Journal Pre-proofs

Fabrication of Polyphosphazene Covalent Triazine Polymer with Excellent

Flame Retardancy and Smoke Suppression for Epoxy Resin

Yunzhi Fang, Junshuai Miao, Xingwen Yang, Yun Zhu, Guiyou Wang

PII: S1385-8947(19)33245-0
DOI: [Link]
Reference: CEJ 123830

To appear in: Chemical Engineering Journal

Received Date: 17 September 2019

Revised Date: 11 December 2019
Accepted Date: 14 December 2019

Please cite this article as: Y. Fang, J. Miao, X. Yang, Y. Zhu, G. Wang, Fabrication of Polyphosphazene Covalent
Triazine Polymer with Excellent Flame Retardancy and Smoke Suppression for Epoxy Resin, Chemical Engineering
Journal (2019), doi: [Link]

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 Fabrication of Polyphosphazene Covalent Triazine Polymer with Excellent
Flame Retardancy and Smoke Suppression for Epoxy Resin
Yunzhi Fang, Junshuai Miao, Xingwen Yang, Yun Zhu, Guiyou Wang*

Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and

Engineering, East China University of Science and Technology, Shanghai 200237, China

* Corresponding to: Guiyou Wang, Email address: guiyouwang@[Link]

GRAPHICAL ABSTRACT

ABSTRACT

A kind of polyphosphazene covalent triazine polymer (PCTP) was fabricated through a facile

trimerization reaction of 4-hydroxybenzonitrile substituted hexachlorocyclotriphosphazene

(HCCP). The as-prepared PCTP containing phosphorus and nitrogen elements was added into

epoxy resins (EP) to improve their fire resistance and smoke suppression property. As obtained

from cone calorimeter test, compared with the neat EP, the values of peak heat release rate

(P-HRR), total heat release (THR) and total smoke production (TSP) of EP@PCTP composites

were reduced by 73%, 69% and 42%, respectively, when 8.7 phr PCTP was loaded into the EP

matrix. Meanwhile, the limiting oxygen index (LOI) value was also increased greatly from 22.3%

to 28.0%, and the EP composites successfully passed UL-94 V-0 rating with 6.4 phr PCTP

incorporated. The results may be resulted from the more compact and higher coherence char layer

of EP@PCTP composites, and PCTP could function both in condensed and gaseous phases due to

the barrier effect and dilution effect during the combustion. The water resistance of the EP matrix

1 / 33
was also enhanced effectively due to the presence of PCTP. In addition, the nearly unchanged

glass transition temperature (Tg) and mechanical properties of the resultant EP@PCTP composites

confirmed the excellent compatibility between PCTP and EP matrix, which endows its promising

application potential in polymer materials.

Keywords: Covalent triazine polymer; Phosphazene derivative; Epoxy resin; Fire safety; Smoke

suppression

2 / 33
1. Introduction

Epoxy resins (EP), a type of prominent thermosetting materials, have been widely used in the

field of adhesives, paints, laminates and structural composites, etc., owing to their excellent

properties such as superior chemical resistance, dimensional stability and outstanding mechanical

performance [1-3]. Unfortunately, like many other organic materials, the poor flame resistance of

EP extremely restricted their further applications in electrical and electronic industries [4-6].

What’s more, the large amounts of dense smoke as well as toxic gases such as CO and NO

generated during the combustion could cause huge damages both to human lives and their

properties, and could also have a serious impact on social and economic development [7, 8].

Over the past decades, extensive efforts have been devoted to reduce the fire hazard of EP.

Halogenated flame retardants (FRs), an efficient strategy in the past, however, have been

prohibited in many countries due to their potential hazards to human health and environment [9].

