polymers

Article
Curing of Epoxy Resin DER-331 by
Hexakis(4-acetamidophenoxy)cyclotriphosphazene
and Properties of the Prepared Composition
Evgeniy M. Chistyakov 1, * , Ivan V. Terekhov 2 , Aleksey V. Shapagin 3 , Sergey N. Filatov 1 and
Vladimir P. Chuev 4
1 D. Mendeleev University of Chemical Technology of Russia, 125047 Moscow, Russia
2 All-Russian Scientific Research Institute of Aviation Materials, 105005 Moscow, Russia
3 A.N. Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences,
119071 Moscow, Russia
4 Belgorod National Research University, 308015 Belgorod, Russia
* Correspondence: ewgenijj@rambler.ru




Received: 30 May 2019; Accepted: 15 July 2019; Published: 17 July 2019


Abstract: The method of optical wedge revealed that the optimum temperature for compatibility of
hexakis(4-acetamidophenoxy)cyclotriphosphazene (ACP) and DER-331 epoxy resin is in the range of
220–260 ◦ C. The interdiffusion time of components at these temperatures is about 30 min. The TGA
and differential scanning calorimetry (DSC) methods revealed the curing temperature of 280 ◦ C for
this composition. IR spectroscopy confirmed that the reaction between the resin and ACP is completed
within 10 min. According to the DSC data, a glass transition temperature of 130 ◦ C was estimated for
the cured resin. Combustion test UL-94 demonstrated that the obtained material can be assigned
to the fireproof category of V-0. Burning droplets were not formed during the burning. The coke
formed during the combustion of samples possessed a dense and porous structure. The shape of
pores is closed, while their size is in the range of 0.2–200 µm.

Keywords: phosphazenes; epoxy resin; noncombustibility; thermostability; amide cure; coke

1. Introduction
The development of technologically simple and cost-efficient composite materials with unique
properties, which can be applied in various fields of science and technology, is a hot topic in the modern
scientific community [1–3].
Many such composites are based on epoxy resin due to its excellent mechanical properties,
low dielectric permittivity, and good resistance to chemicals, solvents, and moisture [4]; but its
high flammability hinders its practical applications [5]. Although traditional halogenated flame
retardants have been designed to solve this problem, they have had to be replaced due to their
health and environmental hazards by halogen-free analogs [6]. Organometallic compounds, especially
organophosphorous ones [7–9], hold a prominent place in the production of such materials. For example,
materials with reduced flammability were created from phosphorus-containing epoxy resin [10]. It was
noted that with an increase in the content of the developed resin, the burning time of the samples
decreased, and the yield of coke increased. A new superbranched phosphorus/nitrogen-containing
flame retardant was investigated in another work [11]. The epoxy resin cured by this compound
does not sustain combustion. The authors explain this by the fact that the structures of the coke
of burned samples without the addition of flame retardant are fragmentary and broken. Coke of
burned samples with modified resin has compact and continuous char layers. Another non-flammable

Polymers 2019, 11, 1191; doi:10.3390/polym11071191 www.mdpi.com/journal/polymers

Polymers 2019, 11, 1191 2 of 12

material was obtained from anhydride-cured epoxy resin with the addition of 26.0 wt % of novel
phosphorus/nitrogen containing polycarboxylic acid [12].
Among different phosphorus flame retardants, phosphazenes are of particular interest due
to the synergistic effect of phosphorus and nitrogen atoms acting simultaneously [4–9,13–22].
Fireproof epoxy compositions based on phosphazenes were prepared, of which resistance to
combustion was achieved by the addition of small amounts of phosphazene modifiers [4,5], e.g.,
hexa(4-maleimidophenoxy)cyclotriphosphazene (9 wt %) [13] or hexa-[4-(hydroxyanilinephosphaph
enanthrenemethyl)-phenoxy]cyclotriphosphazene (10 wt %) [9]. Some phosphazene derivatives have
proven themselves as hardeners of epoxy resins, for example, aminophosphazenes [16,17,22]. A novel
compound containing active amine groups on polyphosphazene was successfully synthesized and applied
as a reactive flame-retardant additive in epoxy resin [22]. It was synthesized from N-aminoethylpiperazine
and hexachlorocyclotriphosphazene. A composite with 9.0 wt % of such phosphazene can pass the
vertical burning tests and have a V-0 rating.
Amines are known as cured at low temperatures [23], which is not always convenient since the
composition may be prematurely hardened during a long-term processing of the resin into a ware.
At this end, amides are of considerable interest due to their less nucleophilic nitrogen atom, while the
reaction between the amide and epoxy groups proceeds at higher temperatures [24].
Hexakis(4-acetamidophenoxy)cyclotriphosphazene (ACP) is the most actively explored among
phosphazene derivatives, since its synthesis is fairly simple [25–28]. This compound may be of
significant interest as a hardener of industrial epoxy resins for the production of non-combustible
materials based on them.

