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Flame-retardant performance and mechanism of epoxy thermosets modified

with a novel reactive flame retardant containing phosphorus, nitrogen, and
sulfur

Article  in  Polymers for Advanced Technologies · August 2017

DOI: 10.1002/pat.4145

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 Polymer Degradation and Stability 131 (2016) 106e113

Contents lists available at ScienceDirect

Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Synthesis of a novel phosphorus-nitrogen type flame retardant

composed of maleimide, triazine-trione, and phosphaphenanthrene
and its flame retardant effect on epoxy resin
Siqi Huo, Jun Wang, Shuang Yang*, Junpeng Wang, Bin Zhang, Bo Zhang, Xi Chen,
Yushan Tang
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, People's Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, a novel phosphorus/nitrogen-containing compound (DMT) constructed by maleimide,
Received 30 May 2016 phosphaphenanthrene and triazine-trione was successfully synthesized. The chemical structure of DMT
Received in revised form was characterized by Fourier transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic
7 July 2016
resonance (NMR). DMT was then blended with diglycidyl ether of bisphenol-A (DGEBA) to prepare a
Accepted 17 July 2016
Available online 18 July 2016
series of flame-retardant epoxy resins. The flame retardancy and combustion behavior were evaluated
using limited oxygen index (LOI), vertical burning (UL94) and cone calorimeter test. The results indicated
that DMT dramatically enhanced the flame retardancy of epoxy resin. When the phosphorus content was
Keywords:
Epoxy resin
only 1.0%, the EP/DMT-1.0 sample had a LOI value of 35.8%, and achieved UL94 V-0 rating. The com-
Flame retardant bustion parameters disclosed that DMT obviously weakened the heat release intensity. Compared with
Phosphaphenanthrene the neat EP sample, the peak of heat release rate (pk-HRR), average of heat release rate (av-HRR) and total
Triazine-trione heat release (THR) of EP/DMT-1.25 sample were decreased by 59.4%, 28.2% and 27.4%, respectively. The
Maleimide decreased av-EHC of EP/DMT thermosets indicated that DMT inhibited the gaseous phase combustion
due to the gaseous phase quenching effect of phosphorus-containing free radicals derived from the
decomposed DOPO group. The condensed phase studies indicated that DMT promoted the charring of EP
matrix and formation of phosphorus-containing char layer with compact and intumescent structure.
DMT exerted bi-phase flame retardant effect.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction attention. Traditionally, incorporating halogenated compounds into

As important industrial materials, epoxy resins (EP) possess
great versatility, toughness, low shrinkage in curing, good moisture
resistance, solvent and chemical resistance, excellent adhesion and
superior electrical and mechanical properties. Therefore, they are
widely used in advanced composite matrix, surface coating and
semiconductor encapsulation applications [1e5]. However, the
flammability of conventional epoxy resins restricts their applica-
tions in some fields which require high flame retardant grade [6,7].
Therefore, the development and application of high performance
flame retardant epoxy resins have attracted a great deal of
* Corresponding author. School of Materials Science and Engineering, Wuhan
University of Technology, 122 Luoshi Road, Hongshan District, Wuhan 430070,
People's Republic of China.
E-mail address: ys583377051@163.com (S. Yang).
epoxy resins is able to effectively enhance the flame retardancy.
Nevertheless, the applications of halogenated compounds are
restricted due to environmental reasons [8,9]. Hence, more and
more researchers focus on halogen-free flame retardants in recent
years.
Over the past decade, much attention has been paid to halogen-
free flame retardants, such as phosphorus- [10e13], silicon-
[14e18], and boron-based [19e22]. Among them, 9,10-dihydro-9-
oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its de-
rivatives have received a great deal of attention due to their high
reactivity, high thermal stability, and flame-retardant efficiency
[23e25]. However, an ideal flame-retardant property could only be
acquired under high phosphorus loading when DOPO-based com-
pounds were used alone [26,27]. Therefore, many efforts have been
made to explore flame retardant epoxy resin systems containing
DOPO and other flame retardant compositions with higher

