ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.
In this work, reactive 3-aminopropyloligomeric silsesquioxane (AP-OSS) was synthesized and studied, and the effect of AP-OSS depending on its content (0.1–1.0 wt.%) on the kinetics of polycyclotrimerization of dicyanate ester of bisphenol E (DCBE) was determined using the dynamic DSC method. AP-OS...
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| Дата: | 2024 |
|---|---|
| Автори: | , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2024
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| Назва журналу: | Ukrainian Chemistry Journal |
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871466049555136512 |
|---|---|
| author | Shulzhenko, Diana Grigoryeva, Olga Gumenna, Mariana Polunkin, Evgen Gorelov, Borys Fainleib, Alexander Grande, Daniel |
| author_facet | Shulzhenko, Diana Grigoryeva, Olga Gumenna, Mariana Polunkin, Evgen Gorelov, Borys Fainleib, Alexander Grande, Daniel |
| author_institution_txt_mv | [
{
"author": "Diana Shulzhenko",
"institution": "ІХВС"
},
{
"author": "Olga Grigoryeva",
"institution": "Institute of Macromolecular Chemistry"
},
{
"author": "Mariana Gumenna",
"institution": "Institute of Macromolecular Chemistry"
},
{
"author": "Evgen Polunkin",
"institution": null
},
{
"author": "Borys Gorelov",
"institution": null
},
{
"author": "Alexander Fainleib",
"institution": null
},
{
"author": "Daniel Grande",
"institution": null
}
] |
| author_sort | Shulzhenko, Diana |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:54Z |
| description | In this work, reactive 3-aminopropyloligomeric silsesquioxane (AP-OSS) was synthesized and studied, and the effect of AP-OSS depending on its content (0.1–1.0 wt.%) on the kinetics of polycyclotrimerization of dicyanate ester of bisphenol E (DCBE) was determined using the dynamic DSC method. AP-OSS was prepared in high yield by the hydrolysis and polycondensation of 3-aminopropyltrimethoxysilane in a mixture of acetonitrile and ethanol, with tetrabutylammonium hydroxide (But4NOH) as a catalyst. The chemical structure of the synthesized AP-OSS was confirmed by the results of FTIR and 1H NMR spectroscopies, as well as by MALDI-TOF method. The FTIR spectra showed broad and intensive stretching absorption bands centered at ν≈ 3431 and ν≈ 3378 cm–1 and bending absorption bands centered at δ≈ 1638 and δ≈ 1599 cm-1 of the N–H in NH2 groups, as well as the absorption bands centered at ν≈1027 and δ≈859 cm–1, attributed to the special characteristic vibrations of the silsesquioxane cage Si–O–Si. MALDI-TOF spectroscopy detected predominantly singly charged protonatedions, indicating that the degree of oligomerization in this silsesquioxane is between n = 3 and 10. It was found that AP-OSS accelerated the DCBE polycyclotrimerization allowing decreasing the final temperature and time of polycyanurate network (PCN) synthesis, the higher content of the AP-OSS the higher acceleration effect has been observed. It was supposed that during the in situ synthesis of the hybrid PCN/AP-OSS nanocomposites, the amino groups on a surface of AP-OSS nanoparticles chemically interact with –O–C≡N-groups of DCBE with formation of isourea fragments providing the covalent embedding of  AP-OSS into the growing PCN matrix. Using DSC method, it was found that all synthesized hybrid  PCN/AP-OSS nanocomposites possessed high glass transition temperatures (Tg>280oC) and can be classified as thermally stable polymer materials. |
| doi_str_mv | 10.33609/2708-129X.90.5.2024.28-43 |
| first_indexed | 2025-09-24T17:43:56Z |
| format | Article |
| fulltext |
28 ISSN 2708-129X. Укр. хім. журн., 2024
UDC: 541.64:678.07:678.65 doi: 10.33609/2708-129X.90.5.2024.28-43
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC
SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE
HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.
D. M. Shulzhenko1,2, O. P. Grigoryeva1*, M. A. Gumenna1, E. V. Polunkin3,
B. M. Gorelov4, A. M. Fainleib1*, D. Grande2
1Institute of Macromolecular Chemistry of the NAS of Ukraine;
2Universitéde Strasbourg, CNRS, Institut Charles Sadron,
UPR 22, Strasbourg, France;
3V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine;
4Chuiko Institute of Surface Chemistry of the NAS of Ukraine.
email: fainleib@i.ua
In this work, reactive 3-aminopropyloligomeric silsesquioxane (AP-OSS) was synthesized and stu
died, and the effect of AP-OSS depending on its content (0.1–1.0 wt.%) on the kinetics of polycyclotri
merization of dicyanate ester of bisphenol E (DCBE) was determined using the dynamic DSC method.
AP-OSS was prepared in high yield by the hydrolysis and polycondensation of 3-aminopropyltrimeth-
oxysilane in a mixture of acetonitrile and ethanol, with tetrabutylammonium hydroxide (But4NOH)
as a catalyst. The chemical structure of the synthesized AP-OSS was confirmed by the results of FTIR
and 1H NMR spectroscopies, as well as by MALDI-TOF method. The FTIR spectra showed broad and
intensive stretching absorption bands centered at ν≈ 3431 and ν≈ 3378 cm–1 and bending absorption
bands centered at δ≈ 1638 and δ≈ 1599 cm-1 of the N–H in NH2 groups, as well as the absorption bands
centered at ν≈1027 and δ≈859 cm–1, attributed to the special characteristic vibrations of the silsesqui-
oxane cage Si–O–Si. MALDI-TOF spectroscopy detected predominantly singly charged protonatedions,
indicating that the degree of oligomerization in this silsesquioxane is between n = 3 and 10. It was found
that AP-OSS accelerated the DCBE polycyclotrimerization allowing decreasing the final temperature and
time of polycyanurate network (PCN) synthesis, the higher content of the AP-OSS the higher accelera-
tion effect has been observed. It was supposed that during the in situ synthesis of the hybrid PCN/AP-
OSS nanocomposites, the amino groups on a surface of AP-OSS nanoparticles chemically interact with
–O–C≡N-groups of DCBE with formation of isourea fragments providing the covalent embedding of
AP-OSS into the growing PCN matrix. Using DSC method, it was found that all synthesized hybrid
PCN/AP-OSS nanocomposites possessed high glass transition temperatures (Tg>280oC) and can be clas-
sified as thermally stable polymer materials.
Keywords: cyanate ester resins, oligomeric silsesquioxane, polycyanurates, synthesis ki-
netics, accelerating effect.
