ACS Applied Polymer Materials,
Год журнала:
2020,
Номер
2(12), С. 5716 - 5725
Опубликована: Ноя. 16, 2020
A
series
of
biobased
polyimine
vitrimers
was
synthesized
by
condensation
between
a
dialdehyde
or
trialdehyde
derived
from
vanillin
and
commercial
aliphatic
amine.
The
structure,
thermal
stability,
mechanical
properties,
reprocessability
with
different
cross-linking
degrees
were
investigated.
results
indicated
that
the
glass
transition
temperature
(Tg)
increased
increase
density.
In
addition,
showed
good
malleability
recyclability
even
high
degree
based
on
fast
imine
metathesis.
degradation
test
suggested
decomposition
rate
rising
temperature,
vitrimer
degraded
rapidly
in
0.1
M
HCl
aqueous
solution.
After
acid
degradation,
aldehyde
monomer
precipitated,
it
can
be
reused
to
prepare
realize
closed-loop
cycle.
Finally,
used
as
adhesives,
shear
tensile
strength
bond
up
6.79
MPa.
Chemical Science,
Год журнала:
2020,
Номер
11(19), С. 4855 - 4870
Опубликована: Янв. 1, 2020
In
this
minireview,
we
survey
recent
advances
in
the
development
of
vitrimer
materials.
Focus
on
how
to
chemically
control
their
material
properties
is
used
highlight
challenges
for
boosting
potential
emerging
class
polymer
Macromolecules,
Год журнала:
2020,
Номер
53(6), С. 1884 - 1900
Опубликована: Март 9, 2020
Vitrimers,
in
stringent
contrast
to
dissociative
networks,
involve
associative
covalent
exchanges
and
remain
fully
cross-linked
at
all
temperatures.
However,
we
have
previously
reported
on
poly(1,2,3-triazolium)
dynamic
networks
that
exhibit
linear
rheological
characterization
indistinguishable
from
vitrimers
although
being
based
a
exchange
process,
i.e.,
de-N-alkylation
re-N-alkylation
reactions.
Herein,
highlight
the
main
features
of
adaptable
(CANs)
discuss
their
respective
behaviors.
After
giving
detailed
overview
extent
potential
polymer
having
1,2,3-triazolium
cross-links
particular
CANs
involving
trans-N-alkylation
general,
perform
comparative
described
aliphatic
1,2,3-triazolium-based
new
bicomponent
thermosetting
system
issued
mixing
polystyrene
chains
complementary
benzyl
iodide
1,2,3-triazole
pendent
groups.
We
propose
simple
but
comprehensive
methodology
enables
proper
comparison
between
types
CANs,
networks.
Owing
combination
high
glass
transition
temperature
network
fast
this
network,
it
is
possible
characterize
both
relaxation
with
single
experiments.
provide
clear
experimental
evidence
located
within
narrow
range,
dependences
these
two
transitions
are
distinct
follow
WLF
Arrhenius
models,
respectively.
ACS Central Science,
Год журнала:
2020,
Номер
6(6), С. 921 - 927
Опубликована: Апрель 29, 2020
Cross-linked
polyurethane
(PU)
is
extensively
used
as
thermoset
foam;
however,
methods
to
directly
reprocess
PU
foam
waste
derived
from
commercial
sources
into
similar
value
materials
have
not
been
developed.
We
demonstrate
that
introducing
dibutyltin
dilaurate
(DBTDL)
cross-linked
foams
and
films
enables
their
reprocessing
at
elevated
temperatures
via
dynamic
carbamate
exchange
reactions.
Both
model
were
continuously
reprocessed
using
twin-screw
extrusion
remove
gaseous
filler
produce
filaments
or
with
elastomeric
rigid
mechanical
properties.
The
properties
of
microcompounded
in
excellent
agreement
film
synthesized
the
same
monomers,
indicating
this
process
occurs
efficiently.
These
findings
will
enable
bulk
inspire
further
development
for
other
thermosets
compatibilization
chemically
distinct
materials.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(9), С. 3609 - 3617
Опубликована: Дек. 17, 2019
Abstract
The
design
of
covalent
adaptable
networks
(CANs)
relies
on
the
ability
to
trigger
rearrangement
bonds
within
a
polymer
network.
Simple
activated
alkynes
are
now
used
as
versatile
reversible
cross‐linkers
for
thiols.
click‐like
thiol–yne
cross‐linking
reaction
readily
enables
network
synthesis
from
polythiols
through
double
Michael
addition
with
and
tunable
second
step.
resulting
thioacetal
moieties
robust
but
dynamic
linkages.
