A
method
is
presented
to
modify
the
degradation
rates
of
copolymers
made
through
vinyl-
and
radical
ring-opening
copolymerization.
Six
(including
five
novel)
7-membered
cyclic
allylic
sulfide
(CAS)
lactones
with
varied
functionality
(H,
ethyl,
decyl,
phenyl,
furyl,
benzo)
at
2
(or
2/3)
position
were
synthesized.
Their
copolymerization
hydroxypropyl
methacrylamide
(HPMAm),
N-isopropylmethacrylamide,
oligo(ethylene
glycol)
methyl
ether
methacrylate
(OEGMA)
led
inclusion
primary
alkyl,
secondary
benzyl,
phenyl
esters
into
backbone.
The
choice
CAS
lactone
comonomer
allowed
tuning
LCST-type
cloud
point
OEGMA
copolymers,
substituents
decreasing
in
order
H
<
ethyl
decyl
≪
∼
benzo.
Hydrolytic
rate
coefficients
determined
on
HPMAm
by
a
factor
3.3,
better
alcohol
leaving
groups
leading
faster
degradation.
Backbone
degraded
aminolysis,
while
benzyl
aliphatic
stable.
Selective
was
also
achieved
block
containing
(oxo)esters
one
thioesters
(from
thionolactone
copolymerization)
other.
These
findings
demonstrate
physical
properties
behavior
enabling
design
degradable
polymers
tailored
properties.
Materials,
Год журнала:
2025,
Номер
18(5), С. 928 - 928
Опубликована: Фев. 20, 2025
Recently,
the
radical
ring-opening
polymerization
of
cyclic
monomers
has
become
one
most
important
topics
because
it
can
impart
degradability
to
vinyl
polymers
by
introducing
functional
groups
and
heteroatoms
into
main
chain
through
copolymerization
with
monomers.
In
this
study,
we
investigated
possibility
sulfone
compounds,
including
sulfolane
sulfolene
derivatives.
First,
reactions
2,5-dimethyl-3-sulfolene
(DMS)
were
predicted
using
density
theory
(DFT)
calculations,
reaction
product
was
actually
examined
after
heating
in
presence
a
initiator.
Next,
synthesized
polymerized
2-vinylsulfolane
(2VS),
which
been
reported
undergo
literature
tried
modify
resulting
containing
unsaturated
via
post-polymerization
ene–thiol
additions.
We
also
decomposition
behavior
polymer
2VS
before
hydrogenation.
Furthermore,
discussed
reactivity
3-exomethylenesulfolane
(3EMS),
is
expected
exhibit
similar
2VS,
as
well
structure
corresponding
polymer.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21868 - 21876
Опубликована: Июль 25, 2024
Recent
advances
in
synthetic
methods
and
monomer
design
have
given
access
to
precision
carbohydrate
polymers
that
extend
beyond
native
polysaccharides.
In
this
article,
we
present
the
synthesis
of
a
class
chemically
recyclable
ester-linked
pseudo-polysaccharides
via
living
anionic
ring-opening
polymerization
glucurono-1,6-lactones.
Notably,
exhibited
defined
chain-end
groups,
well-controlled
molecular
weights,
narrow
weight
distributions,
all
hallmarks
polymerization.
Furthermore,
demonstrate
our
approach
is
modular,
as
evidenced
by
tunable
glass
transition
temperatures
(Tg)
ability
produce
both
amorphous
semicrystalline
adjusting
side
chain
structure.
Lastly,
showcased
complete
catalytic
chemical
recycling
these
back
monomers.
The
flexibility
recyclability
promote
sustainable
circular
economy
while
offering
potential
polysaccharide-like
materials
with
thermal
mechanical
properties.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(44)
Опубликована: Май 31, 2024
Radical
polymerization
is
the
most
widely
applied
technique
in
both
industry
and
fundamental
science.
However,
its
major
drawback
that
it
typically
yields
polymers
with
non-functional,
non-degradable
all-carbon
backbones-a
limitation
radical
ring-opening
(rROP)
allows
to
overcome.
The
last
decade
has
seen
a
surge
rROP,
primarily
focused
on
creating
degradable
polymers.
This
pursuit
resulted
creation
of
first
readily
materials
through
polymerization.
Recent
years
have
witnessed
innovations
new
monomers
address
previous
design
limitations,
such
as
ring
strain
reactivity
ratios.
Furthermore,
advances
integrating
rROP
reversible
deactivation
(RDRP)
facilitated
incorporation
complex,
customizable
chemical
payloads
into
main
polymer
chain.
short
review
discusses
latest
developments
monomer
analysis
their
limitations
broader
historical
context.
Recently
evolving
strategies
for
compatibility
RDRP
are
discussed,
which
key
precision
synthesis.
chemistry
surveyed
expands
horizon
beyond
mere
hydrolytic
degradation.
Now
time
explore
potential
residing
previously
inaccessible
backbone.
Biomacromolecules,
Год журнала:
2024,
Номер
26(1), С. 118 - 139
Опубликована: Дек. 29, 2024
Synthetic
vinyl
polymers
have
long
been
recognized
for
their
potential
to
be
utilized
in
drug
delivery,
tissue
engineering,
and
other
biomedical
applications.
The
synthetic
control
that
chemists
over
structure
properties
is
unmatched,
allowing
polymer-based
materials
precisely
engineered
a
range
of
therapeutic
Yet,
lack
biodegradability
compromises
the
biocompatibility
has
held
back
translation
into
clinically
used
treatments
disease
thus
far.
In
recent
years,
radical
ring-opening
polymerization
(rROP)
emerged
as
promising
strategy
render
biodegradable
bioresorbable.
While
rROP
touted
preparing
applications,
approved
not
yet
realized.
This
review
highlights
opportunities
leveraging
unlock
use
