Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(17), С. 5598 - 5603
Опубликована: Фев. 20, 2019
Molecular
weight
distribution
of
polymers,
termed
dispersity
(Đ),
is
a
fundamental
parameter
for
determining
polymer
material
properties.
This
paper
reports
novel
approach
controlling
Đ
by
exploiting
temperature-selective
radical
generation
in
organocatalyzed
living
polymerization.
The
polymers
with
tailored
were
synthesized
batch
system
without
the
assistance
an
external
pump.
A
unique
aspect
this
that
was
tuneable
from
1.11
to
1.50
any
segment
diblock,
triblock,
and
multiblock
copolymers
form
star
brush
segmental
or
topological
restriction.
amenable
various
monomers
free
metals
thus
attractive
applications.
also
generated
brushes
on
surfaces
Đ.
An
interesting
finding
exhibited
interaction
molecules,
depending
value.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
58(16), С. 5170 - 5189
Опубликована: Авг. 1, 2018
The
application
of
photochemistry
to
polymer
and
material
science
has
led
the
development
complex
yet
efficient
systems
for
polymerization,
post-functionalization,
advanced
materials
production.
Using
light
activate
chemical
reaction
pathways
in
these
not
only
leads
exquisite
control
over
dynamics,
but
also
allows
synthetic
protocols
be
easily
achieved.
Compared
polymerization
mediated
by
thermal,
chemical,
or
electrochemical
means,
photoinduced
can
potentially
offer
more
versatile
methods
macromolecular
synthesis.
We
highlight
utility
as
an
energy
source
mediating
photopolymerization,
present
some
promising
examples
which
are
advancing
production
through
their
exploitation
photochemistry.
Abstract
The
development
of
advanced
materials
based
on
well‐defined
polymeric
architectures
is
proving
to
be
a
highly
prosperous
research
direction
across
both
industry
and
academia.
Controlled
radical
polymerization
techniques
are
receiving
unprecedented
attention,
with
reversible‐deactivation
chain
growth
procedures
now
routinely
leveraged
prepare
exquisitely
precise
polymer
products.
Reversible
addition‐fragmentation
transfer
(RAFT)
powerful
protocol
within
this
domain,
where
the
unique
chemistry
thiocarbonylthio
(TCT)
compounds
can
harnessed
control
vinyl
polymers.
With
intense
recent
focus
RAFT,
new
strategies
for
initiation
external
have
emerged
that
paving
way
preparing
polymers
demanding
applications.
In
work,
cutting‐edge
innovations
in
RAFT
opening
up
technique
broader
suite
researchers
explored.
Emerging
activating
TCTs
surveyed,
which
providing
access
into
traditionally
challenging
environments
polymerization.
latest
advances
future
perspectives
applying
RAFT‐derived
also
shared,
goal
convey
rich
potential
an
ever‐expanding
range
high‐performance
Chemical Reviews,
Год журнала:
2020,
Номер
120(5), С. 2950 - 3048
Опубликована: Фев. 21, 2020
The
past
decades
have
witnessed
an
increasing
interest
in
developing
advanced
polymerization
techniques
subjected
to
external
fields.
Various
physical
modulations,
such
as
temperature,
light,
electricity,
magnetic
field,
ultrasound,
and
microwave
irradiation,
are
noninvasive
means,
having
superb
but
distinct
abilities
regulate
polymerizations
terms
of
process
intensification
spatial
temporal
controls.
Gas
emerging
regulator
plays
a
distinctive
role
controlling
resembles
some
cases.
This
review
provides
systematic
overview
seven
types
external-field-regulated
polymerizations,
ranging
from
chain-growth
step-growth
polymerization.
A
detailed
account
the
relevant
mechanism
kinetics
is
provided
better
understand
each
field
In
addition,
given
crucial
modeling
simulation
mechanisms
investigation,
model
construction
typical
numerical
methods
used
this
well
highlights
interaction
between
experiment
toward
existing
systems
given.
At
end,
limitations
future
perspectives
for
critically
discussed.
state-of-the-art
research
progress
not
only
fundamental
principles
underlying
also
stimulates
new
development
methods.
Chemical Science,
Год журнала:
2019,
Номер
10(38), С. 8724 - 8734
Опубликована: Янв. 1, 2019
The
width
and
shape
of
molecular
weight
distributions
can
significantly
affect
the
properties
polymeric
materials
thus
are
key
parameters
to
control.
This
mini-review
aims
critically
summarise
recent
approaches
developed
tailor
highlights
strengths
limitations
each
technique.
Special
emphasis
will
also
be
given
applications
where
tuning
distribution
has
been
used
as
a
strategy
not
only
enhance
polymer
but
increase
fundamental
understanding
behind
complex
mechanisms
phenomena.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(38), С. 13323 - 13328
Опубликована: Июль 10, 2019
Dispersity
significantly
affects
the
properties
of
polymers.
However,
current
methods
for
controlling
polymer
dispersity
are
limited
to
bimodal
molecular
weight
distributions,
adulterated
chains,
or
low
end-group
fidelity
and
rely
on
feeding
reagents,
flow-based,
multicomponent
systems.
To
overcome
these
limitations,
we
report
a
simple
batch
system
whereby
photoinduced
atom
transfer
radical
polymerisation
is
exploited
as
convenient
versatile
technique
control
both
homopolymers
block
copolymers.
By
varying
concentration
copper
complex,
wide
range
monomodal
distributions
can
be
obtained
(Đ=1.05-1.75).
In
all
cases,
high
was
confirmed
by
MALDI-ToF-MS
exemplified
efficient
copolymer
formation
(monomodal,
Đ=1.1-1.5).
Importantly,
our
approach
utilises
ppm
levels
(as
4
ppm),
tolerant
oxygen
exhibits
perfect
temporal
control,
representing
major
step
forward
in
tuning
various
applications.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(9), С. 3035 - 3097
Опубликована: Янв. 1, 2023
In
this
review,
we
provide
a
brief
history,
progress,
and
applications,
discuss
the
remaining
challenges
of
photocontrolled
reversible
addition-fragmentation
chain
transfer
(RAFT)
polymerization
(i.e.,
photoinduced
electron/energy
transfer-RAFT
(PET-RAFT),
photoiniferter,
photomediated
cationic
RAFT
polymerization).
Among
these,
visible-light-driven
has
attracted
particular
attention
in
recent
years
due
to
its
benefits,
including
low
energy
consumption
safe
reaction
procedure.
Moreover,
incorporation
visible-light
photocatalysis
conferred
attractive
features,
such
as
spatiotemporal
control
oxygen
tolerance;
however,
clear
understanding
mechanism
not
been
completely
provided.
We
also
present
research
efforts
elucidate
mechanisms
with
aid
quantum
chemical
calculations
combined
experimental
evidence.
This
review
offers
an
insight
into
better
design
systems
for
desired
applications
helps
realize
full
potential
both
academic-
industrial-scale
applications.
