Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(48)
Published: Oct. 5, 2023
Abstract
Polymerization‐induced
self‐assembly
(PISA)
is
a
powerful
technique
for
preparing
block
copolymer
nanostructures.
Recently,
efforts
have
been
focused
on
applying
photochemistry
to
promote
PISA
due
the
mild
reaction
conditions,
low
cost,
and
spatiotemporal
control
that
light
confers.
Despite
these
advantages,
chain‐end
degradation
long
times
can
mar
efficacy
of
this
process.
Herein,
we
demonstrate
use
ultrafast
photoiniferter
produce
polymeric
By
exploiting
rapid
photolysis
xanthates,
near‐quantitative
monomer
conversion
be
achieved
within
five
minutes
prepare
micelles,
worms,
vesicles
at
various
core‐chain
lengths,
concentrations,
or
molar
compositions.
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
article
highlights
the
advancements
in
controlled
radical
polymerization
facilitated
by
three
external
regulations
of
oxygen,
light,
and
mechanical
force,
outlines
future
directions
polymerization.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(48)
Published: Oct. 5, 2023
Abstract
Polymerization‐induced
self‐assembly
(PISA)
is
a
powerful
technique
for
preparing
block
copolymer
nanostructures.
Recently,
efforts
have
been
focused
on
applying
photochemistry
to
promote
PISA
due
the
mild
reaction
conditions,
low
cost,
and
spatiotemporal
control
that
light
confers.
Despite
these
advantages,
chain‐end
degradation
long
times
can
mar
efficacy
of
this
process.
Herein,
we
demonstrate
use
ultrafast
photoiniferter
produce
polymeric
By
exploiting
rapid
photolysis
xanthates,
near‐quantitative
monomer
conversion
be
achieved
within
five
minutes
prepare
micelles,
worms,
vesicles
at
various
core‐chain
lengths,
concentrations,
or
molar
compositions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 18848 - 18854
Published: July 3, 2024
While
oxygen-tolerant
strategies
have
been
overwhelmingly
developed
for
controlled
radical
polymerizations,
the
low
concentrations
typically
required
high
monomer
recovery
render
solution
depolymerizations
particularly
challenging.
Here,
an
open-air
atom
transfer
polymerization
(ATRP)
depolymerization
is
presented,
whereby
a
small
amount
of
volatile
cosolvent
introduced
as
means
to
thoroughly
remove
oxygen.
Ultrafast
(i.e.,
2
min)
could
efficiently
proceed
in
open
vessel,
allowing
very
retrieval
be
achieved
∼91%
efficiency),
on
par
with
that
fully
deoxygenated
analogue.
Oxygen
probe
studies
combined
detailed
kinetics
revealed
importance
low-boiling
point
removing
oxygen
prior
reaction,
thus
facilitating
effective
depolymerization.
The
versatility
methodology
was
demonstrated
by
performing
reactions
range
different
ligands
and
at
polymer
loadings
(1
M
repeat
unit
concentration)
without
significantly
compromising
yield.
This
approach
provides
oxygen-tolerant,
facile,
efficient
route
chemically
recycle
ATRP-synthesized
polymers,
enabling
exciting
new
applications.
Macromolecules,
Journal Year:
2024,
Volume and Issue:
57(8), P. 3731 - 3740
Published: April 2, 2024
Ionic
liquids
provide
an
environmentally
friendly
alternative
to
organic
solvents
that
have
previously
been
shown
greatly
improve
the
kinetics
of
photoiniferter
reversible
addition–fragmentation
chain-transfer
polymerization
reactions.
Here,
we
expand
on
previous
work
in
our
group
by
mixing
common
and
monomers
such
as
methyl
methacrylate
with
hydrophobic
ionic
liquids.
We
demonstrate
it
improves
reaction
rate
up
3.3-fold
compared
only
solvent
while
maintaining
a
narrow
polydispersity.
It
was
hypothesized
this
is
due
viscosity
polarity
disfavoring
biomolecular
termination
propagating
chains.
Chain-end
fidelity
achieved
mechanism
demonstrated
chain
extension
experiments.
The
system
exhibited
temporal
control
oxygen
tolerance.
Macromolecules,
Journal Year:
2024,
Volume and Issue:
57(9), P. 4192 - 4198
Published: April 22, 2024
Conducting
controlled
radical
polymerization
(CRP)
under
ambient
conditions
presents
a
formidable
challenge
due
to
the
efficient
radical-quenching
nature
of
molecular
oxygen.
Herein,
we
address
inherent
challenges
by
employing
air-stable
amine–borane
complexes
designed
operate
efficiently
in
presence
These
initiators
demonstrate
selective
activation
mild
thermal
or
water,
releasing
active
radicals
for
polymerization.
Forming
with
diverse
amines,
these
compounds
are
accessible
and
exist
various
forms
from
crystalline
solids
low-viscosity
liquids.
