Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(26), С. 9866 - 9871
Опубликована: Июнь 25, 2021
We
introduce
a
novel
grafting-through
polymerization
strategy
to
synthesize
dynamic
bottlebrush
polymers
and
elastomers
in
one
step
using
light
construct
disulfide-containing
backbone.
The
key
starting
material—α-lipoic
acid
(LA)—is
commercially
available,
inexpensive,
biocompatible.
When
installed
on
the
chain
end(s)
of
poly(dimethylsiloxane)
(PDMS),
cyclic
disulfide
unit
derived
from
LA
polymerizes
under
ultraviolet
(UV)
ambient
conditions.
Significantly,
no
additives
such
as
initiator,
solvent,
or
catalyst
are
required
for
efficient
gelation.
Formulations
that
include
bis-LA-functionalized
cross-linker
yield
with
high
gel
fractions
(83–98%)
tunable,
supersoft
shear
moduli
∼20–200
kPa
range.
An
added
advantage
these
materials
is
bonds
along
each
backbone,
which
allow
light-mediated
self-healing
on-demand
chemical
degradation.
These
results
highlight
potential
simple
scalable
synthetic
routes
generate
unique
based
PDMS.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июль 2, 2021
Abstract
Stretchable
ionic
skins
are
intriguing
in
mimicking
the
versatile
sensations
of
natural
skins.
However,
for
their
applications
advanced
electronics,
good
elastic
recovery,
self-healing,
and
more
importantly,
skin-like
nonlinear
mechanoresponse
(strain-stiffening)
essential
but
can
be
rarely
met
one
material.
Here
we
demonstrate
a
robust
proton-conductive
skin
design
via
introducing
an
entropy-driven
supramolecular
zwitterionic
reorganizable
network
to
hydrogen-bonded
polycarboxylic
acid
network.
The
allows
two
dynamic
networks
with
distinct
interacting
strength
sequentially
debond
stretch,
conflict
among
elasticity,
strain-stiffening
thus
defeated.
representative
polyacrylic
acid/betaine
elastomer
exhibits
high
stretchability
(1600%
elongation),
immense
(24-fold
modulus
enhancement),
~100%
excellent
elasticity
(97.9
±
1.1%
recovery
ratio,
<14%
hysteresis),
transparency
(99.7
0.1%),
moisture-preserving,
anti-freezing
(elastic
at
−40
°C),
water
reprocessibility,
as
well
easy-to-peel
adhesion.
combined
advantages
make
present
very
promising
wearable
iontronic
sensors
human-machine
interfacing.
Advanced Functional Materials,
Год журнала:
2019,
Номер
30(3)
Опубликована: Окт. 22, 2019
Abstract
The
design
and
synthesis
of
supramolecular
self‐healing
polymers
with
high
healing
efficiency
excellent
integrated
mechanical
properties
is
challenging
due
to
conflicting
attributes
dynamic
properties.
Herein,
this
study
introduces
a
concept,
that
is,
“dynamic
hard
domains,”
balance
performance,
strength,
elastic
recovery,
at
the
same
time
obtain
extreme
toughness.
essential
features
domains
include:
(i)
noncrystallized
loose
structure,
(ii)
low
binding
energy
mobility,
(iii)
sequential
dissociation
rapid
rearrangement.
Based
on
strategy,
simple
one‐step
polycondensation
route
reported
synthesize
transparent
polyurethane‐urea
elastomer
(PPGTD‐IDA),
which
successfully
combines
decent
toughness,
outstanding
notch‐sensitiveness,
self‐recoverability,
room‐temperature
self‐healing.
Upon
rupture,
PPGTD‐IDA
completely
restores
within
48
h.
Furthermore,
results
demonstrate
repeatable
prominent
antiaging
healability.
Taking
advantages
merits
PPGTD‐IDA,
it
can
be
utilized
for
fabricating
impact‐resistant
materials
protection
aluminum
alloys
as
well
stretchable
conductors,
exhibits
unique
characteristics
such
stable
conductivity
during
stretching
(even
after
or
notch),
automatic
elimination
notch
stretching/releasing
cycles.