Alternatively, phosphorus-containing FRs are efficient in improving the fire safety of substrate

materials. The blocking and quenching effects of phosphorus and its free radicals contribute to the

enhanced flame retardancy and less smoke of the matrix. However, some flame retardant EPs

suffer from high water absorption due to the hydrophilicity of certain phosphorus-containing FRs

[10-13], which will deteriorate the electronic performance. Nitrogen-based FRs are also candidates

for some polymers due to their dilution effect caused by the ignitable gases generated like N2, NH3

and NO2 [14-17]. Nevertheless, many researches have suggested that there exists a favorable

synergistic effect between phosphorus and nitrogen elements [18-20]. For example, Gaan et al.

investigated the influence of nitrogen-containing additives on the flame retardancy of cotton

cellulose, and the results showed that compared with the cotton samples only containing

phosphorus element, those having both phosphorus and nitrogen elements achieved higher LOI

values and char yields [21]. Duan et al. prepared a phosphorus/nitrogen containing polycarboxylic

acid (TMD), and the investigations revealed that TMD exerted bi-phase flame-retardant effects on

EP [22]. Hu et al. designed a hyper-branched phosphorus/nitrogen-containing FR (HPNFR) via

the transesterification reaction, and it was found that the EP had higher LOI and passed UL-94

V-0 rating [23]. However, these FRs failed to improve the thermal stability of EP, and their

impacts on the water resistance were not studied.

3 / 33
 Hexachlorocyclotriphosphazene (HCCP), a class of representative organic-inorganic hybrid

material with alternating arrangement of phosphorus and nitrogen elements in the backbone, has

aroused great concern due to its tremendous thermal stability and outstanding structural flexibility.

Due to the presence of active P–Cl bonds, a battery of phosphazene derivatives can be prepared

through the reaction of HCCP with amines, phenols, alcohols or thiol compounds [24-26]. The

prepared derivatives could be small molecules, as well as branched and crosslinked polymers,

which have been applied in the fields of biomaterials, liquid crystals, catalysts, and chemical

sensors etc. [27-31]. Until now, many additive and reactive FRs have been prepared from HCCP,

among which the compounds with nitrogen-containing heterocycle such as maleimide, triazole

and triazine have drawn much attention due to their synergistic effect in improving the fire safety

of polymer materials. For instance, Yang et al. reported a phosphazene derivative from HCCP and

maleimide, the compound showed flame retardancy both in condensed and gaseous phases [32].

Chen et al. prepared a series of phosphazene-triazine bi-group FRs from HCCP, amine compounds

and cyanuric chloride, which could effectively improve the fire resistance of polylactic acid when

they were blended with ammonium polyphosphate (APP) [33]. Wen et al. synthesized a

cyclotriphosphazene-based chemical from HCCP and piperazine, the chemical exhibited an

excellent char-forming property to polypropylene when it was used in combination with 10.0-22.5

wt% microencapsulated APP [34]. Nevertheless, most of them were small molecules or required a

complex synthetic procedure. What’s more, they exhibited high flame retardancy only when

mixed with other additives, thus restricting their practical applications.

Covalent triazine polymers (CTPs) are a subclass of covalent organic frameworks (COFs).

The presence of well-defined heteroatoms in the triazine frameworks provides their potential

applications in gas adsorption, catalysis and organic dyes etc. [35-37]. However, in spite the fact

that CTPs are rich in nitrogen element, the application of CTPs as FRs has been rarely carried out

previously. On the other hand, in view of the knowledge that CTPs can be easily prepared through

the trimerization reaction of cheap aromatic nitriles with strong Brønsted acids or ZnCl2 as the

catalyst, and the P–Cl bonds in HCCP can be replaced by the hydroxyls of 4-hydroxybenzonitrile

to obtain a phosphazene monomer containing aromatic nitriles. Thus, a novel CTP with

phosphazene structure can be formed through the trimerization of 4-hydroxybenzonitrile

4 / 33
substituted HCCP. The hyper-crosslinked structure as well as the triazine units would exhibit

better water-resistance and higher thermal stability [34, 38]. To the best of our knowledge, the

preparation of such a CTP with phosphazene units embedded and its application in reducing the

fire hazard of EP have not been reported yet.