http://dx.doi.org/10.1016/j.polymdegradstab.2016.07.013
0141-3910/© 2016 Elsevier Ltd. All rights reserved.
 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113
efficiency. According to some previous reports, multiple flame-
retardant compositions containing phosphaphenanthrene and
other functional groups with certain flame-retardant effects, such
as maleimide [28,29], s-triazine [30,31], triazine-trione [32,33],
phosphazene [34,35], and silsesquioxane [36,37], can endow epoxy
resins with higher flame-retardant properties compared with those
only containing DOPO. Moreover, synergistic effect was observed in
gaseous phase and condensed phase when DOPO and other flame
retardant groups coexisted in flame retardant epoxy resin systems
[24,38,39].
In this paper, a novel flame retardant additive (DMT) containing
phosphaphenanthrene, maleimide and triazine-trione groups was
synthesized by ring-opening addition reaction between DOPO-
HPM and TGIC. The chemical structure of DMT was characterized
by FTIR, 1H and 31P NMR. Thermal properties, flame-retardant
properties and combustion behavior of the EP thermosets were
evaluated by TGA, LOI, vertical burning (UL94) and cone calorim-
eter test. The flame retardant mechanism of DMT in condensed
phase and gaseous phase was also studied.
2. Experimental
2.1. Materials
Diglycidyl ether of bisphenol-A (DGEBA) with an epoxide
equivalent weight (EEW) of about 188 g/equiv was provided by
Yueyang Baling Huaxing Petrochemical Co., Ltd. N-(4-
hydroxyphenyl) maleimide (HPM) was obtained from Puyang
Willing Chemicals Co., Ltd. 9,10-Dihydro-9-oxa-10-
phosphaphenanthrene-10-oxide (DOPO) was purchased from
Huizhou Sunstar Technology Co., Ltd. Triglycidyl isocyanurate
(TGIC) was purchased from Jinan Zian Chemicals Co., Ltd. Triphenyl
phosphine (TPP), 4,40 -Diamino-diphenyl sulfone (DDS), dime-
thylformamide (DMF) and 1,4-dioxane were purchased from
Sinopharm Chemical Reagent Co., Ltd. DOPO-HPM was synthesized
in our laboratory according to our previous research [39]. All the
reagents were used as received.
2.2. Synthesis of DMT
DOPO-HPM (12.15 g, 0.03 mol) and DMF (120 mL) were intro-
duced into a 250 mL, three-neck and round-bottom glass flask
equipped with a mechanical stirrer, reflux condenser and ther-
mometer. The mixture was heated to 135  C and stirred until DOPO-
HPM was fully dissolved. Then, TPP (0.09 g) was added and used as
catalyst. After that, TGIC (2.97 g, 0.01 mol) was added in batches
over 2 h. The solution was further heated to reflux for 5 h. Then the
mixture was distilled to remove DMF. The crude product was
washed with deionized water, and then vacuum-dried at 60  C for
24 h. The reaction formula is shown in Scheme 1. The yield was 95%.
2.3. Preparation of flame-retardant epoxy resins
DGEBA and DMT were blended at 130  C until a homogeneous
solution was obtained. After that, stoichiometric DDS (with respect
to epoxy) was added. After a homogeneous solution was obtained,
the mixture was degassed under vacuum and poured directly into a
preheated mold and thermally cured in an air convection oven at
160  C for 2 h and 180  C for 5 h. All the details of formula are listed
in Table 1.
2.4. Measurements
Fourier Transform Infrared (FTIR) spectra were obtained using a
Nicolet 6700 infrared spectrometer. The powdered samples were
107
thoroughly mixed with KBr and then pressed into pellets.
1
H and 31P NMR spectra were obtained on a Bruker AV400 NMR
spectrometer using DMSO-d6 as the solvent.
Thermogravimetric analysis (TGA) was performed using
NETZSCH STA449F3 at a heating rate of 10  C/min under nitrogen
atmosphere from 40 to 800  C.
The LOI values were measured at room temperature on a JF-3
oxygen index meter (Jiangning Analysis Instrument Company,
China) according to ASTM D2863 and dimensions of all samples
were 100  6.5  3 mm3. Vertical burning (UL-94) tests were car-
ried out on the NK8017A instrument (Nklsky Instrument Co., Ltd.,
China) with the dimension of 130  13  3 mm3 according to the
UL-94 test standard. Cone calorimeter measurements were per-
formed on a FTT cone calorimeter according to the ISO 5660 stan-
dard under an external heat flux of 50 kW/m2. The dimension of
samples was 100  100  3 mm3. The calculating time of cone
calorimeter results is within 490 s. The measurement for each
specimen was repeated three times, and the error values of the
typical cone calorimeter data were reproducible within ±5%.
Py-GC/MS analysis was carried out with an Agilent 7890/
5975 GC/MS. The injector temperature was 250  C, 1 min at 50  C
then the temperature was increased to 280  C at a rate of 8  C/min.
The temperature of the GC/MS interface was 280  C, and the cracker
temperature was 500  C.
Morphological studies on the residual chars were conducted
using a JSM-5610LV scanning electron microscope (SEM) at an ac-
celeration voltage of 20 kV. The SEM instrument was integrated
with an energy dispersive X-ray (EDX) microanalyser for elemental
analysis.
3. Results and discussion
3.1. Structural characterization of DMT
DMT was synthesized through addition reaction between
DOPO-HPM and TGIC using TPP as catalyst. As shown by FTIR
spectrum in Fig. 1, the bands at 1778 and 1714 cm1 were assigned
to the stretching vibration of C]O; the band at 1594 cm1 was
assigned to the absorption peak of triazine ring; the band at
1514 cm1 was assigned to the absorption peak of benzene ring; the
peak at 1394 cm1 was assigned to the stretching vibration of CeN;
the peak at 1200 cm1 was assigned to the stretching vibration of
P]O; the peak at 925 cm1 was assigned to the stretching vibration
of PeOeC. The results indicated the presence of maleimide group,
triazine ring and DOPO group.
1
H and 31P NMR spectra of DMT were shown in Figs. 2 and 3,
respectively. As shown in Fig. 2, 6.6e7.2 ppm was assigned to the
chemical shift of aromatic hydrogen of benzene ring (OeC6H6eN);
7.2e8.5 ppm was assigned to the chemical shift of aromatic
hydrogen of DOPO group; 2.76 and 2.89 ppm was assigned to the
chemical shift of CH2 linked with triazine ring (C3N3eCH2);
3.0e3.3 ppm was assigned to the chemical shift of CH2 in mal-
eimide group (eCH2eC]O); 3.84e3.97 and 4.1e4.4 ppm was
assigned to the chemical shift of CH2 in aliphatic chain (CH2eO-Ar);
4.0 ppm was assigned to the chemical shift of CH in maleimide
group (CHeC]O); 3.6e3.84 ppm was assigned to the chemical shift
of CH in aliphatic chain (CH2eCHeCH2); 5.0e5.5 ppm was assigned
to the chemical shift of secondary hydroxyl group (CHeOH). As
shown in Fig. 3, the 31P NMR spectrum of DMT showed a single peak
at 29.8 ppm. The results further confirmed that DMT was suc-
cessfully synthesized.
3.2. Thermal analysis
Thermal stability of the cured epoxy resins and DMT was
108 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113