Rapid
acrylamides
acrylates
an
open-air
environment
without
external
deoxygenation
yields
well-defined
polymers
low
dispersity,
high
monomer
conversion,
end-group
fidelity.
The
minimum
initiation
temperature
can
be
finely
tuned
over
broad
range
selecting
different
organic
media.
Significantly,
fully
oxygen-tolerant
also
carried
out
at
room
aqueous
media
relying
on
stimuli.
In
addition,
high-throughput
synthesis
series
thermosensitive
copolymers
was
performed
using
this
aerobic
CRP
process
order
quickly
investigate
relationship
between
polymeric
structure
lower
critical
solution
(LCST)
property.
This
simple,
robust,
versatile
approach
may
offer
new
opportunities
application
environments.
Macromolecular Rapid Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 22, 2025
Abstract
Although
the
chemical
recycling
of
polymers
synthesized
by
controlled
radical
polymerization
enables
recovery
pristine
monomer
at
low
temperatures,
it
operates
efficiently
under
strictly
anaerobic
conditions.
Instead,
oxygen‐tolerant
depolymerizations
are
scarce,
and
either
restricted
to
use
a
boiling
co‐solvent
or
performed
in
closed
vessels,
often
suffering
from
conversions.
Here,
an
open‐vessel,
depolymerization
atom
transfer
(ATRP)‐synthesized
is
introduced,
leading
high
percentages
regeneration
(>90%
efficiency).
Dissolved
oxygen
eliminated
utilizing
catalyst
loadings,
lower
loadings
combined
with
initiator.
Notably,
methodology
compatible
various
solvents
(i.e.,
anisole,
1,2,4‐trichlorobenzene
(TCB),
1,2‐dichlorobenzene
(DCB),
etc.)
range
commercially
available
ligands
including
tris
2‐(dimethylamino)ethylamine
(Me
6
TREN)
tris(2‐pyridylmethyl)amine
(TPMA),
as
well
more
inexpensive
alternatives
such
tris(2‐aminoethyl)amine
(TREN)
N,N,N‘,N‘‘,N‘‘
‐pentamethyldiethylenetriamine
(PMDETA).
Macromolecules,
Journal Year:
2023,
Volume and Issue:
56(19), P. 7898 - 7908
Published: Sept. 22, 2023
An
oxygen-tolerant
SI-PhotoRAFT
technique
has
been
developed
for
the
efficient
synthesis
of
surface-tethered
polymer
brushes
under
low-energy
near-infrared
(NIR)
light.
This
takes
advantage
unique
properties
NIR
light,
in
particular
enhanced
penetration,
to
effectively
prepare
polymeric
coatings,
even
through
barriers
that
are
opaque
visible
The
NIR-mediated
polymerization
was
utilized
precisely
modulate
brush
height
direct
correlation
with
irradiation
time.
Additionally,
this
facilitated
sequential
chain
extension,
enabling
fabrication
block
copolymer
brushes.
Moreover,
incorporation
a
photoresponsive
monomer,
7-[4-(trifluoromethyl)coumarin]acrylamide
[2-(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)acrylamide,
TCAm],
within
poly(N,N-dimethylacrylamide)
enables
orthogonal
control
over
and
cross-linking
processes
use
two
different
wavelengths
(NIR
UV
light).
When
exposed
source
(λ
=
365
nm,
18.2
mW/cm2),
TCAm
undergoes
dimerization
triggering
grafted
"arms".
Furthermore,
by
utilizing
penetration
coating
prepared
on
inner
walls
tube
Finally,
process
is
successfully
applied
antifouling
surfaces
poly(dimethylsiloxane)-coated
silicon
wafers,
leading
inhibition
biofouling.
Journal of Polymer Science,
Journal Year:
2024,
Volume and Issue:
62(17), P. 3879 - 3896
Published: March 25, 2024
Abstract
Controlled
radical
polymerization
(CRP)
techniques
enable
the
preparation
of
diverse,
chemically
tailored
polymers
with
a
variety
chain
architectures.
Separately,
light‐mediated
reactions
offer
number
advantages
over
thermal
polymerizations
in
terms
energy
efficiency,
sustainability,
and
versatility.
Recent
work
has
combined
photopolymerization
CRP
to
advance
synthesis
nonlinear
architectures,
including
bottlebrush
polymers,
star
hyperbranched
cyclic
polymers.
These
photoCRP
methods
novel
routes
using
mild
reaction
conditions.
In
this
review,
we
provide
an
overview
for
We
start
discussion
applied
linear
discuss
underlying
mechanisms.
Then,
bottlebrush,
star,
hyperbranched,
cyclic,
surface‐initiated
polymer
brushes.
For
each
case,
synthetic
strategy
unique
properties
characteristics
resulting
perspective
on
potential
future
directions
research.