Herein, we introduce a novel phosphazene-based CTP (PCTP) through the facile

trimerization reaction of hexakis-(4-cyanophenyloxy)cyclotriphosphazenes (HCPCP). The

designed PCTP was prepared under mild condition, and achieved a high yield (94%) without using

triazine-based monomers like melamine, cyanuric chloride and cyanuric acid as the synthesis of

most triazine-containing FRs did, which possess the potential for industrial production. The

as-synthesized PCTP has both triazine and cyclotriphosphazene units as well as the

hyper-crosslinked structure, which might endow it with higher thermal stability, excellent char

forming ability and better water resistance than the other micro-molecular cyclotriphosphazene-

and triazine-based FRs [39, 40]. PCTP was further applied to improve the fire safety of EP. The

morphology, mechanical properties, thermal stability, water absorption, combustion behavior and

smoke suppression properties of EP@PCTP composites were investigated. In addition, the

possible flame-retardant mechanism of PCTP to reduce the fire risk of EP was also discussed.

2. Experimental section

2.1. Materials

HCCP, anhydrous potassium carbonate (K2CO3), 4-hydroxybenzonitrile,

trifluoromethanesulfonic acid (CF3SO3H), 4, 4’-diaminodiphenylmethane (DDM), chloroform and

acetone were purchased from Aldrich Chemical Co., Ltd (Shanghai, China). Diglycidyl ether of

bisphenol A (DGEBA) with the epoxy value of 0.51 mol/100 g was supplied by Jiangyin Wanqian

Chemical Industry Co. Ltd (Jiangsu, China). Before use, K2CO3 was dried at 140 °C for 2 h;

acetone and chloroform were dried with CaSO4 and were redistilled. Other reagents were used as

received.

2.2. Synthesis of HCPCP

HCPCP was synthesized as follows [41]. HCCP (19.97 g, 57.44 mmol),

4-hydroxybenzonitrile (41.07 g, 344.8 mmol), K2CO3 (114.44 g, 828 mmol) and 800 mL acetone

were added to a flask. The mixture was then heated to 55 °C and stirred for 10 h under nitrogen

5 / 33
atmosphere. After that, the mixture was concentrated by rotary evaporation and subsequently

washed with plenty of distilled water to remove the white salt. The obtained crude product was

recrystallized twice in 400 mL DMF, and then dried at 80 °C under vacuum for 24 h to get a white

product with a yield of 86% (Scheme 1).

2.3. Synthesis of PCTP

PCTP was prepared through one-pot superacid catalytic trimerization reaction of HCPCP in

chloroform. In a typical procedure, HCPCP (15.6 g, 18.5 mmol) and 700 mL chloroform were

charged into a pre-dried 2-neck round bottom flask under argon atmosphere. The mixture was

cooled to 0 °C and CF3SO3H (18 g, 120 mmol) was then added dropwise over 30 min. The

reaction was continued for 2 h at 0 °C and then maintained for another 22 h at room temperature.

The hard, yellow precipitate appeared during the reaction process. After that, an NH3/H2O solution

(0.5 mol/L) was added and stirred for another 2 h until the mixture became neutral. Finally, the

mixture was filtered and washed with distilled water, ethanol and THF successively, and then

dried under vacuum for 24 h to obtain a yellow powder with a yield of 94% (Scheme 1).

Scheme 1. Synthetic routines of HCPCP and PCTP.

2.4. Preparation of EP@PCTP composites

6 / 33
 Firstly, calculated amounts of finely grinded PCTP was dispersed in 100 mL THF, then 100 g

DGEBA was added and stirred at 60 °C for 3 h with the aid of ultrasonication. Subsequently, the

THF was removed completely under vacuum at 60 °C. After that, 25.74 g DDM melted at 105 °C

was added into the mixture and stirred at 220 rpm for 1 ~ 2 min. Then, the mixture was poured

into a preheated mold immediately after degassed for another 5 min to remove air bubbles. Finally,

the blend was cured at 100 °C for 2 h and 150 °C for 2 h respectively to get EP@PCTP composite

samples with different PCTP contents. The formulations of the EP@PCTP composites are listed in

Table 1.

Table 1 Formulations of EP and EP@PCTP composites.

DGEBA DDM PCTP PCTP content

Sample
(g) (g) (g) phr wt%
EP 100 25.74 0 0 0
EP@PCTP-4 100 25.74 5.24 4.2 4
EP@PCTP-6 100 25.74 8.03 6.4 6
EP@PCTP-8 100 25.74 10.93 8.7 8
2.5. Measurements

Fourier transform infrared (FTIR) spectra of all samples were recorded on a Nicolet 5700 IR

spectrometer in the range of 4000 ~ 400 cm−1 with a resolution of 4 cm−1. The samples were

grinded with KBr and pressed into pellets before characterization.