O O O N N

O O O
O
N N N
O
N OH O
P N O CH 2 CH CH2
O O P
O O N OH
O O
O

DOPO-HPM TGIC DMT

O
O
N O CH 2 CH CH 2
P
OH
O O

Scheme 1. Synthesis route of DMT.

Table 1
Formulas of the cured epoxy resins.

Sample code DGEBA (g) DDS (g) DMT (g) DMT content (%) P content (%)

EP 100 33.0 0 0 0
EP/DMT-0.25 100 33.0 4.5 3.3 0.25
EP/DMT-0.5 100 33.0 9.5 6.6 0.5
EP/DMT-0.75 100 33.0 14.8 10.0 0.75
EP/DMT-1.0 100 33.0 20.8 13.5 1.0
EP/DMT-1.25 100 33.0 27.3 17.0 1.25

Fig. 1. FTIR spectrum of DMT.

Fig. 2. 1H NMR spectrum of DMT.

assessed by TGA under nitrogen atmospheres. The corresponding

TGA curves are shown in Fig. 4. The characteristic thermal
decomposition parameters, including temperature at 5% weight
loss (T5%), temperature at maximum weight loss rate (Tmax) and
char yields at 800  C are listed in Table 2.
As shown in Table 2, T5% of the neat EP sample was 384  C,
whereas that of DMT was 285  C. DMT decomposed ahead of EP
matrix. With the incorporation of DMT, T5% and Tmax of the EP/DMT
thermosets gradually decreased with the increasing mass fraction
of DMT. Considering the proportion of DMT and EP matix as well as
their respective weight loss at T5%, if the decomposition product of
DMT did not react with EP matrix, the weight loss at the tested T5%
would be less than 5%. Hence, the decomposition product of DMT
catalyzed the decomposition of EP matrix in advance, and the
catalytic decomposition effect was enhanced with the increasing
content of DMT. It was deduced that the less stable PeC bond of
DMT molecule decomposed in advance to form phosphate com-
pounds, which promoted the decomposition of EP matrix. As
shown in Fig. 4, the char yields of EP/DMT thermosets were higher
than that of the neat EP sample during 500e800  C. DMT enhanced
the thermal stability of the char residues at high temperature re-
gion. The char yields of EP/DMT thermosets at 800  C were
increased by about 33% compared with that of the neat EP sample.
 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113 109

Table 3
LOI and UL94 test results of the cured epoxy resins.