A
series
different
have
been
synthesized
systematically
probed
their
produce
linkages,
both
in
kinetic
studies
small
molecule
models,
well
stress
relaxation
creep
measurements
thiol–yne‐based
CANs.
results
further
rationalized
by
DFT
calculations,
showing
that
bond
exchange
rates
can
be
significantly
influenced
choice
alkyne
cross‐linker.
Polymers,
Год журнала:
2020,
Номер
12(8), С. 1660 - 1660
Опубликована: Июль 26, 2020
Thermosets
are
known
to
be
very
reliable
polymeric
materials
for
high-performance
and
light-weight
applications,
due
their
retained
dimensional
stability,
chemical
inertia
rigidity
over
a
broad
range
of
temperatures.
However,
once
fully
cured,
they
cannot
easily
reshaped
or
reprocessed,
thus
leaving
still
unsolved
the
issues
recycling
lack
technological
flexibility.
Vitrimers,
introduced
by
Leibler
et
al.
in
2011,
valiant
step
direction
bridging
chasm
between
thermoplastics
thermosets.
Owing
dynamic
covalent
networks,
can
retain
mechanical
stability
solvent
resistance,
but
also
flow
on
demand
upon
heating.
More
generally,
family
Covalent
Adaptable
Networks
(CANs)
is
gleaming
with
astounding
potential,
thanks
huge
variety
chemistries
that
may
enable
bond
exchange.
Arising
from
this
signature
feature,
intriguing
properties
such
as
self-healing,
recyclability
weldability
expand
horizons
thermosets
terms
improved
life-span,
sustainability
overall
enhanced
functionality
versatility.
In
review,
we
present
comprehensive
overview
most
promising
studies
featuring
CANs
vitrimers
specifically,
particular
regard
industrial
applications.
Investigations
into
composites
sustainable
epoxy-based
elastomeric
networks
covered
detail.
Macromolecules,
Год журнала:
2020,
Номер
53(10), С. 3796 - 3805
Опубликована: Май 13, 2020
A
family
of
biobased
polyimine
elastomeric
vitrimers
was
synthesized
by
reactions
between
di-
and
trifunctional
polyetheramines
a
furan-based
dialdehyde.
By
varying
the
triamine
to
diamine
ratio
molar
mass
diamine,
set
cross-linked
networks
with
similar
chemical
structures
but
different
cross-link
densities
obtained.
All
these
materials
exhibit
vitrimeric
behavior
because
dynamic
nature
imine
bonds.
This
fundamental
study
clearly
reveals
that
density
has
drastic
effect
on
relaxation
properties
vitrimers.
For
instance,
times
activation
energies
reduced
when
vitrimer
decreased.
shows
can
be
controlled
sole
modification
network
physical
without
introduction
catalyst,
change
in
structure,
or
additional
groups.
In
addition,
fast
dual
process
been
evidenced
during
stress
experiments,
which
could
potentially
lead
double
modes
based
supramolecular
interactions.
The
selective
solubility
also
demonstrated,
opening
interesting
possibilities
for
recycling
while
still
offering
robustness
against
aggressive
conditions
such
as
highly
basic
solutions.
Finally,
high
thermal
stability
designed
provide
an
reprocessability
tunable
mechanical
properties,
showing
versatility
this
sustainable
materials.
Macromolecules,
Год журнала:
2021,
Номер
54(9), С. 3927 - 3961
Опубликована: Апрель 19, 2021
Vitrimers
constitute
a
fascinating
class
of
polymer
materials
that
make
the
link
between
historically
opposed
3D
networks
(thermosets)
and
linear
polymers
(thermoplastics).
Their
chemical
resistance,
reshaping
ability,
unique
rheological
behavior
upon
heating
them
promising
for
future
applications
in
industry.
However,
many
vitrimers
require
use
high
catalyst
loadings,
which
raises
concerns
their
durability
limits
potential
applications.
To
cope
with
this
issue,
internal
catalysis
neighboring
group
participation
(NGP)
can
be
used
to
enhance
ability
such
materials.
A
few
studies
report
effect
activating
groups
on
exchange
reactions
vitrimers.
Nevertheless,
knowledge
topic
remains
scarce,
although
research
would
greatly
benefit
from
NGP
already
known
organic
chemistry.
The
present
Perspective
presents
different
types
exchangeable
bonds
implemented
discusses
have
or
potentially
capable
an
enhancing
reactions.
This
analysis
is
underpinned
by
thorough
mechanistic
discussion
various
presented.