29https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
INTRODUCTION. Modern technologies
require multifunctional organo-inorganic po
lymeric nanocomposites for high-tech applica-
tions. Special interest is given to nanocompos-
ites based on polymer matrices possessing high
thermal, chemical, and moisture resistance.
Among them polycyanurate networks (PCN)
synthesized from cyanate ester resins have re-
ceived much attention because of their unique
combination of physical properties, including
high glass transition temperatures (Тg ~ 210–
400 °C), high thermal stability (Td5% >340 ºC),
low dielectric constants (ε = 2.64−3.11) low
toxicity and water absorption (< 3 wt.%), high
adhesion to different substrates, etc.[1-6]. As a
result, PCN are currently used as heat-, chemi
cally- and radiation resistant matrices for car-
bon, glass and organic plastics in structural
and functional materials applicable in micro
electronics, aeronautics, space structures (com-
posite strakes, fins, nose radar domes, heat
shields, antennas), printed circuit boards, as
well as adhesives [3, 7]. However, like for most
thermosets, their main drawback is brittleness
and long high temperature curing.To overcome
this limitations, modification of PCN has been
developed over the last decades, and it is still of
great interest. PCN are modified by synthesis
of nanocomposites of PCN with montmoril-
lonite (MMT), carbon nanotubes, nanosilica,
polyhedral oligomeric silsesquioxanes (POSS)
and other nanofillers.
Nowadays, POSS attract much attention as
one of the most important nanostructured ma-
terials owing to its excellent properties such as
mechanical strength, thermal stability, and low
dielectric constant[8].
POSS represent cage structures with the
formula (RSiO1.5)n where n = 8, 10, 12 and R
is hydrogen, reactive, or non-reactive organic
groups. Each silicon atom is bonded to three
oxygen atoms in a cage and to a single R sub-
stituent out of cage. These substituents improve
compatibility of POSS molecules with poly-
mers or monomers. In the case of reactive R,
3-D POSS molecules with diameters of 1–2 nm
may graft chemically to polymer structures.
New hybrid organic–inorganic PCN-based
thermosets with hydroxy- [9–12], amino- [6,
13–15] or epoxy-functionalized [16–21] POSS
units have thus been obtained with improved
thermal and mechanical properties.
In the last decade, Zhang and co-authors
[11] investigated the effect of amino-POSS
with eight primary amino groups on the cur-
ing behavior of dicyanate ester of bisphenol A
(DCBA) with PCN formation.They concluded
that both temperature and POSS content influ-
ence on the curing reaction of DCBA. Authors
noted that amino-POSS displayed the catalytic
effect mainly at high temperature and the pe-
culiarities were more complex at lower temper-
ature. The incorporation of amino-POSS into
PCN matrix led to the improvement in thermal
stability and hot/wet resistance. Nanocompo
site sample containing 1 wt.% of amino-POSS
showed the best dielectric properties: the low-
est dielectric constant and the lowest dielectric
loss.
In previous work [6] we studied the effect of
amino-POSS on structure-property relation-
ships of thermostable hybrid cyanate ester re
sin based nanocomposites. We discovered that
the addition of a small quantity (0.1 wt.%) of
three different reactive amino-POSS chemical-
ly grafted to the PCN network led to increasing
thermal stability of PCN matrix by 12–15 °С,
depending on the type of amino-POSS. A sig-
nificant increase of the glass transition tem-
perature, Tg (DSC data), and the temperature
30 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
of α relaxation, Tα (DMTA data), by 45–55 ºС
of PCN matrix with loading of the nanofi
llers was evidenced. PCN/POSS films exhibit-
ed a higher storage modulus than that of neat
PCN in the temperature range investigated. It
was evidenced that PCN/aminopropylisobu-
tyl (APIB)-POSS, PCN/N-phenylaminopropyl
(NPAP)-POSS, and PCN/aminoethylamino-
propylisobutyl (AEAPIB)-POSS nanocom-
posites demonstrated a more homogenous
α relaxation phenomenon with higher Tα va
lues and an enhanced elastic behavior. The va
lue of storage modulus, Е', at 25 ºC increased
from 2.72 GPa for pure PCN matrix to 2.99–
3.24 GPa for the nanocomposites with ami-
no-POSS nanoparticles.
Recently, some authors investigated[22]
the kinetic regularities of forming thermo-
stable polycyanurate networks (PCN) from
dicyanate ester of bisphenol E (DCBE) with
reactive APIB-POSS. They found that even
0.1 wt.% of APIB-POSS catalyzed high-tem-
perature polycyclotrimerization of DCBE, en-
abling polymerization at lower temperatures
and within a narrower time frame, resulting
in a PCN/APIB-POSS nanocomposite with
a higher Tg value. Notably, small amounts of
APIB-POSS did not introduced effects into
the PCN matrix. Additionally, the catalytic ef-
fect of NPAP-POSS, containing eight reactive
secondary amino groups, was examined[23]
in synthesizing hybrid nanocomposites based
on PCN from DCBE. FTIR and DSC analyses
revealed a reduced on set time for auto-ac-
celeration, accelerated conversion of cyanate
groups, increased maximum reaction rates,
and decreased polycyclotrimerization dura-
tion. Dynamic DSC measurements confirmed
NPAP-POSS's catalytic impact, showing sig-
nificant changes in exothermic maximum
temperature, increased reaction enthalpy,
and non-monotonic variation in induction
period and reaction rate based on nanofiller
content.
Oligoaminopropylsilsesquioxanes (OSS)
are very promising reactive compounds, which
can be used as initial components for synthe-
sis of different polymer materials, oligo- or
polysiloxanes, as effective modifiers, or as har
deners for thermosetting resins, for preparing
nanocomposites via reactive amino groups
[24–26]. For the best of our knowledge, no
papers were published on PCN/OSS synthesis
and characterization.
Therefore, the aim of the present work is to
investigate the influence of reactive 3-amino-
propyl oligomeric silsesquioxane (AP-OSS) on
the kinetics of in situ synthesis of thermosta-
ble hybrid organic-inorganic nanocomposites
based on PCN and thermophysical properties
of the nanocomposites obtained depending on
the content of the nanofiller used.
EXPERIMENT AND DISCUSSIONS OF
THE RESULTS. The cyanate ester monomer
used in this work was1,1-bis(4-cyanatophenyl)
ethane (DCBE, Primaset LECy from Lonza,
Switzerland). The nanosized reactive organi-
cally functionalized OSS, aminopropyl oligo-
meric silsesquioxane (AP-OSS) was synthe-
sized by the hydrolysis and polycondensation
of trifunctional monomer 3-aminopropyltri
methoxysilane (see below for thefurther details).