Abstract
3D
printing
is
a
rapidly
growing
technology
that
has
an
enormous
potential
to
impact
wide
range
of
industries
such
as
engineering,
art,
education,
medicine,
and
aerospace.
The
flexibility
in
design
provided
by
this
technique
offers
many
opportunities
for
manufacturing
sophisticated
devices.
most
widely
utilized
method
extrusion‐based
solid‐freeform
fabrication
approach,
which
extremely
attractive
additive
both
academic
industrial
research
communities.
This
versatile,
with
the
ability
print
dimensions,
multimaterial,
multifunctional
structures.
It
also
very
affordable
prototyping.
However,
lack
variety
printable
polymers
advanced
material
properties
becomes
main
bottleneck
further
development
technology.
Herein,
comprehensive
review
provided,
focusing
on
strategies
achieve
or
enhance
printability
including
thermoplastics,
thermosets,
hydrogels,
other
extrusion
techniques.
Moreover,
diverse
exhibited
printed
polymers,
mechanical
strength,
conductance,
self‐healing,
well
integrated
are
highlighted.
Lastly,
stimuli
responsiveness
polymeric
materials
shape
morphing,
degradability,
color
changing
discussed.
ACS Nano,
Год журнала:
2021,
Номер
15(7), С. 11667 - 11680
Опубликована: Июнь 25, 2021
Lightweight
polymeric
foam
is
highly
attractive
as
thermal
insulation
materials
for
energy-saving
buildings
but
plagued
by
its
inherent
flammability.
Fire-retardant
coatings
are
suggested
an
effective
means
to
solve
this
problem.
However,
most
of
the
existing
fire-retardant
suffer
from
poor
interfacial
adhesion
during
use.
In
nature,
snails
and
tree
frogs
exhibit
strong
a
variety
surfaces
hydrogen-bonding
mechanical
interlocking,
respectively.
Inspired
their
mechanisms,
we
herein
rationally
design
with
phase-separated
micro/nanostructures
via
facile
radical
copolymerization
hydroxyethyl
acrylate
(HEA)
sodium
vinylsulfonate
(VS).
The
resultant
waterborne
poly(VS-co-HEA)
copolymers
rigid
polyurethane
(PU)
other
substrates,
better
than
current
adhesives
because
combination
interlocking.
Besides
superhydrophobic
feature,
poly(VS-co-HEA)-coated
PU
can
self-extinguish
flame,
exhibiting
desired
V-0
rating
vertical
burning
low
heat
smoke
release
due
high
charring
capability,
which
superior
previous
counterparts.
Moreover,
well-preserved
agrees
well
theoretical
calculations.
This
work
offers
biomimetic
strategy
creating
advanced
adhesive
many
flammable
substrates.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(14), С. 7947 - 7955
Опубликована: Янв. 15, 2021
Abstract
We
designed
and
synthesized
a
colorless
transparent
glassy
polyurethane
assembled
using
low‐molecular‐weight
oligomers
carrying
large
number
of
loosely
packed
weak
hydrogen
bonds
(H‐bonds),
which
has
glass
transition
temperature
(
T
g
)
up
to
36.8
°C
behaves
unprecedentedly
robust
stiffness
with
tensile
Young's
modulus
1.56±0.03
GPa.
Fast
room‐temperature
self‐healing
was
observed
in
this
polymer
network:
the
broken
(GPU)
specimen
can
recover
strength
7.74±0.76
MPa
after
healing
for
as
little
10
min,
is
prominent
compared
reported
polymers.
The
high
density
loose‐packed
reversibly
dissociate/associate
below
GPU
(that
secondary
relaxation),
enables
reconfiguration
damaged
network
fractured
interfaces,
despite
extremely
slow
diffusion
dynamics
molecular
chains
under
room
temperature.
This
shows
potential
application
an
optical
lens.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Янв. 27, 2021
Self-repairable
materials
strive
to
emulate
curable
and
resilient
biological
tissue;
however,
their
performance
is
currently
insufficient
for
commercialization
purposes
because
mending
toughening
are
mutually
exclusive.
