrate)
(P3HB)
polymerizable
monomers
subsequent
polymerization
toward
degradable
recyclable
polymers.
bicyclic
monomer
4-methyloctahydro-2H-benzo[b][1,4]dioxepin-2-one
(4-MOHB)
was
first
synthesized
from
P3HB
through
efficient
steps.
obtained
underwent
bulk
ring-opening
(ROP)
catalyzed
by
stannous
octoate
(Sn(Oct)2)
give
amorphous
materials.
With
benzyl
alcohol
(BnOH)
as
initiator,
Sn(Oct)2
can
effectively
catalyze
ROP
ether–ester
in
a
controllable
fashion.
Moreover,
poly(4-methyloctahydro-2H-benzo[b][1,4]dioxepin-2-one)
(P(4-MOHB))
showed
closed-loop
recovery
property
due
fused
structure.
selective
depolymerization
P(4-MOHB)
homopolymer
back
4-MOHB
be
easily
realized
using
p-toluenesulfonic
acid
(TsOH)
or
catalyst
solution
bulk.
This
recycle
bioplastics
materials
has
promising
application
prospect
beneficial
extend
life
cycle
environment-friendly
Macromolecules,
Год журнала:
2023,
Номер
56(10), С. 3641 - 3649
Опубликована: Май 11, 2023
Chemical
recycling
to
monomers
(CRMs)
of
A–B–A
block
copolymers
is
governed
by
the
chemical
structure
and
thereby
thermodynamic
behavior
different
constituents.
Here,
we
show
how
a
toolkit
based
on
cyclic
monomer
solvent
properties
can
be
utilized
in
design
recyclable
with
varying
material
properties.
By
combining
four
lactide,
ε-decalactone,
2,2-diethyltrimethylene
carbonate,
trimethylene
three
were
created,
suitable
for
CRM
scenarios.
The
soft
midblock
(ε-decalactone
or
carbonate)
appeared
have
critical
impact
both
ring-closing
depolymerization
mechanical
properties,
where
changing
from
polyester
polycarbonate
increased
Young's
modulus
14
200
MPa.
Hence,
this
work
demonstrates
complexity
as
well
opportunities
macromolecular
structures
circular
economy.
Macromolecules,
Год журнала:
2023,
Номер
57(2), С. 490 - 502
Опубликована: Дек. 29, 2023
We
studied
and
established
the
dual
nature
of
non-isocyanate
polythiourethane
(NIPTU)
dynamic
chemistry
capitalized
on
our
understanding
to
achieve
multidimensional
chemical
recycling
a
cross-linked
NIPTU,
also
known
as
poly(mercapto-thiourethane).
This
NIPTU
includes
first
demonstration
recovery
valuable
small
molecules
in
addition
reprocessability
with
full
cross-link
density
recovery.
In
particular,
we
performed
investigation
using
small-molecule
analogues.
identified
two
types
chemistry:
reversible
cyclic
thiocarbonate
aminolysis,
where
thiourethane
(NITU)
groups
reversibly
dissociate
into
thiocarbonates
amines,
trans(thio)carbamoylation,
thionourethane
linkages
within
NITU
undergo
exchange
reactions
alcohol.
synthesized
renewable
glycerol-based
(GNIPTU)
high
biowaste-derivable
content.
Capitalizing
recovered
pure
di(thiocarbamate)
94
mol
%
yield,
one
highest
yields
among
reported
studies
polymers.
The
GNIPTU
network
exhibited
property
after
reprocessing,
providing
another
effective
method
recycling.
With
robust
properties,
content,
capability
excellent
recovery,
reprocessability,
exemplifies
how
low-cost,
renewable,
polyurethane-like
materials
can
be
developed
both
high-performance
characteristics
potential
contribute
meaningfully
polymer
circularity.
Macromolecules,
Год журнала:
2023,
Номер
56(15), С. 6117 - 6125
Опубликована: Июль 21, 2023
It
is
attractive
to
develop
chemically
recyclable
polymers
with
desirable
performances
from
commercial
monomers
avoid
the
expensive
and
time-consuming
scalable
process
for
completely
new
monomers.
In
this
contribution,
we
present
rapid
controlled
ring-opening
polymerization
(ROP)
of
bio-sourced
alkyl-δ-lactones
produce
closed-loop
polyesters
in
presence
an
organophosphazene
base
(tBu-P2)/urea
binary
catalyst.
The
obtained
are
capable
recycling
back
pristine
by
simply
heating
them
bulk
stannous
octanoate
(Sn(Oct)2)
as
effects
alkyl
substituent
length
on
kinetics,
thermodynamics,
well
properties
resultant
poly(alkyl-δ-lactone)s
were
investigated.
Well-defined
triblock
copolymers
consisting
soft
middle
block
PLLA
hard
end
successfully
prepared
one-pot,
sequential
ROP
l-lactide
(l-LA).
These
can
be
used
pressure-sensitive
adhesives
without
addition
tackifiers
or
other
additives.
chemical
these
recover
ethyl
lactate
high
yields
was
achieved
alcoholysis
then
distillation
under
reduced
pressure.
Polymer Chemistry,
Год журнала:
2023,
Номер
14(28), С. 3270 - 3276
Опубликована: Янв. 1, 2023
The
study
investigates
the
potential
in
solvent
triggered
chemical
recycling
and
how
power
of
effect
is
influenced
by
monomer
structure.
Catalyst
selectivity
utilized
to
demonstrate
mixed
polymer
waste.
Macromolecules,
Год журнала:
2022,
Номер
55(21), С. 9697 - 9704
Опубликована: Окт. 20, 2022
The
upcycling
of
plastic
waste
into
value-added
products
is
a
promising
strategy
to
reduce
pollution
and
create
sustainable
style
for
polymeric
materials.
We
report
here
the
synthesis
novel
N-heterocyclic
lactone,
5-methyl-N-Boc-1,4-oxazepane-7-one
(MeOxPBoc)
corresponding
poly(amine-alt-ester)
through
poly(3-hydroxybutyrate)
(P3HB)
biopolymer.
Specifically,
tens
grams
MeOxPBoc
can
be
easily
prepared
from
P3HB
in
satisfactory
yield.
Well-controlled
ring-opening
polymerization
(ROP)
was
achieved
give
an
amorphous
P(MeOxPBoc)
with
targeted
molecular
weight,
narrow
weight
dispersity,
well-defined
terminal
groups
toluene
using
stannous
2-ethyl
hexanoate
(Sn(Oct)2)
as
catalyst.
obtained
could
depolymerized
back
its
pristine
monomer
either
trimethylbenzene
at
120
°C
Sn(Oct)2
catalyst
or
bulk
150
presence
ZnCl2
After
simple
purification
by
recrystallization,
recycled
repolymerized
produce
virgin-quality
polymers.
Remarkably,
converted
cationic
polymer
simply
removing
pendent
t-butoxycarbonyl
protecting
group.
This
study
provides
new
insight
address
end-of-use
problem
functional
closed-loop
life
cycle.
