Angewandte Chemie,
Год журнала:
2023,
Номер
135(44)
Опубликована: Сен. 15, 2023
Abstract
To
synthesize
high
molecular
weight
poly(phenolic
ester)
via
a
living
ring‐opening
polymerization
(ROP)
of
cyclic
phenolic
ester
monomers
remains
critical
challenge
due
to
serious
transesterification
and
back‐biting
reactions.
Both
bonds
in
monomer
polymer
chains
are
highly
active,
it
is
difficult
so
far
distinguish
them.
In
this
work,
an
unprecedented
selectively
bifunctional
catalytic
system
tetra‐n‐butylammonium
chloride
(TBACl)
was
discovered
mediate
the
syntheses
salicylic
acid‐based
copolyesters
ROP
salicylate
esters
(for
poly(salicylic
methyl
glycolide)
(PSMG),
M
n
=361.8
kg/mol,
Ð
<1.30).
Compared
previous
catalysis
systems,
side
reactions
were
suppressed
remarkably
because
bond
can
be
cleaved
over
that
during
progress.
Mechanistic
studies
reveal
halide
anion
alkyl‐quaternaryammonium
cation
work
synergistically,
where
moiety
interacts
with
carbonyl
group
substrates
non‐classical
hydrogen
bonding.
Moreover,
these
recycled
dimeric
under
solution
condition,
original
monomeric
without
catalyst
sublimation
condition.
Chemical Reviews,
Год журнала:
2024,
Номер
124(7), С. 4393 - 4478
Опубликована: Март 22, 2024
Polyesters
carrying
polar
main-chain
ester
linkages
exhibit
distinct
material
properties
for
diverse
applications
and
thus
play
an
important
role
in
today's
plastics
economy.
It
is
anticipated
that
they
will
even
greater
tomorrow's
circular
economy
focuses
on
sustainability,
thanks
to
the
abundant
availability
of
their
biosourced
building
blocks
presence
bonds
can
be
chemically
or
biologically
cleaved
demand
by
multiple
methods
bring
about
more
desired
end-of-life
plastic
waste
management
options.
Because
this
potential
promise,
there
have
been
intense
research
activities
directed
at
addressing
recycling,
upcycling
biodegradation
existing
legacy
polyesters,
designing
biorenewable
alternatives,
redesigning
future
polyesters
with
intrinsic
chemical
recyclability
tailored
performance
rival
commodity
are
either
petroleum
based
and/or
hard
recycle.
This
review
captures
these
exciting
recent
developments
outlines
challenges
opportunities.
Case
studies
poly(lactic
acid),
poly(3-hydroxyalkanoate)s,
poly(ethylene
terephthalate),
poly(butylene
succinate),
poly(butylene-adipate
presented,
emerging
recyclable
comprehensively
reviewed.
Macromolecules,
Год журнала:
2024,
Номер
57(5), С. 1919 - 1940
Опубликована: Фев. 22, 2024
The
large
production
and
indiscriminate
disposal
of
plastics
have
resulted
in
serious
resource
global
environmental
crises,
which
has
raised
a
demand
to
develop
more
sustainable
circular
economy.
An
ideal
strategy
address
the
end-of-life
issue
is
next-generation
polymers
with
closed-loop
life
cycles,
can
be
selectively
depolymerized
back
monomers
at
end
their
service
life.
Aliphatic
polyesters
prepared
by
ring-opening
polymerization
(ROP)
moderately
strained
lactones
shown
great
potential
recyclable
polymers.
This
Perspective
highlights
recent
achievements
for
that
are
derived
from
four-,
five-,
six-,
seven-membered
focusing
on
discussion
thermodynamic
kinetic
considerations,
monomer
design
principles
polymer
preparations,
material
properties,
chemical
recyclability.
Finally,
current
challenges
possible
directions
also
discussed.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Сен. 15, 2023
To
synthesize
high
molecular
weight
poly(phenolic
ester)
via
a
living
ring-opening
polymerization
(ROP)
of
cyclic
phenolic
ester
monomers
remains
critical
challenge
due
to
serious
transesterification
and
back-biting
reactions.
Both
bonds
in
monomer
polymer
chains
are
highly
active,
it
is
difficult
so
far
distinguish
them.
In
this
work,
an
unprecedented
selectively
bifunctional
catalytic
system
tetra-n-butylammonium
chloride
(TBACl)
was
discovered
mediate
the
syntheses
salicylic
acid-based
copolyesters
ROP
salicylate
esters
(for
poly(salicylic
methyl
glycolide)
(PSMG),
Mn
=361.8
kg/mol,
Ð<1.30).
Compared
previous
catalysis
systems,
side
reactions
were
suppressed
remarkably
because
bond
can
be
cleaved
over
that
during
progress.
Mechanistic
studies
reveal
halide
anion
alkyl-quaternaryammonium
cation
work
synergistically,
where
moiety
interacts
with
carbonyl
group
substrates
non-classical
hydrogen
bonding.
Moreover,
these
recycled
dimeric
under
solution
condition,
original
monomeric
without
catalyst
sublimation
condition.
Macromolecules,
Год журнала:
2023,
Номер
56(15), С. 6019 - 6026
Опубликована: Июль 22, 2023
The
development
of
chemically
recyclable
polymers
with
closed-loop
life
cycles
is
believed
to
be
the
most
attractive
strategy
in
creating
circular
plastic
economy.
Here,
we
successfully
prepared
a
pair
enantiopure
O-heterocyclic
lactones
bearing
pendent
phenyl
substituent,
which
are
named
(2S,7R)-7-methyl-2-phenyl-1,4-dioxepan-5-one
(SR-M1)
and
(2R,7R)-7-methyl-2-phenyl-1,4-dioxepan-5-one
(RR-M2),
respectively,
by
using
methanolysis
product
poly(3-hydroxybutyrate)
(P3HB)
as
raw
material.
well-controlled
ring-opening
polymerizations
SR-M1
RR-M2
were
achieved
presence
MeAl[salen]
catalyst
produce
poly(ether-ester)s
controlled
molecular
weights,
narrow
dispersities,
well-defined
terminal
groups.
monomer
stereoconfiguration
has
big
impact
on
their
polymerization
kinetics
thermodynamics
well
thermal
mechanical
properties
resultant
polyesters.
Both
P(SR-M1)
P(RR-M2)
exhibited
recyclability.
depolymerization
polyesters
back
pristine
monomers
can
easily
realized
stannous
octoate
solution.
Fundamental Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 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.