Sample code P content (%) LOI (%) UL-94 (3 mm) Dripping

EP 0 22.5 NR Yes
EP/DMT-0.25 0.25 31.2 NR No
EP/DMT-0.5 0.5 32.8 NR No
EP/DMT-0.75 0.75 34.4 V-1 No
EP/DMT-1.0 1.0 35.8 V-0 No
EP/DMT-1.25 1.25 33.0 V-0 No

DMT-0.25 sample loaded with phosphorus content of only 0.25%

surged to 31.2%. However, EP/DMT-0.25 sample failed to pass the
UL94 vertical burning test. When the DMT content was further
increased, the LOI values as well as the corresponding UL94 rating
of EP/DMT samples were gradually promoted. However, when the
phosphorus content reached 1.25%, the LOI value of EP/DMT-1.25
sample was decreased to 33.0%. Excess content of DMT led to a
deviation from the optimal ratio of the flame retardant content,
thus resulting in negative effect on LOI performance. It was worth
Fig. 3. 31
P NMR spectrum of DMT. noting that there was no dripping phenomenon for EP/DMT sam-
ples. DMT endowed the EP thermosets with good anti-dripping
property. It was inferred that thick melt was formed through
chemical reactions between EP matrix and the pyrolytic products of
DMT in condensed phase.

3.4. Combustion behaviors

Cone calorimetry test was used to investigate the combustion

behaviors of the EP thermosets. The characteristic parameters, such
as the time to ignition (TTI), average of heat release rate (av-HRR),
peak of heat release rate (pk-HRR), average of effective heat of
combustion (av-EHC), average CO yield (av-COY), average CO2 yield
(av-CO2Y), total smoke production (TSP) and char yields at 400 s are
summarized in Table 4.
As shown in Table 4, the TTI of the neat EP was 47s whereas
those of the EP/DMT thermosets were shortened to some extent.
EP/DMT-1.25 sample with the highest phosphorus content had the
minimum value of TTI. According to the above discussion on TGA,
DMT decomposed in advance and induced the degradation of EP
matrix, which weakened the resistance to ignition, resulting in the
Fig. 4. TGA curves of the EP thermosets and DMT under N2 atmosphere. decrease in TTI.
The curves of heat release rate (HRR) are shown in Fig. 5. The
neat EP burned fiercely after ignition and the HRR reached a sharp
Table 2
Thermal parameters of the cured epoxy resins and DMT.
peak with a pk-HRR of 1208 kW/m2. With the addition of DMT, the
combustion intensity of EP/DMT thermosets was remarkably
Sample code T5% ( C) Tmax ( C) Char yields at 800  C (%)
weakened. Compared with the neat EP sample, the av-HRR and pk-
EP 384 410 17.3 HRR of EP/DMT-1.25 sample were decreased by 28.2% and 59.4%,
EP/DMT-0.25 356 405 22.0 respectively. The degradation of EP/DMT thermosets ahead of time
EP/DMT-0.5 335 396 23.5
facilitated the carbonization of EP matrix during combustion which
EP/DMT-0.75 325 397 22.1
EP/DMT-1.0 315 385 23.3 was benefit for hindering the heat and oxygen from reaching the
EP/DMT-1.25 311 382 22.8 inner EP matrix and thus weakened the combustion intensity.
DMT 285 e 29.3 Fig. 6 shows the THR curves of the cured epoxy resins. It was
obvious that the THR was gradually decreased with the increasing
mass fraction of DMT. The THR value at 490 s of EP/DMT-1.25
However, the char yields were not further increased with the sample was decreased by 27.4% compared with that of the neat
increasing content of DMT [24,25,35]. EP sample. DMT effectively suppressed the heat release amount as
well as the heat release intensity during combustion process, and
thus reduced the fire hazard.
3.3. Flame retardancy The char yields during combustion were also investigated. As
shown in Table 4, char yields of the EP thermosets after cone
The flame retardancy of the prepared EP thermosets was eval- calorimeter test were distinctly increased with the incorporation of
uated by limited oxygen index (LOI) and UL94 vertical burning test. DMT, disclosing the flame retardant effect of DMT in condensed
The related data are listed in Table 3. As shown in Table 3, the LOI phase. Compared with the neat EP sample, the char yield of EP/
value of the neat EP sample was just 22.5%, whereas that of the EP/ DMT-0.75 sample was increased by 77%. When the DMT content
110 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113

Table 4
Combustion parameters of the cured epoxy resins obtained from cone calorimeter test.

