Phosphorus, sulfur, and silicon and the related elements,
Год журнала:
2024,
Номер
unknown, С. 1 - 8
Опубликована: Ноя. 23, 2024
DFT
calculations
were
carried-out
for
some
of
novel
designed
structures
with
basicity
and
superbasicity
potentials.
In
this
research,
two
series
cyclic
phosphorus-containing
compound
inspiring
from
1,3,5,7-tetraazaadamantane
1,4-diazabicyclo[2,2,2]octane.
The
proton
affinity
(PA)
in
the
gas
phase
was
calculated
each
1–14.
Most
found
to
have
higher
than
that
1,8-bis(dimethylamino)
naphthalene
(DMAN)
as
threshold
(3,
4,
7,
10–14).
effect
heteroatom
substituents
type
ring
well
internal
bond
angles
on
evaluated.
It
structure
14
possesses
highest
PA
value
1198.27
kJ
mol−1
phase.
According
obtained
results,
values
significantly
amplified
by
substitution
electron
releasing
groups
molecular
framework.
Also,
limitations
created
donation
substitutents
neighborhood
main
phosphazene
group
are
discussed.
Journal of Polymer Science,
Год журнала:
2023,
Номер
62(1), С. 42 - 91
Опубликована: Ноя. 3, 2023
Abstract
This
comprehensive
review
aims
to
provide
an
in‐depth
analysis
of
the
catalytic
performance
1,5,7‐triazabicyclo[4,4,0]dec‐5‐ene
(TBD)
in
polymer
synthesis.
TBD,
a
well‐established
organic
superbase,
possesses
distinctive
bifunctional
character
that
grants
it
exceptional
capabilities,
particularly
processes
such
as
transesterification
or
transamidation.
TBD
has
garnered
considerable
attention
since
its
initial
report
by
Hedrick
and
Waymouth
2006,
played
pivotal
role
diverse
polymerization
reactions.
Its
versatility
spans
various
modes,
including
chain‐growth
step‐growth
polymerization,
post‐polymerization
modification,
network
thermoset
formation.
More
recently,
utility
extended
green
chemical
recycling
polymers.
By
providing
encompassing
overview
TBD's
historical
journey,
this
delves
into
past
accomplishments
while
shedding
light
on
present
future
potential
organocatalysts
science.
Physical Chemistry Chemical Physics,
Год журнала:
2023,
Номер
25(41), С. 27936 - 27941
Опубликована: Янв. 1, 2023
The
structure-activity
relationships
of
1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD)
based
protic
ionic
salts
for
polyethylene
terephthalate
(PET)
glycolysis
by
ethylene
glycol
(EG)
were
comprehensively
investigated
through
theoretical
prediction
and
experimental
verification.
proton
capture
ability
the
anionic
ligand
from
EG
is
positively
correlated
with
activity
catalyst,
as
generation
EG-
was
crucial
chain
breaking
reaction
via
nucleophilic
attack
on
carbonyl
group.
Furthermore,
density
functional
theory
calculations
demonstrated
that
HTBD
cation
ligands
work
in
a
cooperative
manner
PET
reaction,
where
abstract
to
generate
provide
produce
bis(hydroxyalkyl)terephthalate
(BHET)
product.
rate-determining
step
step,
Gibbs
energy
barriers
(ΔG≠)
increase
order
29.7
kcal
mol-1
(HTBD-OAc)
<
30.2
(HTBD-CH3CH2COO)
31.4
(HTBD-HCOO)
35.7
(HTBD-CH3COCOO)
36.9
(HTBD-NO3).
This
confirmed
results
BHET
yields
decrease
84.8%
>
82.4%
80.2%
73.6%
4.7%
These
findings
offer
valuable
guidance
designing
more
efficient
metal-free
salts,
promoting
sustainable
recycling.
Polymer Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
CO
2
-binding
alcohols
enable
selective
PVC
functionalization,
integrating
into
polymer
modification
while
minimizing
waste
and
unwanted
side
reactions.
Macromolecules,
Год журнала:
2023,
Номер
56(17), С. 7006 - 7022
Опубликована: Авг. 22, 2023
In
this
work,
a
novel,
straightforward,
robust,
fast,
and
organocatalyst-mediated
phospha-Michael
reaction
(OCPMR)
was
developed
for
the
addition
of
phosphorus
nucleophiles
to
electron-deficient
alkynes.
Several
P–H
bond-bearing
compounds
with
either
fully
aliphatic
or
aromatic
units
were
utilized
newly
reaction,
it
found
that
phosphorous
species
containing
only
groups
reacted
activated
alkynes
within
5
min
at
room
temperature.
The
led
fast
double-addition
triple
bond
An
in-depth
analysis
mechanism
selectivity
OCPMR
performed
using
computational
methods.
Using
method,
double-phosphorylated
allyl-functional
monomers
synthesized
subsequently
used
synthesis
linear
crosslinked
polymers
via
thiol-ene
photopolymerization.
thermoset
materials
exhibited
LOI
values
as
high
26.4%.
We
also
showed
polyesters
having
bonds
could
be
easily
functionalized
compounds.
synthetic
method
proposed
herein
promises
easy
P–C
formation
under
mild
conditions,
is
straightforward
phosphorus-containing
monomers,
polymers,
polymer
post-functionalization.
believe
feature
will
great
interest
not
material
chemists
scientists
but
organic
chemists,
pharmaceutical
researchers,
etc.
Communications Chemistry,
Год журнала:
2024,
Номер
7(1)
Опубликована: Март 21, 2024
Abstract
Organocatalytic
ring-opening
polymerization
(ROP)
is
a
versatile
method
for
synthesizing
well-defined
polymers
with
controlled
molecular
weights,
dispersities,
and
nonlinear
macromolecular
architectures.
Despite
spectacular
advances
in
organocatalytic
ROP,
precision
synthesis
of
polysiloxanes
remains
challenging
due
to
the
mismatch
polarity
between
highly
polar
initiators
nonpolar
monomers
difficulty
suppressing
formation
scrambling
products
via
transetherification
reactions
during
ROP
cyclic
siloxanes.
Here,
we
describe
binary
(BOROP)
hexamethylcyclotrisiloxane
(D3)
employing
organic
bases
as
catalysts
(thio)ureas
cocatalysts.
The
BOROP
D3
using
triazabicyclodecene
(TBD)
generates
polydimethylsiloxanes
(PDMSs)
narrow
dispersity
(
M
w
/
n
<
1.1).
similar
basicities
TBD
1,8-bis(tetramethylguanidino)naphthalene
(TMGN),
which
known
proton
sponge,
unitary
system
TMGN
was
inactive
D3.
When
paired
acidic
urea,
yielded
PDMSs
Data
suggest
that
synergetic
effect
urea
results
an
unprecedented
activation–deactivation
equilibrium
dormant
propagating
species.
benefits
present
are
demonstrated
by
PDMS
elastomers
more
uniform
network
structures
stretchy
have
excellent
mechanical
properties.