2. Experimental Section

2.1. Materials and Methods

Hexachlorocyclophosphazene (HCP) (Fushimi Pharmaceutical Co., Ltd., Tokyo, Japan) was
purified by the recrystallization from n-hexane with the consequent sublimation. The epoxy resin
(DER-331) was purchased from DOW Chemical Company (Berlin, Germany), while the other reagents
were obtained from Sigma-Aldrich (St. Louis, MO, USA). 4-Acetamidophenol and metallic sodium
were used without any purification. Diglyme and THF were dried over CaH2 and distilled in vacuo.
Ethanol was distilled over aluminum amalgam.
Thermal analysis of the obtained compounds was performed by synchronous thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC) using a NETZSCH STA 449 F3 Jupiter
instrument (Erich NETZSCH GmbH & Co. Holding KG, Selb, Germany) coupled with FT-IR Bruker
Tensor 27 (Billerica, MA, USA) (10 ◦ C min−1 ). Argon was used as a purge gas (70 mL/min). IR spectra
were recorded on a Nicolet 380 FTIR spectrometer (Thermo Fisher Scientific, Waltham, MA, USA)
equipped with the FTIR prefix spectrometer in the transmission mode in the range of 4000–400 cm−1 .
1 H, 13 C, and 31 P NMR spectra were recorded on a Bruker CXP–300 spectrometer (Billerica, MA,

USA). To determine the size of ACP particles, a MSP-1 stereoscopic pancratic microscope equipped
with a LOMO MS-5 digital camera and MCView software (AO Lomo, St. Petersburg, Russia) were
used. Shear strength was measured on a PUMA-2 tensile testing machine (Tochmashpribor, Ivanovo,
Russia). X-ray fluorescence analysis was performed on an ARL PFX-101 spectrometer (Thermo Fisher
Scientific, Waltham, MA, USA). Elemental analysis was performed on an ЕA 1110 elemental analyzer
(Antwerpen, Belgium).

2.2. Synthesis of Hexakis(4-acetamidophenoxy)cyclotriphosphazene (ACP)

ACP was synthesized according to a known procedure [28].
1 H NMR (DMSO-d , TMS, ppm): 9.90 (1H, –NH), 6.81–7.47 (4H, dd, Ar–H), 2.06 (3H, –CH ).
6 3
13 C NMR (DMSO-d , TMS, ppm): 168.2 (C=O), 145.1 (C–O), 136.6 (C–N), 120.7 (CH), 119.8 (CH),
6
24.0 (CH3 ). 31 P NMR (DMSO-d6 , ppm): 9.82 (s).
Polymers 2019, 11, 1191 3 of 12

2.3. Determination of Compatibility and Interdiffusion for ACP and DER-331

The optical interferometry method was used to estimate the compatibility of ACP and DER-331.
The measurements were carried out using an ODA-2 laser diffusiometer (Moscow, Russia) [29].
This method is based on the phenomenon of multibeam interference from two polished glass plate
surfaces forming an angle of ≈2◦ between them. Inner surfaces of the glasses are covered with a layer
of translucent metal possessing a high index of reflection.
ACP powder was placed between the glass plates and thermostated above its melting temperature,
while DER-331 was injected into a wedge at the temperature of experiment. The moment of contact of
the fronts was considered as the beginning of the diffusion mixing process.
The interdiffusion measurements performed in the isothermic mode. To estimate the compatibility
of components, the temperature was raised and lowered in a stepped mode with a step of 10 ◦ C in
the range from 20 to 270 ◦ C. The interdiffusion coefficients were calculated by the moving-boundary
method at the laboratory coordinate system [30].