Sample code TTI (s) av-HRR (kW/m2) pk-HRR (kW/m2) av-EHC (MJ/kg) av-COY (kg/kg) av-CO2Y (kg/kg) TSP (m2) Char yields (%)

EP 47 177 1208 22.2 0.063 1.589 30.0 10.4

EP/DMT-0.25 39 147 837 19.8 0.075 1.325 22.5 13.3
EP/DMT-0.5 35 137 685 19.5 0.086 1.247 22.0 15.1
EP/DMT-0.75 37 136 544 18.8 0.105 1.155 23.0 18.4
EP/DMT-1.0 36 133 506 17.9 0.162 1.088 23.5 19.1
EP/DMT-1.25 34 127 491 16.0 0.224 1.029 23.7 18.1

DMT-1.25 sample was decreased by 28%. In addition, the av-COY

increased whereas the av-CO2Y decreased with the increasing
mass fraction of DMT. The results disclosed that the incorporation
of DMT resulted in more incomplete combustion products (CO) and
less complete combustion products (CO2). DMT exerted flame
retardant effect in gaseous phase. Further evidence will be given in
the subsequent section.
Smoke in a real fire means more risk of suffocation, even more
fatal than heat release. As shown in Table 4, the TSP values of EP/
DMT thermosets were obviously lower than that of the neat EP
sample. The TSP of EP/DMT-0.5 sample was decreased by 26.7%
compared with that of the neat EP sample. The results indicated
that DMT had a certain effect in smoke suppression on DGEBA
thermosets.

3.5. Py-GC/MS analysis

Fig. 5. HRR curves of the cured epoxy resins. In order to further disclose the flame retardant mechanism in
gaseous phase, DMT were investigated by Py-GC/MS. The typical
fragment flows with some characteristic ionic peaks selected, and
the results are illustrated in Fig. 7.
As shown in Fig. 7, the m/z of fragments at 78, 79 and 80 were
considered as the triazine free radicals [25]. The m/z of fragments at
168, 169, and 170 were determined as dibenzofuran, o-phenyl-
phenoxyl free radical, and o-phenylphenol, respectively [38]. The
m/z of fragment at 141 was considered as the O]PeOePh free
radical [25]. The m/z of fragment at 115 was considered as the
carboxylic acid fragment derived from maleimide group [25]. The
m/z of fragments at 63 and 64 were considered as PO2 and HPO2
free radicals produced by the PO free radicals from the broken
phosphaphenanthrene group combining with OH, H, or O free
radicals [38]. The m/z of fragment at 93 was considered as phenoxy
radical. The results indicated that DMT decomposed to release free
radicals with quenching effect and incombustible nitrogen-
containing fragments, thus exerting flame retardant effect in
gaseous phase.

3.6. Morphology and chemical analyses of residual chars

Fig. 6. THR curves of the cured epoxy resins.

3.6.1. Morphology analysis of residual chars after cone calorimeter

test
was further increased, the char yields were not obviously changed.
The char residues of the neat EP and EP/DMT-1.25 sample after
This was consistent with the TGA results. More carbonizations
cone calorimeter test were measured by visual observation and
meant less flammable pyrolytic gas products, and thus less com-
SEM. Fig. 8 showed the SEM and digital images of the char residues
bustion heat.
after cone calorimeter test. As shown in Fig. 8, the neat EP sample
The gaseous phase combustion as well as the corresponding
characteristic data including av-EHC, av-COY and av-CO2Y was also formed a broken structure with a small amount of residue which
was unable to serve as a protective layer. However, the char of EP/
discussed. Av-EHC, which is the ratio of average of heat release rate
DMT-1.25 sample exhibited higher char yields than that of the neat
(av-HRR) to the average mass loss rate from the cone calorimetry
EP sample. As seen from the top view of the char residues, the char
test, discloses the burning rate of volatile gases in gaseous phase
layer of EP/DMT-1.25 sample was more coherent and compact than
flame during combustion. As shown in Table 4, the av-EHC was
that of EP sample. As seen from the side view of the char residues,
dramatically decreased with the increasing content of DMT, indi-
expansion ratio of EP/DMT-1.25 sample was obviously elevated
cating that DMT was capable of inhibiting the gaseous phase
with the addition of DMT.
combustion. Compared with the neat EP sample, the av-EHC of EP/
The char structures were further investigated by SEM. As shown
 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113 111

Fig. 7. Typical Py-GC/MS spectra of DMT at different retention time.