3-Aminopropyltrimethoxysilane (APTMS),
ethanol, acetonitrile and tetrabutylammonium
hydroxide were purchased from Sigma-Aldrich
and used as received.
AP-OSS was prepared following the me
thod described in the literature [24](with some
modifications). 7 mL of distilled water, 4 mL
31https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
of anhydrous ethanol, 1 mL of acetonitrile,
and 0,7 mL of tetrabutylammonium hydroxi
de (10% aqueous solution) were put into a
three-neck flask equipped with a mechanical
stirrer and a condenser, and mixed by stirring
(1100 rpm). 3-aminopropyltrimethoxysilane
(17.9 g) was added dropwise into the mix-
ture for 10 min at vigorous stirring (800 rpm).
The reaction was conducted at 50 °C for 24 h.
A straw gelatinous product was yielded dur-
ing the reaction. The product was washed with
acetonitrile for three times, and finally, it was
dried under reduced pressure at 70 °C for 24 h.
A white crystalline product was obtained (the
yield was 94%).
Different content of the nanofiller obtained,
i.e. AP-OSS (0, 0.1, 0.5 and 1 wt %) was added
to the liquid DCBE (~200 mg) and thorough-
ly grinded in an agate mortar for ~10 min at
the ambient temperature until a transparent,
i.e. homogenous, mixture was formed. Then
the resulting mixture (~10 mg) was placed in
a hermetic aluminium pan for dynamic curing
during DSC measurements.
1H-NMR spectra were performed using
Varian VNMRS spectrometer (Agilent Inc.,
USA) at 400 MH zat temperature of about
20ºC. The spectra were recorded in deuterated
DMSO.
FTIR spectra were recorded using a Tensor
37 spectrometer (Bruker Daltonics Inc., Ger-
many) at room temperature in the range of
4000–600 cm-1. The sample was pressed into
pellets with KBr.
Matrix-assisted UV-MALDI-TOF mass
spectroscopy was performed using an Aut-
oflex II (Bruker Daltonics Inc., Germany)
equipped with a pulsed nitrogen laser (λ =
337 nm). The selected matrix was 2,5-dihy-
droxybenzoic acid. Sample was irradiated just
above the threshold laser power to obtain mo-
lecular ions.
Differential scanning calorimetry (DSC)
with Discovery DSC 25 Differential Scanning
Calorimeter (TA Instruments, USA) was used
to estimate the effect of the nanofiller on the ki-
netic characteristics of polycyclotrimerization
of DCBE, i.e. the duration of induction period
(τi) and total reaction time (τtot), the maximal
rate of reaction (Wmax), temperature of exo-
thermic peaks (Tр(max)), total enthalpy of reac-
tion (∆Htot), conversion of cyanate groups (α)
etc. For nanocomposites synthesized the glass
transition temperature, Tg, heat capacity jump,
∆Cp, and other thermophysical characteristics
were found. The first and second scan with the
heating rate of 5 and 20 °C/min, respectively,
over the temperature range from 25 to 350 °C
in nitrogen atmosphere were performed.
Fig.1 represents the FTIR spectrum of
AP-OSS synthesized. The wide and intensive
peaks at 3431 and 3378 cm–1are attributed
to the stretching vibrationand at 1638 and
1599 cm-1 to bending vibrationof N–H in NH2
groups. There is also some weak shoulder at
3308 cm-1 that belongs to O–H stretching of
the OH groups.The strong double peak at
2929 and 2866 cm–1 corresponds to the C–H
stretching of the CH2 groups in the amino-
propyl fragment. The absorption band at
1122 cm–1 is the characteristic vibration of
Si–O–Si bond. The absorption peaks at 1027
and 859 cm–1 are attributed to the special
characteristic vibration of silsesquioxane cage
Si–O–Si framework. The peak at 757 cm–1 re-
lates to the bending vibration of Si–C bond
in Si–CH2. So, the FTIR spectrum of the pro
duct synthesized gives good assignment to
the structure of AP-OSS [24].
32 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
Fig.1 shows the 1H NMR spectrum of AP-
OSS in DMSO-d6. Four peaks with chemical
shifts of 0.56 ppm (CH2 in the α position to the
silicon atom (a)),1.43 ppm (CH2 in the β po-
sition to the silicon atom (b), 2.67 ppm (CH2
in the α position to the primary amino group
(c)) and 3.26 ppm (OH-group (d)), appear in
the spectrum [27]. Each of them is assigned
to one type of the hydrogen atoms of the same
chemical environment, further supporting the
structure of AP-OSS prepared.
Fig.1. FTIR spectra of AP-OSS.
Fig.1 shows the 1HNMR spectrum of AP-OSS in DMSO-d6. Four peaks with chemical shifts of
0.56 ppm (CH2 in the position to the silicon atom (a)),1.43 ppm (CH2 in the position to the
silicon atom (b), 2.67 ppm (CH2 in the position to the primary amino-group (c)) and 3.26ppm
(OH-group (d)), appear in the spectrum [27]. Each of them is assigned to one type of the hydrogen
atoms of the same chemical environment, further supporting the structure of AP-OSS prepared.
Fig. 2. 1H NMR spectra of AP-OSS(DMSO-d6).
3600 3200 2800 2400 2000 1600 1200 800
(Si–O–Si)cage
(Si–O–Si)cage
N–H
Si–C
16
38
Si–O–Si
C–H
N–H
75
7
859
11
22 10
27
28
6629
29
A
bs
or
ba
nc
e
Wavenumber, cm-1
33
7834
31
15
99
33
08
O–H
5 4 3 2 1 0
n
NH2
NH2
OH
OH
OH Si
OH
O
NH2
OH
Si
O
Si
b
c
a
d
d
c
b
H, ppm
a
DMSO-d6
H2O
Fig.1. FTIR spectra of AP-OSS.
Fig.1 shows the 1HNMR spectrum of AP-OSS in DMSO-d6. Four peaks with chemical shifts of
0.56 ppm (CH2 in the position to the silicon atom (a)),1.43 ppm (CH2 in the position to the
silicon atom (b), 2.67 ppm (CH2 in the position to the primary amino-group (c)) and 3.26ppm
(OH-group (d)), appear in the spectrum [27]. Each of them is assigned to one type of the hydrogen
atoms of the same chemical environment, further supporting the structure of AP-OSS prepared.
Fig. 2. 1H NMR spectra of AP-OSS(DMSO-d6).