2.4. Preparation of the Composition Based on ACP and DER-331

The weight fraction of ACP relative to the resin was calculated according to the formula:
X = E × M/(43 × n), wherein E is the weight fraction of epoxy groups in the resin, M is the molecular
weight of ACP, 43 corresponds to the molecular weight of one epoxy group, and n is the functionality
of ACP. Putting numbers into this equation gave 20 × 1035/(43 × 6) = 80.2 (%) (based on the mass of
DER-331). The mass fractions of components used for the composition preparation were 44 and 56%
for ACP and DER-331, respectively.
To prepare the samples, APC was ground in a mortar (the size of particles did not exceed 200 µm),
the epoxy resin was added, and the mixture was ground again. The resulting paste was placed into a
mold, vacuumized, heated to 220 ◦ C, and held for 30 min at this temperature. The temperature was
then elevated to 280 ◦ C and maintained for 10 min.

2.5. Combustion Test of the Samples

The resistance to combustion for the prepared compositions was determined according to the
UL-94 test.

2.6. Estimation of Gel Fraction

A weighed sample of the cured epoxy resin was placed into a paper bag and tightly closed.
The bag with the sample was weighed and placed in a Soxhlet apparatus, and the soluble fraction was
extracted with hot ethanol. Ethanol was selected since the both epoxy resin and ACP are soluble in it.
Once the extraction was finished, the paper bag was removed from the apparatus, dried in vacuo at
100 ◦ C, and weighed. The amount of gel fraction was calculated as the mass difference of the samples
before and after extraction.

2.7. Investigation of Microstructure of the Coke Covers

A sample of composition taken after the combustion test was evaluated. To prepare it for the
microstructural studies, the surface of the coke covers was cut from the sample. The resulting fragment
was attached to the holder by a conductive carbon tape, and edges of the sample were covered with a
silver-based glue. In a Q150R ES vacuum system (Quorum Technologies, Lewes, UK), a gold layer of
20 nm was then applied onto the sample. Microstructural analysis of the samples was carried out on a
TESCAN VEGA 3 XMU (Brno, Czech Republic) scanning electron microscope (SEM) in the secondary
electron (SE) mode. Quantitative processing of the obtained data was performed using the ImageScope
Color software (Systems for microscopy and analysis, Moscow, Russia) designed for image analysis.
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The content of the elements in the ACP, DER-331, and the cured composition was calculated
2.8.theoretically.
Elemental Analysis
To determine the phosphorus content in coke, X-ray fluorescence analysis was used.
The content of C, N and H was determined according to ISO 17247: 2013.
The content of the elements in the ACP, DER-331, and the cured composition was calculated
theoretically. To determine
2.9. Shear Strength the phosphorus content in coke, X-ray fluorescence analysis was used.
Determination
The content of C, N and H was determined according to ISO 17247: 2013.
Plates from carbon steel of the St-3 trademark (MMK, Magnitogorsk, Russia) were used to
determine the shear strength of the adhesive bond. Composition for bonding was prepared and cured
2.9. Shear Strength Determination
in accordance with Section 2.4. The tests were carried out according to ISO 4587.
Plates from carbon steel of the St-3 trademark (MMK, Magnitogorsk, Russia) were used to
3. Results
determine and
the Discussion
shear strength of the adhesive bond. Composition for bonding was prepared and cured
in accordance
ACP waswith Section 2.4.
synthesized The tests
according were carried
to Scheme out 1).
A (Figure according to ISO 4587.
This compound can be an efficient
curing agent for epoxy resins, since the ACP molecule contains six amide groups, and each of them
3. Results
can reactand
withDiscussion
an oxirane cycle of the epoxy resin. This will result in a highly cross-linked polymer,
whose structure may be represented by that shown in Figure 1B.
ACP was synthesized according to Scheme A (Figure 1). This compound can be an efficient curing
To evaluate the application of ACP as a hardener of epoxy resins, it was necessary to evaluate
agent for epoxy resins, since the ACP molecule contains six amide groups, and each of them can react
their mutual compatibility. Since ACP is a crystalline substance according to the DSC data (Figure
with ansolution-melts
2,c), oxirane cycleofofACP
the epoxy resin. This
with DER-331 epoxywill result
resin in abehighly
should cross-linked
described polymer, whose
by a constitutional
structure
diagrammay be represented
containing by that
the crystalline shown in Figure 1B.
equilibrium.

Figure 1. Synthesis of hexakis(4-acetamidophenoxy)cyclotriphosphazene (ACP) (A) and a proposed

Figure 1. Synthesis of hexakis(4-acetamidophenoxy)cyclotriphosphazene (ACP) (A) and a proposed
structure of the cured epoxy resin (B).
structure of the cured epoxy resin (B).