1H NMR spectrum of HCPCP was obtained at room temperature on a Bruker AVANCE 400

MHz spectrometer. Dimethyl sulfoxide-d6 (DMSO-d6) was used as solvent.

The solid-state 31P CP/MAS NMR spectrum was obtained using an AVANCEIII 500 MHZ

super conducting Fourier NMR spectrometer.

Electrospray ionization mass spectrometry (ESI-MS) of HCPCP was performed by using a

XEVO G2 TOF apparatus.

X-Ray photoelectron spectroscopy (XPS) measurement was conducted on a Thermo

ESCALAB 250XI spectrometer to obtain the relative elemental compositions and the valence

states of PCTP.

Energy-dispersive X-ray spectroscopy (EDS) was performed by using a QUANTAX 400-30

apparatus.

Differential scanning calorimetry (DSC) were achieved on a DSC Q2000 (TA Instruments) to

7 / 33
obtain the glass transition temperatures (Tg) of EP and its composites. All the measurements were

performed under N2 atmosphere with a heating rate of 10 °C·min−1 from room temperature to

200 °C.

Thermo-gravimetric analysis (TGA) of samples was monitored by using the NETZSCH

STA409PC/4/H TGA thermal analyzer. Each sample (8 ~ 10 mg) was placed in a platinum pan

and heated from room temperature to 800 °C at a heating rate of 10 °C·min−1 under the N2 or air

atmosphere with a flow rate of 20 mL·min−1.

The limiting oxygen index (LOI) values were measured on a JF-3 oxygen index instrument

according to ASTM D2863-06, with the specimen size of 130 × 6.5 × 4 mm3. The vertical burning

(UL-94) were conducted on a FTT0082 instrument according to ATSM D3801, with the specimen

size of 130 × 13 × 3.2 mm3.

The water resistance of EP@PCTP composites was measured according to the following

process. The samples were soaked in distilled water at 70 °C, and the water was refreshed every

24 h. After certain periods, the samples subjected to tests were taken out and the water on the

surface of samples was wiped carefully. The water absorption percentage (WAP) of the samples

was calculated using the following equation:

WAP = [(W1-W0) / W0] ×100% (1)

Where W0 represents the initial mass, and W1 is the mass of treated samples after immersed in

water for different periods of time.

The combustion behaviors of EP and EP@PCTP composites were evaluated on a FTT cone

calorimeter at a heat flux of 35 kW·m−2, which corresponds to a mild fire scenario. The size of the

specimens was 100 × 100 × 4 mm3 and each specimen was mounted on aluminum foil during the

test.

Morphological studies of char residues and fracture surface of EP and EP@PCTP composites

were carried out using an S-3400N scanning electron microscope (SEM) at an acceleration voltage

of 15 kV.

Thermogravimetric analysis/Fourier transform infrared spectrometry (TG-FTIR) was

characterized by utilizing a NETZSCH TG 209F3 thermal analyzer connected with a Nicolet 6700

IR spectrometer. The sample (around 8 mg) was heated from 35 to 800 °C at 10 °C·min−1 under

8 / 33
N2 atmosphere.

Laser Raman spectroscopy (LRS) measurements were conducted on an INVIA reflex Laser

Micro-Raman Spectrometer at room temperature with a 514.5 nm argon laser line.

Tensile and flexural tests were performed on a SANS tester at room temperature according to

ASTM D638-2010 and ASTM D790-2003, respectively. The size of dump-bell shaped tensile

samples was 115 × 20 × 4 mm3, and the size of bending samples was 80 × 10 × 4 mm3. The values

of both tests reflected an average of five tests.

3. Results and discussion

3.1 Characterization of HCPCP

The structure of HCPCP was characterized by FTIR, 1H NMR and ESI. In the FTIR spectrum

of HCPCP (Fig. 1a), typical peaks at 1201 and 846 cm−1 were attributed to P=N and P–N

stretching vibration of the phosphazene groups, respectively [42, 43]. The distinct absorption of

P–O–CAr band can be observed at 1017 and 944 cm−1. Compared with FTIR spectrum of HCCP,

the appearance of a new sharp absorption band of C ≡ N at 2232 cm−1 and the disappearance of

P–Cl band at 600 and 519 cm−1 confirmed the reaction between HCCP and 4-hydroxybenzonitrile.