3600 3200 2800 2400 2000 1600 1200 800
(Si–O–Si)cage
(Si–O–Si)cage
N–H
Si–C
16
38
Si–O–Si
C–H
N–H
75
7
859
11
22 10
27
28
6629
29
A
bs
or
ba
nc
e
Wavenumber, cm-1
33
7834
31
15
99
33
08
O–H
5 4 3 2 1 0
n
NH2
NH2
OH
OH
OH Si
OH
O
NH2
OH
Si
O
Si
b
c
a
d
d
c
b
H, ppm
a
DMSO-d6
H2O
Fig.1. FTIR spectra of AP-OSS.
Fig. 2. 1H NMR spectra
of AP-OSS (DMSO-d6).
33https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
The analysis of the MALDI-TOF mass spec-
trum (Fig.3) of the synthesized AP-OSS shows
the predominantly singly charged protonated
ions, indicating that the degree of oligomeri-
zation within this silsesquioxane ranges from
n = 3 to 10. It can be seen that the m/z sig-
nal peaks of AP-OSS are distributed between
300 and 1200, and the signal peaks with dif-
ferent m/z values correspond to AP-OSS with
different numbers of Si atoms, means to the
atomic fragments of the condensate (SiO1.5-
(CH2)3-NH2)n with m/z = (110 D)n at different
values of the n index, as well as their products
of altered composition due to incomplete syn-
thesis reaction or destruction under the laser
excitation. The spectrum shows the difference
in the atomic composition of the synthesized
fragments with even and odd n index. Thus,
AP-OSS complexes with odd indices 7 and 9
include an atomic fragment with a lower oxy
gen content SiO – ((CH2)3-NH2) with m/z
102 D. The presence of fragments with differ-
ent oxygen content in the condensate struc-
ture leads to reduction in the atomic weight of
the condensate and a shift of its mass line by
m/z = 8 D.
Besides, there is AP-OSS structure with
n = 9 and m/z 990 D, built only by complex-
es with m/z = 110 D, where the atomic group
with m/z 27 D (NCH or CH2CH) is absent. The
complexes with even values of n = 6, 8 and 10
have the incomplete content due to vacancies
of atomic groups with m/z = 17 (OH) and 26 D
(NC or HCCH) in the AP-OSS space struc-
tures with n = 9 and m/z 990 D, built only by
(SiO1.5-(CH2)3-NH2) fragments.
Note, that the condensate with n = 8 is
completely formed by eight fragments of
(SiO1.5-(CH2)3-NH2) is detected. However, at
lower index values, when n = 5, line m/z 524,
the AP-OSS condensate is formed by five
fragments with m/z 110 D without the NC or
CHCH (m/z 26) atomic groups. The line with
m/z 423 and n = 4 indicates the formation of
an AP-OSS complex built by four fragments
(SiO1.5-(CH2)3-NH2) without one hydroxyl group.
Thus, as a result of the synthesis, an
AP-OSS condensate was obtained, whose
Fig. 3. Mass spectrum of the synthesized AP-OSS.
The analysis of the MALDI-TOF mass spectrum (Fig.3) of the synthesized AP-OSS shows
the predominantly singly charged protonated ions, indicating that the degree of oligomerization
within this silsesquioxane ranges from n = 3 to 10. It can be seen that the m/z signal peaks of AP-
OSS are distributed between 300 and 1200, and the signal peaks with different m/z values
correspond to AP-OSS with different numbers of Si atoms, means to the atomic fragments of the
condensate (SiO1.5-(CH2)3-NH2)n with m/z = (110 D)n at different values of the n index, as well as
their products of altered composition due to incomplete synthesis reaction or destruction under the
laser excitation. The spectrum shows the difference in the atomic composition of the synthesized
fragments with even and odd n index. Thus, AP-OSS complexes with odd indices 7 and 9 include
an atomic fragment with a lower oxygen content SiO – ((CH2)3-NH2) with m/z 102 D. The presence
of fragments with different oxygen content in the condensate structure leads to reduction in the
atomic weight of the condensate and a shift of its mass line by m/z = 8 D.
Besides, there is AP-OSS structure with n = 9 and m/z 990 D, built only by complexes with
m/z = 110 D, where the atomic group with m/z 27 D (NCH or CH2CH) is absent. The complexes
with even values of n = 6, 8 and 10 have the incomplete content due to vacancies of atomic groups
with m/z = 17 (OH) and 26 D (NC or HCCH) in the AP-OSS space structures with n = 9 and m/z
990 D, built only by (SiO1.5-(CH2)3-NH2) fragments.
Note, that the condensate with n = 8 is completely formed by eight fragments of (SiO1.5-
(CH2)3-NH2) is detected. However, at lower index values, when n = 5, line m/z 524, the AP-OSS
condensate is formed by five fragments with m/z 110 D without the NC or CHCH (m/z 26) atomic
groups. The line with m/z 423 and n = 4 indicates the formation of an AP-OSS complex built by
four fragments (SiO1.5-(CH2)3-NH2) without one hydroxyl group.
Thus, as a result of the synthesis, an AP-OSS condensate was obtained, whose the spatial
structure is built by complexes (SiO1.5-(CH2)3-NH2), which include fragments of SiO - ((CH2)3-
NH2)) with a lower oxygen content and is characterized by the presence of vacancy clusters related
with atomic groups OH, NC, CHCH, NCH, H2CCH.
Tab. 1 gives the approximate structures of AP-OSS corresponding to different m/zcalculated
values.It can be seen that the m/z value of 880 represents the completely condensed
cageT8structures; the m/z values of 763 and 863represent the incompletely condensed polygonal
cage T7 andT8 structures containing Si–OH.In the incomplete condensation structure, it is noted that
the actual molecular mass of some structures is inconsistent with the m/z value. For example, in the
400 600 800 1000 1200
0
500
1000
1500
2000
2500
3000
96
3
88
0
10
83
n=7
n=5 n=9 n=10
n=6
n=8
n=4
52
4
98
2
86
3
76
2
74
4
64
3
62
5
42
3
m/z
I,
a.
u.
30
4
40
5
n=3
(-SiO1,5-(CH2)3-NH2)n
32
2
Fig. 3. Mass spectrum of the
synthesized AP-OSS.
34 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
the spatial structure is built by complexes
(SiO1.5-(CH2)3-NH2), which include fragments
of SiO - ((CH2)3-NH2)) with a lower oxygen
content and is characterized by the presence
of vacancy clusters related with atomic groups
OH, NC, CHCH, NCH, H2CCH.