To evaluate the application of ACP as a hardener of epoxy resins, it was necessary to evaluate
their mutual compatibility. Since ACP is a crystalline substance according to the DSC data (Figure 2c),
solution-melts of ACP with DER-331 epoxy resin should be described by a constitutional diagram
containing the crystalline equilibrium.
Interdiffusion zones of the components were investigated by optical interferometry in a wide
temperature range. Typical interference patterns at different temperatures are shown in Figure 3.
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Figure 2. TGA Figure 2. TGA curves

curves for (a)cured
for (a) cured composition and (b) mixture
composition and of ACP
(b) and DER-331;
mixture of and differential
ACP and DER-331; and
scanning calorimetry (DSC) curves for (c) ACP, (d) mixture of ACP and DER-331, and (e) cured
differential scanning calorimetry
composition.
(DSC) curves for (c) ACP, (d) mixture of ACP and DER-331, and (e)
cured Polymers
composition.
2019, 11, x FOR PEER REVIEW 6 of 13
Interdiffusion zones of the components were investigated by optical interferometry in a wide
temperature range. Typical interference patterns at different temperatures are shown in Figure 3.

Figure 3. Interference patterns of the interdiffusion zones of the ACP–DER-331 system obtained at (a)
Figure 3. Interference patterns of the interdiffusion zones of the ACP–DER-331 system obtained at (a)
20, (b) 18020,
and ◦ C.
(b)(c)
180270
and (c) 270 °C.

The complete compatibility of the components in the ACP–DER-331 system has been achieved
above the melting point of ACP, which is evidenced by the resolved interference pattern
characterized by a continuous concentration profile in the interdiffusion region (Figure 2c, and Video
Abstract). It should be noted that the crystallization of phosphazene was observed upon cooling the
ACP solution in the resin down to 200 °C, which precludes obtaining a homogeneous system at the
Polymers 2019, 11, 1191 6 of 12

The complete compatibility of the components in the ACP–DER-331 system has been achieved
above the melting point of ACP, which is evidenced by the resolved interference pattern characterized
by a continuous concentration profile in the interdiffusion region (Figure 2c, and Video Abstract in
Supplementary Materials). It should be noted that the crystallization of phosphazene was observed
upon cooling the ACP solution in the resin down to 200 ◦ C, which precludes obtaining a homogeneous
system at the lower temperatures.
Taking into account the movement of iso-concentration planes inside the interdiffusion zones
(Figure 4), it was established that the process of mixing the components obeys the diffusion
mechanism since it is described by the equation of х~kt1/2 , wherein k is a constant associated with the
Polymers 2019, 11, x FOR PEER REVIEW 7 of 13
interdiffusion coefficient.