Herein,
we
report
a
carbonate-type
thermoplastic
polyurethane
elastomer
that
self-heals
at
35
°C
exhibits
tensile
strength
of
43
MPa;
this
as
strong
the
soles
used
in
footwear.
Distinctively,
it
has
abundant
carbonyl
groups
soft-segments
fully
amorphous
with
negligible
phase
separation
due
poor
hard-segment
stacking.
It
operates
dual
mechano-responsive
mode
through
reversible
disorder-to-order
transition
its
hydrogen-bonding
array;
heals
when
static
toughens
dynamic.
In
mode,
non-crystalline
hard
segments
promote
dynamic
exchange
disordered
hydrogen-bonds
self-healing.
The
forms
stiff
crystals
stretched
orders
inter-chain
hydrogen
bonding.
strain
return
pre-stressed
state
after
release
repeat
healing
process.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(32), С. 12804 - 12814
Опубликована: Июль 26, 2019
Programming
the
hierarchical
self-assembly
of
small
molecules
has
been
a
fundamental
topic
great
significance
in
biological
systems
and
artificial
supramolecular
systems.
Precise
highly
programmed
can
produce
architectures
with
distinct
structural
features.
However,
it
still
remains
challenge
how
to
precisely
control
pathway
desirable
way
by
introducing
abundant
information
into
limited
molecular
backbone.
Here
we
disclose
strategy
that
directs
sodium
thioctate,
molecule
origin,
ordered
layered
network.
By
combining
unique
dynamic
covalent
ring-opening-polymerization
thioctate
an
evaporation-induced
interfacial
confinement
effect,
direct
this
simple
scheduled
pathway,
resulting
structure
long-range
order
at
both
macroscopic
scales,
which
is
revealed
small-angle
wide-angle
X-ray
scattering
technologies.
The
layers
are
found
be
able
bind
water
as
water,
works
interlayer
lubricant
modulate
material
properties,
such
mechanical
performance,
self-healing
capability,
actuating
function.
Analogous
many
reversibly
self-assembled
systems,
polymeric
network
degraded
monomers
reformed
water-mediated
route,
exhibiting
full
recyclability
facile,
mild,
environmentally
friendly
way.
This
approach
for
assembling
commercial
structurally
complex
materials
paves
low-cost
functional
based
on
synthetically
procedures.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(5), С. 2022 - 2033
Опубликована: Янв. 6, 2022
The
development
of
a
dynamic
chemistry
toolbox
to
endow
materials
behavior
has
been
key
the
rational
design
future
smart
materials.
rise
supramolecular
and
covalent
offers
many
approaches
construction
polymers
that
can
adapt,
respond,
repair,
recycle.
Within
this
toolbox,
building
blocks
based
on
1,2-dithiolanes
have
become
an
important
scaffold,
featuring
their
reversible
polymerization
mediated
by
disulfide
bonds,
which
enables
unique
class
at
intersection
adaptable
networks.
This
Perspective
aims
explore
as
versatile
structural
unit
for
summarizing
state
art
well
providing
overview
fundamental
challenges
involved
in
research
area
its
potential
directions.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(13), С. 5278 - 5283
Опубликована: Фев. 25, 2020
Supramolecular
polymers
that
can
heal
themselves
automatically
usually
exhibit
weakness
in
mechanical
toughness
and
stretchability.
Here
we
exploit
a
toughening
strategy
for
dynamic
dry
supramolecular
network
by
introducing
ionic
cluster-enhanced
iron-carboxylate
complexes.
The
resulting
simultaneous
exhibits
tough
strength,
high
stretchability,
self-healing
ability,
processability
at
room
temperature.
excellent
performance
of
these
distinct
is
attributed
to
the
hierarchical
existence
four
types
combinations
high-density
network,
including
covalent
disulfide
bonds,
noncovalent
H-bonds,
complexes
clustering
interactions.
extremely
facile
preparation
method
this
polymer
offers
prospects
high-performance
low-cost
material
among
others
coatings
wearable
devices.