Tab. 1 gives the approximate structures of
AP-OSS corresponding to different m/z calcu-
lated values. It can be seen that the m/z value
of 880 represents the completely condensed
cage T8 structures; the m/z values of 763 and
863 represent the incompletely condensed po-
lygonal cage T7 and T8 structures containing
Si–OH.In the incomplete condensation struc-
ture, it is noted that the actual molecular mass
of some structures is inconsistent with the m/z
value. For example, in the T9 structure, the cal-
culated molecular weight is 999, but there is
a signal peak with m/z value of 982 [28]. The
difference between the m/z value of 982 and
the calculated molecular weight of 999 is 17,
which is exactly the mass number of 1 OH-
group.Similarly, in the T8 structure, the calcu-
lated molecular weight of the incomplete con-
densation structure with Si–OH is 898, and the
actual m/z value is 863. The difference between
the m/z value and the calculated molecular
weight is 34, which is the mass number of 2
OH-groups.The reason for this phenomenon
may be that a part of the incompletely con-
densed AP-OSS dropped OH-groups during
the detection process [28].
Table 1.
Structures of AP-OSS.
m/z Molecular structure Molecular weight Type
304 Si3O3(C3H6NH2)3(OH)3 -3OH 357 T3
322 Si3O3(C3H6NH2)3(OH)3 -2OH 357 T3
423 Si4O5(C3H6NH2)4(OH)2-2OH 458 T4
643 Si6O7(C3H6NH2)6(OH)4 -3OH 697 T6
744 Si7O9(C3H6NH2)7(OH)3-3OH 797 Т7
762 Si7O9(C3H6NH2)7(OH)3-2OH 797 Т7
863 Si8O10(C3H6NH2)8(OH)2-2OH 898 Т8
880 Si8O12(C3H6NH2)8 880 Т8
982 Si9O13(C3H6NH2)9(OH)1-1OH 999 Т9
Possible parallel and sequential chemical re-
actions, which can occur during the synthesis
of AP-OSS are presented in Fig. 4. They include
hydrolysis, alcohol condensation, water con-
densation of APTMS [24] followed by hydro
lysis, polymerization, intramolecular conden-
sation of the intermediate products obtained
with formation of fully condensed POSS or
silene structures (in the Fig. 5, as example, the
structures with n=4 are shown). The formation
of a fully condensed polyhedral silsesquioxane
is favored in-solution as it is catalyzed by the
acidic environment.On the other hand, the
formation in solution of Si=C bonds in silenes
is less possible [29].
35https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
Fig. 4. Possible reactions, which occur during synthesis of AP-OSS (n=4) from APTMS with formation
of a fully condensed POSS or silene by intramolecular condensation [24, 29].
36 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
The acceleration effect of the AP-OSS on
polycyclotrimerization of DCBE[1, 2] was ob-
served at DSC investigation. Fig. 5 shows the
DSC thermograms of polycyclotrimerization
and the time dependence of the conversion of
cyanate groups for the individual DCBE and
DCBE/AP-OSS compositions with different
AP-OSS content. The main kinetic characte
ristics are provided in Tab. 2.
Fig. 5. DSC kinetic profiles (a) and time dependencies of conversion (b) for the individual DCBE
and DCBE/AP-OSS compositions (AP-OSS content is indicated in the plot).
Fig. 5. DSC kinetic profiles (a) and time dependencies of conversion (b) for the individual DCBE and
DCBE/AP-OSS compositions (AP-OSS content is indicated in the plot).
It is clear from the data provided in Tab.2 that the incorporation andincrease of the AP-OSS
content significantly change the kinetic characteristics of DCBE polycyclotrimerization.This is
confirmed by the fact that і and end decrease by ~6,5 % and 2–5 %, respectively, Tp(max) reduces by
11–24 oC, Wmax increases by 0,4–6,1 %/min, the Hfvalue forsynthesis of PCN/AP-OSS networks
decreases as well compared to pure PCN. As far as primary amino groups exhibit high reactivity
towards cyanate groups [30, 31], it is expected that the amino groups on a surface of AP-OSS
nanoparticles chemically interact with the –O–CN groups of the DCBE moleculesduring the in
situ synthesis of the nanocomposite samples. This process results in the covalent embedding of AP-
OSS into the forming PCN matrix. The chemistry of the embedding process is schematically shown
in Fig.6. Isourea fragments formed are supposed to be a good catalyst for polycyclotrimerization of
cyanate ester resins [30].
In addition, the processes of incorporation and conversion occur with the heat release and they
are the first kind of phase transition. The thermal effect of the transition is characterized by a non-
monotonic dependence of its intensity on the AP-OSS content Fig. 5a), whereas the embedding rate
of AP-OSS complexes and formation of hybrid composites smoothly increases with growing AP-
POSS content. The behavior of thermodynamic parameters indicates that the conversion process has
an island character. At a low AP-OSS content, the formation of the hybrid PCN/AP-OSS network
realizes in the vicinities of localization of separated complexes AP-OSS, while with rise of their
content the hydride conversion occurs in the entire reaction volume and its speed increases with the
value of released heat.
Table 2.
Kinetic parameters of DCBE polymerization as well as in situof different contents of AP-OSS and
thermal characteristics of PCN/AP-OSS nanocomposites synthesized.
Characteristics AP-OSS content, wt.%
Reactive DCBE/AP-OSSblends 0 0.1 0.5 1.0
Induction period, і, min 30.7 28.8 28.4 28.5
Reaction end time, end, min 59.0 57.8 56.6 56.0
Maximumreactionrate, Wmax, %/min 12.3 12.7 14.5 18.4
Time to reachWmax,max,min 49.4 47.3 45.5 44.5
Total time of reaction, tot,min 28 29 28 28
Temperature atWmax, Tp(max),oC 272 261 253 248
Conversion of cyanate groups atWmax,, % 56.2 53.1 47.3 45.3
Total enthalpy of reaction, Htot, J/g 984 842 873 818
PCN/AP-OSSnanocomposites
150 180 210 240 270 300 330
0,0
0,6
1,2
1,8
2,4
3,0
0
0.1
0.5
1.0
H
ea
t f
lo
w
, W
/g
Temperature, oC
Ex
o a)
0 25 30 35 40 45 50 55 60
0
20
40
60
80
100
0
0.1
0.5
1.0
C
on
ve
rs
io
n,
%
Time, min
b)
It is clear from the data provided in Tab.2
that the incorporation and increase of the AP-
OSS content significantly change the kinetic
characteristics of DCBE polycyclotrimeriza-
tion.This is confirmed by the fact that τі and
τend decrease by ~6,5 % and 2–5 %, respectively,
Tp(max) reduces by 11–24 oC, Wmax increases by
0,4–6,1 %/min, the ∆Hf value for synthesis of
PCN/AP-OSS networks decreases as well com-
pared to pure PCN. As far as primary amino
groups exhibit high reactivity towards cyanate
groups [30, 31], it is expected that the amino
groups on a surface of AP-OSS nanoparticles
chemically interact with the –O–C≡N groups
of the DCBE molecules during the in situ syn-
thesis of the nanocomposite samples. This
process results in the covalent embedding of
AP-OSS into the forming PCN matrix. The che
mistry of the embedding process is schemati-
cally shown in Fig.6. Isourea fragments formed
are supposed to be a good catalyst for polycyclo
trimerization of cyanate ester resins [30].