Fig. 8. SEM and digital images of the char residues after cone calorimeter test.

in Fig. 8, continuous and sealed structure was observed in the

exterior surface of EP/DMT-1.25 sample. The interior char of EP/
DMT-1.25 thermoset exhibited honeycomb-like structure with
numerous bubbles separated by very thin layers. The continuous
and sealed surface of the char residue was able to retard the release
of pyrolysis gases. Then the pyrolysis gases were accommodated by
the underlying char layers to form an intumescent structure. The
compact surface sealed the combustible volatiles generated by
thermoset, consequently to cut off the supply of fuel and thus
weaken the combustion intensity. In addition, intumescent struc-
ture acted as an insulating barrier to reduce the efficiency of heat-
and oxygen-exchange. As a result, the incorporation of DMT into EP
thermosets led to the promoted flammability property.

3.6.2. Chemical analysis of residual chars

For purpose of further revealing the condensed phase flame
retardant mechanism, the char residues were investigated by FTIR
and EDX.
The FTIR spectra of the char residues of EP/DMT-1.25 and the Fig. 9. FTIR spectra of the char residues after cone calorimeter test.
neat EP sample after UL94 test are shown in Fig. 9. The absorption
peaks at 1592 and 1508 cm1 assigning to aromatic structure were
observed in both spectra curves. Apart from the absorption peaks at were assigned to C]O and CeN, respectively [29,39]. It was
1592 and 1508 cm1, new absorption peaks at 1768, 1704, 1376, 946, deduced that maleimide and triazine-trione groups with good
754 and 719 cm1 appeared in the FTIR spectrum of EP/DMT-1.25 thermal stability retarded the decomposition of EP thermosets
sample. The absorption peaks at 1764, 1704, 717 and 1376 cm1
112 S. Huo et al. / Polymer Degradation and Stability 131 (2016) 106e113
Table 5
Elemental composition and content of the residual char.
Sample code Element composition (wt%)
C N P O S
EP 87.30 4.48 0 7.90 0.28
EP/DMT-1.0 75.02 11.03 1.51 11.17 1.27
EP/DMT-1.25 77.89 8.42 1.82 10.85 1.02
during combustion and the corresponding pyrolytic fragments
were retained in the char residues. In addition, the new absorption
peaks at 946 and 754 cm1 assigning to PeOeC further proved the
condensed phase flame retardant effect of DMT [11,40].
Element analyses of the residual chars after cone calorimeter
test were studied using EDX. We selected three different regions of
the char surface to detect the element contents and calculated the
averages to ensure the reliability of data. The elemental contents of
different samples were shown in Table 5. As shown in Table 5, EP/
DMT-1.0 and EP/DMT-1.25 samples possessed higher phosphorus,
nitrogen and oxygen contents compared with the neat EP sample.
The results indicated that part of DOPO groups decomposed to form
phosphate and polyphosphate which promoted the charring of EP
matrix and formation of phosphorus-rich viscous char layer in
condensed phase [41,42]. In addition, the nitrogen-containing
fragments derived from maleimide and triazine-trione groups
remained in the residues, and thus increased the nitrogen content.
The EDX results were consistent with the FTIR results as discussed
above. The results further demonstrated the condensed phase
flame-retarded effect of DMT.
4. Conclusions
A novel flame retardant additive (DMT) containing phospha-
phenanthrene, maleimide and triazine-trione groups was suc-
cessfully synthesized and then blended with DGEBA to prepare
flame-retardant epoxy resins. LOI and UL94 test results indicated
that the flame retardancy of EP/DMT thermosets was significantly
enhanced with the incorporation of DMT. The combustion param-
eters indicated that DMT inhibited the heat release intensity and
reduced the heat release amount of EP/DMT thermosets. During
combustion, DMT decomposed to release phosphorus-containing
free radicals with quenching effect and incombustible nitrogen-
containing gaseous. In addition, DOPO group of DMT decomposed
to produce phosphorus-containing compounds which catalyzed
the charring of EP matrix; thermal stable maleimide and triazine-
trione groups of DMT retarded the decomposition of EP matrix,
leaving pyrolytic fragments in the char residues. DMT exerted bi-
phase flame retardant effect.
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