Figure 4. Typical kinetic dependences of the iso-concentration planes movement in the interdiffusion
Figure 4. Typical
zone. The kinetic
numbers dependences
indicate values of of
thethe iso-concentration
mass planes movement in the interdiffusion
fraction of DER-331.
zone. The numbers indicate values of the mass fraction of DER-331.
Taking into account the data shown in Figure 4, the concentration dependences of the diffusion
Taking were
coefficients into account
calculated theatdata shown inof
temperatures Figure 4, the
220, 240, andconcentration
260 ◦ C. It wasdependences
revealed that theof the diffusion
dependences
coefficients
possess a similar character in the range of studied temperatures (Figure 5). It was shownthat
were calculated at temperatures of 220, 240, and 260 °С. It was revealed thatthe
the
dependences
values of thepossess a similar
interdiffusion character in
coefficients the
are 10range
–6 cmofsstudied
2 –1 in thetemperatures (Figure
region of diluted 5). solutions
ACP It was shownand
that the values
are nearly of upon
stable the interdiffusion
temperaturecoefficients
changes. Asare the10concentration
–6 cm2 s–1 in the region of diluted ACP solutions
shifts to the value of concentrated
and are nearly
phosphazene stable upon
solutions, temperature
the diffusion changes.
processes As theto concentration
slows down 10–7 cm2 s–1 . Itshifts
shouldtobethe value
noted thatof
in
concentrated
this region ofphosphazene
concentrationsolutions,
within thethe diffusion temperature
investigated processes slowsrange,down
the to 10 –7 cm2 sof
magnitude –1. It should be
interdiffusion
noted that invaries
coefficients this region
withinoftheconcentration
order of 0.5.within
Thus,the investigated
in the temperature
area of limiting range, thethe
concentrations, magnitude
diffusion
of interdiffusion
coefficient of ACPcoefficients
in DER-331 varies within
is one orderthe
oforder of 0.5. higher
magnitude Thus, inthan
the area of limiting
that of DER-331concentrations,
in ACP.
the diffusion coefficient of ACP in DER-331 is one order of magnitude higher than that of DER-331
in ACP.
Polymers 2019, 11, 1191 7 of 12
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Figure 5. Concentration dependences of the interdiffusion coefficient on semi logarithmic scale at 220,
Figure 5. Concentration dependences of the interdiffusion coefficient on semi logarithmic scale at 220,
240, and 260 ◦ C.
240, and 260 °С.
To prepare the composition based on ACP and DER-331, their fractions were calculated to be 44
To prepare
and 56%, the composition
respectively. It should be based
notedon that
ACPthe anddiffusion
DER-331, their
rate fractions
at the were calculated
ACP concentration ofto be 44
44% in
and 56%, respectively. It should be noted that the diffusion rate at the
the epoxy resin does not change within the temperature interval shown in Figure 5, which can be ACP concentration of 44% in
the epoxy by
explained resin does not change
a depression of the within the temperature
ACP melting point. Meltinginterval shown
of the ACPininFigure 5, which
the mixture can be
begins at
explained
◦ by a depression of the ACP melting point. Melting
~200 C (Figure 2d), while the pure ACP melts only at 258 C (see Figure 2c). ◦of the ACP in the mixture begins at ~200 °C
(Figure
The2,d), whileof
duration thethepure ACP melts
dissolution only of
process at ACP
258 °С in (see Figure
DER-331 can2,c).
be calculated from the calculated
The duration
diffusion constantsof the dissolution
(Figure 5). Using process of ACP
the formula t = inR2DER-331
× (2D)−1 can be calculated
(wherein from the calculated
t is the diffusion relaxation
diffusion constants (Figure 5). Using the formula t = R 2 × (2D)−1 (wherein t is the diffusion relaxation
time, D is the diffusion coefficient, and R is the radius of ACP particle), one can conclude that ACP
time, D ismeasuring
particles the diffusion
200 coefficient,
µm in size will anddissolve
R is the in
radius of ACP
the resin at 220particle), one can
◦ C in about conclude that ACP
30 min.
particles
The curing temperature of ACP–DER-331 composition was estimated bymin.
measuring 200 µ m in size will dissolve in the resin at 220 °C in about 30 the DSC method.
The
Figure 2d curing
shows an temperature
exothermic of ACP–DER-331
effect above the meltingcomposition was estimated
point of ACP, which is caused by the by DSC method.
the beginning
Figure
of 2d shows between
the interaction an exothermic effect above
the components. Thethe melting of
maximum point
peakofis ACP,
at 280 which
◦ C, whileis caused by the
a degradation
beginning of the interaction between the components.
◦ The maximum
of the material is already observable at 300 C, which is also confirmed by TGA data (Figure 2b). of peak is at 280 °С, while a
degradation of the material is already observable at 300 °C, which is also
At this end, the composition was cured at 280 ◦ C for 10 min. In this interval of time, the interaction confirmed by TGA data
(Figure 2,b).
between At this end, was
the components the composition
completed, whichwas cured at 280 °C by
was confirmed forIR10spectroscopy.
min. In this interval of time, the
The IR spectrum of
interaction between the components was completed, which
–1 was confirmed
epoxy resin (Figure 6b) contains a band of about 915 cm corresponding to the asymmetric stretching by IR spectroscopy. The
IR spectrum
vibrations of epoxy
of the resinthis
ring, while (Figure
band 6b) contains
is absent in the a band
spectrumof about
of ACP 915 cm–1 corresponding
(Figure 6a) and disappears to the
in
asymmetric stretching vibrations of the ring, while this band is absent in
the spectrum of cured composition (Figure 6c). The occurrence of reaction between the components the spectrum of ACP (Figure
6a) and
was also disappears
confirmed by in athe
highspectrum of cured
content (98%) composition
of the gel fraction. (Figure 6c). The occurrence of reaction
between the components was also confirmed by a high content (98%) of the gel fraction.
Polymers 2019, 11, 1191 8 of 12
Polymers 2019, 11, x FOR PEER REVIEW 9 of 13

Figure6.6.IR
Figure IRspectra
spectra of
of (a) ACP, (b)
(a) ACP, (b) DER-331,
DER-331,and
and(c)
(c)cured
curedcomposition.
composition.