In addition, the processes of incorporation
and conversion occur with the heat release and
they are the first kind of phase transition. The
thermal effect of the transition is characterized
by a non-monotonic dependence of its inten-
sity on the AP-OSS content Fig. 5a), whereas
the embedding rate of AP-OSS complexes and
formation of hybrid composites smoothly in-
creases with growing AP-OSS content. The
behavior of thermodynamic parameters in-
dicates that the conversion process has an is-
land character. At a low AP-OSS content, the
37https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
formation of the hybrid PCN/AP-OSS network
realizes in the vicinities of localization of se
parated complexes AP-OSS, while with rise of
their content the hydride conversion occurs
in the entire reaction volume and its speed in-
creases with the value of released heat.
Table 2.
Kinetic parameters of DCBE, DCBE/AP-OSS polymerization and thermal characteristics
of synthesized PCN/AP-OSS nanocomposites.
Characteristics AP-OSS content, wt.%
Reactive DCBE/AP-OSSblends 0 0.1 0.5 1.0
Induction period, τі, min 30.7 28.8 28.4 28.5
Reaction end time, τend, min 59.0 57.8 56.6 56.0
Maximum reaction rate, Wmax, %/min 12.3 12.7 14.5 18.4
Time to reachWmax,τmax,min 49.4 47.3 45.5 44.5
Total time of reaction, τtot,min 28 29 28 28
Temperature atWmax, Tp(max),
oC 272 261 253 248
Conversion of cyanate groups atWmax,α, % 56.2 53.1 47.3 45.3
Total enthalpy of reaction, ∆Htot, J/g 984 842 873 818
PCN/AP-OSS nanocomposites
Tg,
oC 285,6 286,6 282,6 281,8
Tg(onset)/Tg(end), °C/°C 278/293 279/294 276/290 274/289
∆Тg,
oC 15 15 14 15
∆Cp, J/g·°C 0.245 0.227 0.240 0.156
Using DSC method (Fig.7) it was found out
that, as for the individual PCN, high values of
Tg are observed for the synthesized PCN/AP-
OSS nanocomposites (Tab.2). However, with
an increase in the AP-OSS content by 10 times
(from 0.1 wt.% to 1.0 wt.%), the Tg value slight-
ly decreases from Tg = 286.6°C to Tg = 281.8°C,
respectively. One can suppose that the nano-
particles of AP-OSS embedded into the PCN
network structure play the role of the addition-
al inorganic network junctions. This phenom-
enon should limit the relaxation of the kinetic
segments of the polymer chains in the hybrid
PCN/AP-OSS network that leads to increas-
ing Tg value and decreasing the ∆Cp. However,
at the same time, the presence of a significant
number of flexible linear organic fragments
out of cage of AP-OSS nanoparticles can facil-
itate the relaxation of the kinetic segments of
the hybrid network formed and lead to a de-
creasing Tg value. The total effect of these two
competitive processes provides the close values
of Tg for individual PCN and PCN/AP-OSS
nanocomposites. It is worth noting that for the
38 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
sample with the highest content of nanofiller
(1.0 wt.%), a significant decrease (~1.6 times)
of the ∆Cpvalue is observed compared to the
unfilled PCN matrix. It is known that this is a
manifestation of an increase in the density of
network junctions for crosslinked polymers
[32]. It can be concluded that the PCN/AP-
OSS nanocomposite sample with 1.0 wt.% of
AP-OSS demonstrates the highest crosslinked
density.
Fig. 6. Schematic presentation of the initial stage of chemical incorporation of AP-OSS
particles into the growing PCN network (example for n = 8).
Tg, oC 285,6 286,6 282,6 281,8
Tg(onset)/Tg(end), °C/°C 278/293 279/294 276/290 274/289
∆Тg, oC 15 15 14 15
∆Cp, J/g·°C 0.245 0.227 0.240 0.156
Fig. 6. Schematic presentation of the initial stage of chemical incorporation of AP-OSS particles into the
growing PCN network (example for n = 8).
Using DSC method (Fig.7) it was found out that, as for the individual PCN, high values of
Tg are observed for the synthesized PCN/AP-OSS nanocomposites (Tab.2). However, with an
increase in the AP-OSS content by 10 times (from 0.1 wt.% to 1.0 wt.%), the Tg value slightly
decreases from Tg = 286.6°C to Tg = 281.8°C, respectively. One can suppose that the nanoparticles
of AP-OSS embeddedinto the PCN network structure play the role of the additional inorganic
39https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
Fig. 7. DSC thermograms (2nd scan) for the neat
PCN and PCN/AP-OSS nanocomposites formed.
CONCLUSIONS. In this work, the reactive
amino-functionalized AP-OSS has been syn-
thesized and characterized, the effect of the AP-
OSS content (0.1–1.0 wt.%) on the kinetics of
polycyclotrimerization of DCBE was studied
by using dynamic DSC method. AP-OSS was
prepared in high yield by hydrolysis and poly-
condensation of H2NCH2CH2CH2Si(OCH3)3
monomer in the mixture of acetonitrile and
ethanol, with tetrabutyl ammonium hydroxide
(But4NOH) as the catalyst.The chemical struc-
ture of the synthesized AP-OSS was confirmed
by the results of FTIR and 1H NMR spectros-
copy, as well as by MALDI-TOF methods.