In the 1H NMR spectrum (Fig. 1b), the signals at 7.18 and 7.84 ppm were assigned to the protons

in the benzene rings of aromatic nitriles, and the integrated area ratio of the two peaks was close to

1:1. No extra signals arising from impurity were detected, indicating that the structure of HCPCP

was consistent with our expectation. In addition, ESI-MS result in Fig. S1 showed that the

measured m/z of HCPCP (866.0961 [M + Na]⁺) was very close to the calculated value (866.0960

[M + Na]⁺), which further proved that HCPCP was synthesized successfully.

9 / 33
(a) 4-Cyanophenol (b) NC CN

Transmittance (%) O O
b N
P
N

HCCP 3288 a NC O P
N
P O CN
O O
a b

NC CN

HCPCP
600
519 DMSO

H2O
2232 846
1201 1017 944

4000 3500 3000 2500 2000 1500 1000 500 10 9 8 7 6 5 4 3 2 1

Chemical shift (ppm)
Wavenumber (cm-1)

(c) HCPCP (d)

Transmittance (%)

-1.46

PCTP 2232

1677
* *
1366

4000 3500 3000 2500 2000 1500 1000 500 -90 -60 -30 0 30 60 90
Chemical shift (ppm)
Wavenumber (cm-1)

Fig. 1. FTIR spectra of (a) HCPCP and (c) PCTP; (b) 1H NMR spectrum of HCPCP and (d) 31P

NMR spectrum of PCTP.

3.2 Characterization of PCTP

As illustrated in Fig. 1c, compared with the FTIR spectrum of HCPCP, the two new strong

bands appeared at 1677 and 1366 cm−1 proved the generation of triazine rings [44, 45]. Meanwhile,

the intensity of carbonitrile band at around 2232 cm−1 in the PCTP sample was decreased

significantly, which indicated that there only existed a few terminal nitrile moieties in PCTP. In

addition, the solid-state 31P CP/MAS NMR spectrum of PCTP (Fig. 1d) exhibited only one

resonance signal at -1.46 ppm, which implied that all the P atoms in PCTP were under a

magnetically equivalent environment [46, 47].

10 / 33
 (a) (b) C 1s
C 1s C=C

Intensity (a.u.)
Intensity (a.u.)

O 1s

N 1s
C=N

P 2p

800 600 400 200 0 292 290 288 286 284 282 280
Binding energy (eV) Binding energy (eV)

(c) N 1s
(d) P 2p

Intensity (a.u.)
Intensity (a.u.)

P=N
pyridinic N
P-O
phosphazene N

406 404 402 400 398 396 394 392 140 138 136 134 132 130
Binding energy (eV) Binding energy (eV)

Fig. 2. (a) XPS survey spectrum of PCTP; high-resolution XPS spectra of PCTP in the (b) C 1s, (c)

N 1s, and (d) P 2p regions.

According to the XPS survey spectrum in Fig. 2a, the atomic percentage of C, N, O and P

was 69.16%, 12.11%, 14.40% and 4.33%, respectively, which nearly matched the calculated

values (C:70%, N:15%, O:10%, P:5%). Fig. 2b-d portrayed the high-resolution scans of the C 1s,

N 1s, and P 2p. The C 1s signal of the PCTP exhibited two main peaks with binding energies at

286.3 and 284.6 eV, which were attributed to C=N and C=C bonds, respectively [48]. In the N 1s

spectrum, two binding states could be separated, one at 398.8 eV was derived from the pyridinic

nitrogen (C=N–C) in the triazine units of PCTP, and the other at 397.9 eV could be ascribed to the

nitrogen in phosphazene [49-51]. In addition, the P 2p spectrum indicated the co-existence of the

P-O (134.9 eV) and the P=N bonds (134.1 eV) in the structure [52, 53]. The above analysis

confirmed that the structure of PCTP was identical with the expected design.