TheTheshape
shapeofofDSC
DSCcurve
curvefor forthe
the cured
cured resin (Figure2e)
resin (Figure 2e)isisanother
anotherconfirmation
confirmation that
that thethe reaction
reaction
between components of the composition has completely proceeded under
between components of the composition has completely proceeded under the reported conditions. the reported conditions.
This curve
This does
curve not contain
does not containany thermal effectseffects
any thermal in the interval between between
in the interval the glass the
transition temperature
glass transition
of temperature
compositionof(130 ◦ C) and the temperature corresponding to the beginning of its decomposition
composition (130 °C) and the temperature corresponding to the beginning of its
(300 ◦ C, TGA, Figure 2b). It is known that the decomposition temperature of epoxy resin cured with
decomposition (300 °C, TGA, Figure 2b). It is known that the decomposition temperature of epoxy
aromatic amines
resin cured withdepends
aromatic little on the
amines amountlittle
depends andon type
theofamount
flame retardant
and type [11,22].
of flameFor DER-331
retardant or E-44
[11,22].
epoxy resins, itor
For DER-331 300 ◦epoxy
is E-44 C. Therefore,
resins, itthe thermal
is 300 stability the
°C. Therefore, of the curedstability
thermal ACP resin is cured
of the quite ACP
satisfactory.
resin
Results
is quite of the combustion test allowed us to assign the ACP-cured epoxy resin to the highest
satisfactory.
fireproofResults of the
category combustion
V-0. The combustiontest allowed
timeusoftovertically
assign thefixedACP-cured
samplesepoxy
uponresin to the
the first highest
and second
fireproofto
exposures category
flame wasV-0.only
The 1combustion time ofdroplets
s, while burning vertically fixed
were notsamples uponIt the
produced. canfirst and secondthat
be concluded
theexposures
resultingtomaterial
flame was only 1 s, while
is extremely burning droplets
non-flammable were notphosphorus-nitrogen
and exceeds produced. It can be concluded
[11] andthat
other
the resulting material is extremely non-flammable and exceeds
phosphazene-containing flame retardants [16] in its flame-retardant properties. phosphorus-nitrogen [11] and other
phosphazene-containing
The coke covers formed flame
afterretardants
combustion [16] in
of its
theflame-retardant
cured resin was properties.
porous according to the data of
The coke covers formed after combustion of the cured
microstructural studies and quantitative processing of the microphotographs resin was porous according
(Figureto7a).
theThe
datapores
of
microstructural studies and quantitative processing of the microphotographs (Figure 7a). The pores
were closed, while their size varied in the range from 0.2 to 200 µm, wherein the smaller pores were
were closed, while their size varied in the range from 0.2 to 200 μm, wherein the smaller pores were
predominant (Figure 7b).
predominant (Figure 7b).
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Figure 7. (a) SEM image of the coke cap and (b) the relative size distribution of pores after the
Figurecombustion
7. (a) SEMtest
image of the coke cap and (b) the relative size distribution of pores after the
of composition.
combustion test of composition.
The formed coke was dense, and its content at 600 ◦ C was about 55% according to the TGA
dataformed
The (see Figure
coke 2a). The TGA-FTIR
was dense, spectra
and its content atfurther
600 °С was disclosed
about the
55%pyrolysis
according information
to the TGA(Figure
data 8).
From Figure 8aTGA-FTIR
it can be observed that thedisclosed
release rate of gas firstly has a big(Figure
peak at8). 355 ◦ C, then
(see Figure 2,a). The spectra further the pyrolysis information From
reduces slightly, and then ◦ C. The curve at 355 ◦ C belongs to