The predominantly singly charged protonated
ions, indicating that the degree of oligomeri-
zation within this silsesquioxane ranges from
n = 3 to 10 were found by MALDI-TOF me
thod. It was found that AP-OSS accelerated the
polycyclotrimerization of DCBE allowing de-
creasing the final temperature and time of PCN
network synthesis, the higher content of the
AP-OSS the higher acceleration effect has been
observed. As far as during the in situ synthesis
of the PCN/AP-OSS nanocomposites, the ami-
no groups on a surface of AP-OSS nanoparticles
can chemically interact with –O–C≡N-groups
of DCBE with formation of isourea fragments,
the covalent embedding of AP-OSS into the
growing PCN matrix with formation of the hy-
brid PCN/AP-OSS network occurs. It was found
also that all synthesized PCN/AP-OSS nano-
composites have high Tg values (Tg> 280 °C)
similar to individual PCN. A slight decrease
in Tg (from 286.6 °C to 281.8 °C, respectively)
and ∆Cp (by 1.6 times compared to PCN) at in-
creasing amount of the AP-OSS used was ob-
served. It was explained by the competition of
two factors: 1) the presence of a number of fle
xible linear fragments of AP-OSS in the hybrid
crosslinked matrix promotes the relaxation of
the kinetic segments of the hybrid network and
leads to a decrease in the Tg value; 2) incorpo-
ration into the PCN network of the inorganic
nanoparticles, which act as the additional net-
work junctions increases a crosslink density of
the network hindering relaxation and increas-
ing Tg value of the hybrid network. The synthe-
sized and investigated PCN/AP-OSS nanocom-
posites belong to the class of high-performance
thermostable polymer materials with controlled
structure and properties suitable for application
in extreme conditions.
The work was performed with the finan-
cial support of the National Academy
of Sciences of Ukraine and the “Centre
National dela Recherche Scientifique” through
French-Ukrainian International Research Pro-
ject “POLYTHERMAT”. Sincere thanks from
D. M. Shulzhenko for the partial financial sup-
port of this work with in the framework of the
"NADIYA"-Engineering Scholarship (2024)
from the French Embassy in Ukraine.
network junctions. This phenomenon should limit the relaxation of the kinetic segments of the
polymer chains of the in the hybrid PCN/AP-OSS network that leads to increasing Tg value and
decreasing the ∆Cp. However, at the same time, the presence of a significant number of flexible
linear organic fragments out of cage ofAP-OSS nanoparticles can facilitate the relaxation of the
kinetic segments of the hybrid network formed and lead to a decreasing Tg value. The total effect of
these two competitive processes provides the close values of Tg for individual PCN and PCN/AP-
OSS nanocomposites. It is worth noting that for the sample with the highest content of nanofiller
(1.0 wt.%), a significant decrease (~1.6 times) of the ∆Cpvalue is observed compared to the unfilled
PCN matrix. It is known that this is a manifestation of an increase in the density of network
junctions for crosslinked polymers [32]. It can be concluded that the PCN/AP-OSS nanocomposite
sample with 1.0 wt.% of AP-OSS demonstrates the highest crosslinked density.
Fig. 7. DSC thermograms (2nd scan) for the neat PCN and PCN/AP-OSS nanocomposites formed.
CONCLUSIONS. In this work, the reactive amino-functionalized AP-OSS has been
synthesized and characterized, the effect of the AP-OSS content (0.1–1.0 wt.%) on the kinetics of
polycyclotrimerization of DCBE was studiedby using dynamic DSC method. AP-OSS was prepared
in high yield by hydrolysis and polycondensation of H2NCH2CH2CH2Si(OCH3)3monomer in the
mixture of acetonitrile and ethanol, with tetrabutyl ammonium hydroxide (But4NOH) as the
catalyst.The chemical structure of the synthesized AP-OSS was confirmed by the results of FTIR
and 1H NMR spectroscopy, as well as by MALDI-TOF methods. The predominantly singly charged
protonated ions, indicating that the degree of oligomerization within this silsesquioxane ranges from
n = 3 to 10 were found by MALDI-TOF method. It was found that AP-OSS accelerated the
polycyclotrimerization of DCBE allowing decreasing the final temperature and time of PCN
network synthesis, the higher content of the AP-OSS the higher acceleration effect has been
observed. As far as during the in situ synthesis of the PCN/AP-OSS nanocomposites, the amino
groups on a surface of AP-OSS nanoparticles can chemically interact with –O–CN-groups of
DCBE with formation of isourea fragments, the covalent embedding of AP-OSS into the growing
PCN matrix with formation of the hybrid PCN/AP-OSS network occurs. It was found also that all
synthesized PCN/AP-OSS nanocomposites have high Tg values (Tg> 280 °C) similar to individual
PCN. A slight decrease in Tg (from 286.6 °C to 281.8 °C, respectively) and ∆Cp (by 1.6 times
compared to PCN) at increasing amount of the AP-OSS used was observed. It was explained by the
competition of two factors: 1) the presence of a number of flexible linear fragments of AP-OSS in
the hybrid crosslinked matrix promotes the relaxation of the kinetic segments of the hybrid network
and leads to a decrease in the Tg value; 2) incorporation into the PCN network of the inorganic
nanoparticles, which act as the additional network junctions increases a crosslink density of the
100 150 200 250 300 350
0
0,1
0,5
1,0
H
ea
t f
lo
w
, W
/g
Temperature, oC
Еx
о
40 ISSN 2708-129X. Укр. хім. журн., 2024
ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS
OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK.ORGANIC CHEMISTRY
AND CHEMISTRY OF POLYMERS
КАТАЛІТИЧНИЙ ВПЛИВ 3-АМІНОПРОПІЛОЛІГО
МЕРНОГО СИЛСЕСКВІОКСАНУ НА КІНЕТИКУ
ФОРМУВАННЯ ТЕРМОСТІЙКИХ ГІБРИДНИХ
НАНОКОМПОЗИТІВ НА ОСНОВІ ПОЛІЦІАНУ
РАТНОЇ СІТКИ
Д. M. Шульженко 1,2, O. П. Григор’єва 1*,
M. A. Гуменна 1, Є. В. Полункін3,
Б. M. Горєлов4, О. M. Файнлейб1*, Д. Ґранде 2
1Інститут хімії високомолекулярних спо-
лук НАН України;
2 Universitéde Strasbourg, CNRS, Institut Char
les Sadron,
UPR 22, Strasbourg, France;
3 Інститут біоорганічної хімії та нафтохі-
мії ім. В. П. Кухаря НАН України;
4Інститут хімії поверхні ім. О. О. Чуйка
НАН України.
email: fainleib@i.ua
У цій роботі було синтезовано і дослі-
джено реакційно здатний 3-амінопропіл
олігомерний силсесквіоксан (AP-OSS) та
визначено вплив AP-OSS залежно від його
вмісту (0,1–1,0 мас.%) на кінетику поліци-
клотримеризації диціанового естеру біс-
фенолу Е (ДЦБE) з використанням методу
динамічної ДСК. AP-OSS був отриманий
шляхом гідролізу та поліконденсації 3-амі-
нопропілтриметоксисилану з суміші аце-
тонітрилу та етанолу, з гідроксидом тетра-
бутиламонію (But4NOH) як каталізатором.
