Angewandte Chemie,
Год журнала:
2024,
Номер
136(25)
Опубликована: Март 23, 2024
Abstract
Although
sulfurated
polymers
promise
unique
properties,
their
controlled
synthesis,
particularly
when
it
comes
to
complex
and
functional
architectures,
remains
challenging.
Here,
we
show
that
the
copolymerization
of
oxetane
phenyl
isothiocyanate
selectively
yields
polythioimidocarbonates
as
a
new
class
sulfur
containing
polymers,
with
narrow
molecular
weight
distributions
(
M
n
=5–80
kg/mol
Đ
≤1.2;
,max
=124
kg/mol)
high
melting
points
up
181
°C.
The
method
tolerates
different
substituent
patterns
on
both
isothiocyanate.
Self‐nucleation
experiments
reveal
π‐stacking
substituents,
presence
unsubstituted
polymer
backbones,
kinetically
linkage
selectivity
are
key
factors
in
maximising
points.
increased
tolerance
macro‐chain
transfer
agents
propagation
allows
synthesis
double
crystalline
amphiphilic
diblock
copolymers,
which
can
be
assembled
into
micellar‐
worm‐like
structures
amorphous
cores
water.
In
contrast,
crystallization
driven
self‐assembly
ethanol
gives
cylindrical
micelles
or
platelets.
Macromolecules,
Год журнала:
2023,
Номер
56(17), С. 6798 - 6805
Опубликована: Авг. 22, 2023
The
conversion
of
CS2,
which
is
discarded
on
a
large
scale
as
pollutant,
into
valuable
sulfur-containing
polymers
significance
for
both
environmental
and
polymer
science.
However,
the
copolymerization
CS2
cyclic
ether
suffers
from
complex
structures
massive
byproducts.
Here,
we
use
cooperative
organocatalyst
system
composed
alkyl
borane
onium
salts
oxetane
copolymerization.
Of
interest,
highly
efficient
with
turnover
frequency
up
to
1103
h–1,
avoids
small-molecule
byproducts,
yields
previously
inaccessible
polythiocarbonates
bearing
regular
sequences.
in-chain
sulfur
atoms
make
polythiocarbonate
demonstrate
desirable
thermal
mechanical
properties,
melting
temperature
83
°C,
an
ultimate
tensile
strength
20.7
±
3.1
MPa,
elongation
at
break
480
20%.
For
mechanism,
Lewis
acid
activates
well
forms
borate
growing
anion,
revealed
by
density
functional
theory
studies.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Фев. 29, 2024
Abstract
Our
society
has
been
pursuing
high‐performance
biodegradable
polymers
made
from
facile
methods
and
readily
available
monomers.
Here,
we
demonstrate
a
library
of
enzyme‐degradable
with
desirable
properties
the
first
reported
step
polyaddition
diamines,
COS,
diacrylates.
The
contain
in‐chain
ester
thiourethane
groups,
which
can
serve
as
lipase‐degradation
hydrogen‐bonding
physical
crosslinking
points,
respectively,
resulting
in
possible
biodegradability
well
upgraded
mechanical
thermal
properties.
Also,
are
scalable
due
to
versatile
method
wide
variety
We
obtain
46
tunable
performance
covering
high‐
T
m
crystalline
plastics,
thermoplastic
elastomers,
amorphous
plastics
by
regulating
polymer
structure.
Additionally,
polymerization
is
highly
efficient,
atom‐economical,
quantitatively
yield,
metal‐
even
catalyst‐free.
Overall,
promising
green
materials
given
their
degradability,
simple
modular
synthesis,
remarkable
properties,
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(42)
Опубликована: Май 28, 2024
Abstract
Using
carbon
disulfide
(CS
2
)
and
carbonyl
sulfide
(COS)
as
sulfur‐containing
one‐carbon
feedstocks
to
make
value‐added
products
is
paramount
for
both
pure
applied
chemistry
environmental
science.
One
of
the
practical
strategies
copolymerize
these
bulk
chemicals
with
epoxides
produce
polymers.
This
approach
contributes
improving
sustainability
polymer
manufacturing,
provides
highly
desired
functional
materials,
has
attracted
much
attention.
However,
copolymerizations
invariably
exhibit
intensely
complicated
O/S
exchange
reaction,
leading
polymers
diverse
architectures.
As
understanding
continues
deepen,
recent
efforts
have
guided
significant
advances
in
synthesis
CS
‐
COS‐based
review
examines
summarizes
progress
this
field
promote
further
advance
synthesizing
from
COS.
Chemical Communications,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Terpolymerization
reactions
of
epoxides,
CO
2
,
and
the
third
monomers
such
as
cyclic
anhydrides,
lactones,
lactides,
heteroallenes,
olefins
give
polymers
with
controlled
structures
properties.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Март 23, 2024
Abstract
Although
sulfurated
polymers
promise
unique
properties,
their
controlled
synthesis,
particularly
when
it
comes
to
complex
and
functional
architectures,
remains
challenging.
Here,
we
show
that
the
copolymerization
of
oxetane
phenyl
isothiocyanate
selectively
yields
polythioimidocarbonates
as
a
new
class
sulfur
containing
polymers,
with
narrow
molecular
weight
distributions
(
M
n
=5–80
kg/mol
Đ
≤1.2;
,max
=124
kg/mol)
high
melting
points
up
181
°C.
The
method
tolerates
different
substituent
patterns
on
both
isothiocyanate.
Self‐nucleation
experiments
reveal
π‐stacking
substituents,
presence
unsubstituted
polymer
backbones,
kinetically
linkage
selectivity
are
key
factors
in
maximising
points.
increased
tolerance
macro‐chain
transfer
agents
propagation
allows
synthesis
double
crystalline
amphiphilic
diblock
copolymers,
which
can
be
assembled
into
micellar‐
worm‐like
structures
amorphous
cores
water.
In
contrast,
crystallization
driven
self‐assembly
ethanol
gives
cylindrical
micelles
or
platelets.
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Factors
determining
sequence
selectivity
in
sulfur-containing
ring-opening
copolymerization
are
governed
by
the
types
of
chain
ends
generated
so
that
monomers
which
lead
to
primary
alkoxide
and
thiolate
ends,
particularly
suitable.
Catalysts
combining
commercial
borane
Lewis
acids
and
potassium
acetate
complexes
achieve
the
selective
ring-opening
copolymerization
(ROCOP)
of
oxetanes
with
diverse
sulfur-containing
monomers.