EDS analysis was further conducted to verify the elemental compositions of PCTP. It is

observed from the EDS-mapping images in Fig. 3 that C, O, N, and P elements existed in the

11 / 33
sample and all of the elements in PCTP dispersed uniformly in the skeleton of polymers, which

further corroborated the successful preparation of PCTP.

Fig. 3. (a) Digital photograph of bulk PCTP; (b) SEM image, and (c-f) EDS-mapping images of

PCTP.

PCTP was not dissolved in any common solvents such as THF, acetone, DMF, and DMSO,

etc. Its thermal stability was characterized by TGA (Fig. S2). The 10 wt% loss temperature (T10%)

of PCTP was 429 °C, and the char yield at 800 °C (R800) reached up to 67 wt%, which indicated its

high thermal stability and good charring property. Such pretty properties came from the thermally

stable cyclotriphosphazene and triazine groups, and the hyper-crosslinked structure of PCTP. In

the DTG curve (Fig. S2), a three-step decomposition process of PCTP can be observed, which

could be ascribed to the weight loss of small amount of residual water in post-treatment process,

the breakdown of skeleton and decomposition of char residues, respectively.

3.3 Thermal properties of EP@PCTP composites

Tg is generally considered to be a significant parameter in evaluating the thermal and

compatibility properties of polymeric materials. Fig. 4a shows that the EP@PCTP composite

samples presented a slightly higher Tg than that of pure EP sample, indicating the increase of

rigidity and the favorable compatibility between EP matrix and PCTP particles. The results may

be caused by two factors. On the one hand, the rigid nature of PCTP may confine the mobility of

EP chains to some extent; on the other hand, the residual terminal nitrile groups in the PCTP may

12 / 33
react with the epoxide groups during the curing process and thus increase the compatibility and

crosslink density of composites [54]. Interestingly, the EP@PCTP composites displayed a good

transparency (Fig. 4b), which suggests their potential applications in some fields such as LED

packaging materials [19].

Fig. 4. (a) DSC curves of EP and EP@PCTP composites; (b) digital photographs of EP and

EP@PCTP composite samples.

In order to investigate the influence of PCTP on the thermal degradation properties of EP

matrix, the thermal stability of EP@PCTP composites in nitrogen and air atmospheres was

evaluated (Fig. 5), and the detailed data such as T10%, the temperature at maximum weight loss

rate (Tmax) and R800 are summarized in Table S1. Fig. 5a shows that in nitrogen atmosphere, EP

and EP@PCTP composites displayed only one decomposition process. T10% and Tmax of all the

composites were lower than those of pure EP, and they decreased with the increase of PCTP

content. This may be attributed to the breakdown of unstable P–O–C bonds existed in the PCTP

[55, 56]. However, EP@PCTP composites exhibited a higher R800 value than pure EP. For

instance, the R800 of EP@ PCTP-8 (24.9 wt%) was much higher than that of neat EP (17.9 wt%).

This result implied that PCTP could promote the formation of compact char layer, and the

phosphorus-rich char layer could play as an effective shield to delay and prohibit the heat and

mass transfer, hence, the thermal resistance of EP matrix was improved [57].

In air atmosphere (Fig. 5c), the thermal degradation behavior of EP@PCTP composites was

mainly divided into two stages. The decomposition trend of the former stage was similar to those

in nitrogen atmosphere, while the second stage took place at 470-650 °C was ascribed to the

thermal oxidation degradation of the unstable char residues formed in the former stage. In DTG

curves (Fig. 5d), the changing trend of Tmax2 was not obvious with the increasing content of PCTP,
13 / 33
which may be due to the fact that Tmax2 was mainly determined by the EP matrix itself. The Tmax2

values for EP@PCTP composites were a bit higher than that of the pure EP, demonstrating that

EP@PCTP composites were more stable in high temperature region. Furthermore, the

improvement of Tmax2 was more obvious than other reported FRs employed in EP [58-60],

suggesting that PCTP has a more positive impact on the thermal stability of EP under air

atmosphere. In addition, the R800 of pure EP was only 0.33 wt%, while those of EP@PCTP

composites improved significantly from 0.33 wt% to 2.14 wt% with the increase of PCTP. Such

properties would greatly benefit the flame retardancy of EP matrix.