Хімічну структуру синтезованого AP-OSS
було підтверджено результатами ФТІЧ та
1H ЯМР-спектроскопії, а також методом
MALDI-TOF. На ФТІЧ-спектрах виявле-
но широкі та інтенсивні смуги поглинань
валентних коливань із максимумами за
ν≈3431 см–1і ν≈3378 см–1 та смуги поглинань
деформаційних коливань із максимумами
заδ≈1638 см–1 та δ≈1599 см–1 зв’язку N–H
у групах NH2, а також смуги поглинань за
ν≈1027 та δ≈859 см–1, які відносять до харак-
терних вібрацій сил сесквіоксанового ядра
Si–O–Si. Методом MALDI-TOF було вияв-
лено переважно однозарядні протоновані
іони, що вказує на те, що ступінь олігоме-
ризації в цьому силсесквіоксані коливаєть-
ся від n = 3 до 10. Було виявлено, що AP-OSS
прискорює поліциклотримеризацію ДЦБЕ,
що зумовлює зменшення кінцевої темпера-
тури та часу синтезу поліціануратної сітки
(ПЦС), при цьому що вищий вміст AP-OSS,
то вищий ефект прискорення реакції. Вва-
жаємо, що під час in situ синтезу гібридних
ПЦС/AP-OSS нанокомпозитів аміногрупи
на поверхні наночастинок AP-OSS хімічно
взаємодіють з ціанатними групами ДЦБE
з утворенням фрагментів ізосечовини,
що забезпечує ковалентне вбудовування
AP-OSS у ПЦС-матрицю, що формується.
Методом ДСК встановлено, що всі синте-
зовані гібридні ПЦС/AP-OSS-нанокомпо-
зити мають високі температури склування
(Tск> 280°C), що дозволяє їх класифікувати
як термостійкі полімерні матеріали.
Ключові слова: ціанатестерні смоли,
олігомерний силсесквіоксан, поліціанурат,
кінетика синтезу, ефект прискорення.
41https://ucj.org.ua
D. M. Shulzhenko, O. P. Grigoryeva, M. A. Gumenna, E. V. Polunkin, B. M. Gorelov, A. M. Fainleib, D. Grande UCJ № 5 / Vol. 90
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Стаття надійшла 14.03.2024.
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-665 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:11:45Z |
| publishDate | 2024 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/d1/464b569f2207a8d5d113799cb66be0d1.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-6652026-07-22T08:23:54Z ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. Shulzhenko, Diana Grigoryeva, Olga Gumenna, Mariana Polunkin, Evgen Gorelov, Borys Fainleib, Alexander Grande, Daniel cyanate ester resins, oligomeric silsesquioxane, polycyanurates, synthesis kinetics, accelerating effect. In this work, reactive 3-aminopropyloligomeric silsesquioxane (AP-OSS) was synthesized and studied, and the effect of AP-OSS depending on its content (0.1–1.0 wt.%) on the kinetics of polycyclotrimerization of dicyanate ester of bisphenol E (DCBE) was determined using the dynamic DSC method. AP-OSS was prepared in high yield by the hydrolysis and polycondensation of 3-aminopropyltrimethoxysilane in a mixture of acetonitrile and ethanol, with tetrabutylammonium hydroxide (But4NOH) as a catalyst. The chemical structure of the synthesized AP-OSS was confirmed by the results of FTIR and 1H NMR spectroscopies, as well as by MALDI-TOF method. The FTIR spectra showed broad and intensive stretching absorption bands centered at ν≈ 3431 and ν≈ 3378 cm–1 and bending absorption bands centered at δ≈ 1638 and δ≈ 1599 cm-1 of the N–H in NH2 groups, as well as the absorption bands centered at ν≈1027 and δ≈859 cm–1, attributed to the special characteristic vibrations of the silsesquioxane cage Si–O–Si. MALDI-TOF spectroscopy detected predominantly singly charged protonatedions, indicating that the degree of oligomerization in this silsesquioxane is between n = 3 and 10. It was found that AP-OSS accelerated the DCBE polycyclotrimerization allowing decreasing the final temperature and time of polycyanurate network (PCN) synthesis, the higher content of the AP-OSS the higher acceleration effect has been observed. It was supposed that during the in situ synthesis of the hybrid PCN/AP-OSS nanocomposites, the amino groups on a surface of AP-OSS nanoparticles chemically interact with –O–C≡N-groups of DCBE with formation of isourea fragments providing the covalent embedding of &nbsp;AP-OSS into the growing PCN matrix. Using DSC method, it was found that all synthesized hybrid &nbsp;PCN/AP-OSS nanocomposites possessed high glass transition temperatures (Tg&gt;280oC) and can be classified as thermally stable polymer materials. V.I.Vernadsky Institute of General and Inorganic Chemistry 2024-06-28 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/665 10.33609/2708-129X.90.5.2024.28-43 Ukrainian Chemistry Journal; Vol. 90 No. 5 (2024): Ukrainian Chemistry Journal; 28-43 Украинский химический журнал; ##issue.vol## 90 ##issue.no## 5 (2024): Ukrainian Chemistry Journal; 28-43 Український хімічний журнал; Том 90 № 5 (2024): Ukrainian Chemistry Journal; 28-43 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/665/331 Copyright (c) 2024 Diana Shulzhenko, Olga Grigoryeva, Mariana Gumenna, Evgen Polunkin, Borys Gorelov, Alexander Fainleib, Daniel Grande https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Shulzhenko, Diana Grigoryeva, Olga Gumenna, Mariana Polunkin, Evgen Gorelov, Borys Fainleib, Alexander Grande, Daniel ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title | ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title_full | ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title_fullStr | ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title_full_unstemmed | ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title_short | ACCELERATING EFFECT OF 3-AMINOPROPYLOLIGOMERIC SILSESQUIOXANE ON FORMATION KINETICS OF THERMOSTABLE HYBRID NANOCOMPOSITES BASED ON POLYCYANURATE NETWORK. |
| title_sort | accelerating effect of 3-aminopropyloligomeric silsesquioxane on formation kinetics of thermostable hybrid nanocomposites based on polycyanurate network. |
| topic_facet | cyanate ester resins oligomeric silsesquioxane polycyanurates synthesis kinetics accelerating effect. |
| url | https://ucj.org.ua/index.php/journal/article/view/665 |
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