Figure 8a it can be observed thathasthe two
releasemoreratepeaks
of gasatfirstly
480 andhas580
a big peak at 355 °C, then reduces
the and
first then
degradation −1
slightly, has twostage. The peak
more peaks at 3622
at 480 and cm580 °C. is the
Theabsorption
curve at 355 of °C
freebelongs
hydroxyl to group,
the firstand it
indicatesstage.
degradation production
The peak of water
at 3622 and cm–OH
−1 is containing
the absorption organic compounds
of free hydroxylduring group,the andinitial degradation.
it indicates
The peaks at 3040, −1
production of water and1600,
–OH1190 and 760
containing cm are
organic typical absorptions
compounds during the of aromatic
initial rings and
degradation. Thephenol
peaksgroups.
at 3040, The1600,peaks
1190 at and2962
760andcm−11350 cm−1 can
are typical indicate the
absorptions presencerings
of aromatic of alkane groups.groups.
and phenol Both these
groupsatof2962
The peaks peaks andconfirm
1350 cmthe−1 presence
can indicateof aromatic rings and
the presence aliphatic
of alkane moieties,
groups. Bothwhich
thesecan be attributed
groups of
peakstoconfirm
isopropylphenol,
the presence formed from the rings
of aromatic DER-331 andpart of the moieties,
aliphatic polymer. which
The peakscan at be2350 and 1790
attributed to cm−1
are typical for
isopropylphenol, CO2 , which
formed from the started
DER-331 to form
part at
ofthis temperature.
the polymer. The peaks
The peaks near
at 2350 and1350
1790 and −1 are cm−1
cm1250
can
typical forindicate
CO2, whichthe presence
started of to C–N
form groups in the pyrolysis
at this temperature. Thegas products.
peaks near 1350When and the1250
temperature
cm −1 can rises
up the
to 480 ◦ C, theofpeaks of isopropylphenol cangas
still be observed,
indicate presence C–N groups in the pyrolysis products. Whenbut thethey become rises
temperature smaller.
up to At the
same
480 °C, the time
peaksthe peaks for water and
of isopropylphenol CO2be
can still are getting larger.
observed, but they 580 ◦ C smaller.
Atbecome the peaks Atshow
the samemainly
timewater
and CO in theand pyrolysis −1 at 580 ◦ C can be considered as
the peaks for 2water CO2 aregas products.
getting larger. A At
small
580 peak
°С the atpeaks
1219 cm show mainly water and CO2 in
absorption
the pyrolysis gasof PO free radicals.
products. A small peak Fromatthe elemental
1219 cm−1 at 580analysis
°C canofbe
coke, it can beas
considered concluded
absorption (Table
of PO1) that
organic fragments undergo considerable destruction during the pyrolysis
free radicals. From the elemental analysis of coke, it can be concluded (Table 1) that organic fragments of the cured resin, as there
is a significant
undergo considerable reduction
destructionin the carbon
during and
the hydrogen
pyrolysis of content
the cured after pyrolysis.
resin, as thereAtisthe same time, the
a significant
relative
reduction content
in the carbonof phosphorus
and hydrogen atoms increases,
content after while nitrogen
pyrolysis. content
At the sameslightly
time, the decreases. As a result, it
relative content
can be considered that the fragments at gas phase mainly come
of phosphorus atoms increases, while nitrogen content slightly decreases. As a result, it can from the degraded organic parts beof the
polymer,
considered thatandthethat phosphazene
fragments at gasmoieties
phase mainlyof obtained
comepolymer
from themake a major
degraded contribution
organic parts of tothe
thermal
stability
polymer, and and
that coke formation.
phosphazene Thus, thermal
moieties stability
of obtained polymercan be controlled
make a majorusing differentto
contribution epoxy resins.
thermal
stability and coke formation. Thus, thermal stability can be controlled using different epoxy resins.
Polymers 2019, 11, 1191 10 of 12
Polymers 2019, 11, x FOR PEER REVIEW 11 of 13

Figure 8. 3D
Figure 8. FTIR
3D FTIRspectra ofofthe
spectra thepyrolysis
pyrolysis gas productsofofACP
gas products ACP cured
cured composition
composition fromfrom
TGATGA (a) and
(a) and
FTIRFTIR spectra
spectra of pyrolysis
of pyrolysis gasgas productsatatdifferent
products different temperatures
temperatures(b).
(b).

Table The
1. 1.
Table Theelemental
elemental content ofthe
content of thesubstances
substances (wt.
(wt. %).%).

Element Element ACP ACP DER-331

DER-331 Cured resin Coke
Cured Resin Сoke
C C 55.65 55.65 72.12
72.12 64.82 64.82 42.09 42.09
O O 18.55 18.55 18.82
18.82 18.68 18.68 – –
H H 4.64 4.64 7.06
7.06 5.84 5.84 2.00 2.00
N N 12.16 12.16 –– 6.14 6.14 5.17 5.17
P P 9.00 9.00 –– 4.54 4.54 9.40 9.40
The developed composition on the basis of ACP has been tested as an adhesive for steel. The
shear strength was 4 ± 0.1 MPa. At the same time, a cohesive break was observed. Cohesive break
The developed composition on the basis of ACP has been tested as an adhesive for steel. The shear
and a low value of tensile strength can be explained by the high brittleness of the cured resin. This
strength was 4 ± 0.1 MPa. At the same time, a cohesive break was observed. Cohesive break and a low
disadvantage can be eliminated either through the introduction of fillers, or through the use of other
valuetypes
of tensile strength
of resins, whichcan besubject
is the explained by the
of further high brittleness of the cured resin. This disadvantage
research.
can be eliminated either through the introduction of fillers, or through the use of other types of resins,
which4. is the subject of further research.
Conclusions
In summary, the composition based on the industrial epoxy resin DER-331 cured with ACP (a
4. Conclusions
phosphazene containing amide groups) has been designed and prepared. The obtained resin
possesses
In summary, the glass
the transition
composition temperature
based on of 130
the °C, the decomposition
industrial epoxy resin temperature
DER-331ofcured 300 °Cwith
and ACP
the shear strength
(a phosphazene of 4 MPa.
containing Moreover,
amide groups) thishas
composition demonstrated
been designed very high The
and prepared. flame-retardant
obtained resin
properties.
possesses The damping
the glass transition time after the first
temperature of and
130 second
◦ C, theexposures to flametemperature
decomposition was only 1 s,of which
300 ◦isC and
probably due to the porous and dense structure of the formed coke, as well as its high content. Since
the shear strength of 4 MPa. Moreover, this composition demonstrated very high flame-retardant
the coke is incombustible, it creates a protective layer and contributes to the damping of the resin. It
properties. The damping time after the first and second exposures to flame was only 1 s, which is
also hinders heat propagation in the sample, thereby preventing the thermal decomposition of
probably due toareas
unaffected the porous and dense
of the material and structure
the releaseofofthe
lowformed coke,
molecular as well
weight as its high
combustible content. that
substances Since the
coke are
is incombustible,
the main source of flames. The pores inside the formed coke improve the thermal insulation ofIt also
it creates a protective layer and contributes to the damping of the resin.
hinders heat propagation
the material; therefore, in
an the sample,
increase thereby
in the numberpreventing the thermal
of closed pores preventsdecomposition of unaffected
the spread of flames. All
areasthis
of the
makesmaterial and thecomposition
the developed release of low molecular
promising weight combustible
for practical substances
use as non-flammable that are
thermally the main
stable
adhesives
source and matrices
of flames. The pores forinside
different
thecompositions.
formed coke improve the thermal insulation of the material;
therefore, an increase
Supplementary in theThe
Materials: number of closed
following pores
are available prevents
online the spread of flames.
at www.mdpi.com/xxx/s1, FigureAll
S1: this
title, makes
Table the
developed
S1: title,composition
Video S1: title. promising for practical use as non-flammable thermally stable adhesives and
matrices
Author forContributions:
different compositions.
Conceptualization, E.M.C.; methodology, E.M.C. and A.V.S., validation, E.M.C. and
I.V.T.; formal analysis, A.V.S., I.V.T. and V.P.C.; investigation, E.M.C., S.N.F. and I.V.T.; data curation, E.M.C.,
Supplementary Materials:
V.P.C. and S.N.F.; The following
writing—original draftare availableE.M.C.
preparation, onlineand
at http://www.mdpi.com/2073-4360/11/7/1191/s1,
I.V.T.; writing—review and editing, E.M.C.,
The raw/processed data
I.V.T. and S.N.F.; required is
visualization, presented
E.M.C., I.V.T.in theA.V.S.;
and manuscript and Video
supervision, E.M.C.;Abstract.
funding acquisition, E.M.C.
Author The work Conceptualization,
Contributions:
Funding: was supported by D. E.M.C.; methodology,
Mendeleev UniversityE.M.C. and A.V.S.,
of Chemical validation,
Technology E.M.C.
of Russia. and I.V.T.;
Project
formal analysis,
Number A.V.S., I.V.T. and V.P.C.; investigation, E.M.C., S.N.F. and I.V.T.; data curation, E.M.C., V.P.C. and
019-2018.
S.N.F.; writing—original draft preparation, E.M.C. and I.V.T.; writing—review and editing, E.M.C., I.V.T. and
S.N.F.; visualization, E.M.C., I.V.T. and A.V.S.; supervision, E.M.C.; funding acquisition, E.M.C.
Funding: The work was supported by D. Mendeleev University of Chemical Technology of Russia. Project
Number 019-2018.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2019, 11, 1191 11 of 12

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