3.0
(a) 100
EP
EP@PCTP-4
(b) EP
EP@PCTP-4
EP@PCTP-6 Deriv. Weight (%/°C) 2.5 EP@PCTP-6
EP@PCTP-8 EP@PCTP-8
80 2.0
Weight (%)

1.5
60

1.0
40
0.5

20 0.0

100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (°C)

2.5
(c) 100 EP
EP@PCTP-4
(d) EP
EP@PCTP-4
EP@PCTP-6 2.0 EP@PCTP-6
Deriv. Weight (%/°C)

80 EP@PCTP-8 EP@PCTP-8
Weight (%)

1.5
60

1.0
40

20 0.5

0 0.0

100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (°C)

Fig. 5. TGA and DTG curves of EP and EP@PCTP composites in nitrogen (a, b) and air (c, d)

atmospheres.

3.4 Combustion behaviors of EP@PCTP composites

The flame retardancy of PCTP was firstly evaluated by LOI and UL-94 tests. As shown in

Table 2, the LOI values increased dramatically from 22.3% to 28.0% when the PCTP content was

increased from 0 to 8.7 phr. As for UL-94 test, the pure EP achieved a longer burning time and

received no rating. However, the UL-94 rating of EP composites was promoted with the addition

of PCTP and passed the UL-94 V-0 rating when the PCTP content was 6.4 or 8.7 phr. The results

14 / 33
indicated that the incorporation of PCTP could greatly enhance the flame resistance of the EP

matrix.

Table 2 LOI and UL-94 results of EP and EP@PCTP composites.

UL-94
Sample LOI (%)
t1/t2 (s)a Dripping Rating
EP 22.3 86.2/7.7 No No rating
EP@PCTP-4 23.8 17.8/3.3 No V-1
EP@PCTP-6 26.5 5.3/2.5 No V-0
EP@PCTP-8 28.0 3.2/2.4 No V-0
a Average burning time after the 10 s ignition.

Cone calorimetry is another significant technique in bench scale to quantitatively assess the

fire properties of materials, in which some critical parameters are closely related to the real

combustion behaviors. Fig. 6a-d display the heat release rate (HRR), total heat release (THR),

smoke release rate (SPR), and total smoke production (TSP) curves of prepared composites, and

the specific values are listed in Table 3. Table 3 shows that the time to ignition (TTI) of

EP@PCTP-4 was much lower than that of pure EP, while the TTI values increased appreciably

when the PCTP content further moved to 6.4 and 8.7 phr. It was possible that the lower TTI value

of EP@PCTP-4 came from the lower T10% value compared with the pure EP. However, when the

loading of PCTP reached up to a higher proportion, enough nonflammable gases produced could

in turn to dilute the ignitable gases, which could cause a higher TTI value [61, 62].

Fig. 6a and 6b show that pure EP burned dramatically after ignition with a peak HRR

(P-HRR) value of 847.6 kW·m−2 and a THR value of 106.7 MJ·m−2, while the corresponding

values changed largely with the incorporation of PCTP. The P-HRR and THR dropped sharply by

55% and 32%, respectively, with only 4.2 phr loading of PCTP in the EP matrix. Furthermore, the

8.7 phr loading of PCTP in the EP brought about a maximum 73% and a maximum 69%

diminutions in P-HRR and THR, respectively, demonstrating the superior fire hazard resistance of

PCTP to the EP matrix. In order to compare the efficiency of flame retardancy of PCTP, Table 4

summarizes the cone calorimeter data of several phosphorus/nitrogen-based FRs applied in the EP.

Obviously, PCTP exhibited superb flame retardancy in comparison to other FRs.

15 / 33
 1000 120
(a) EP
EP@PCTP-4
(b) EP
EP@PCTP-4
800 EP@PCTP-6 100 EP@PCTP-6
EP@PCTP-8 EP@PCTP-8
80
HRR (KW/m2)

THR (MJ/m2)
600
60
400
40
200
20

0 0

0 100 200 300 400 500 600 0 100 200 300 400 500 600
Time (s) Time (s)

(c) 0.25
EP
EP@PCTP-4 (d) 35 EP
EP@PCTP-4
EP@PCTP-6 30 EP@PCTP-6
0.20 EP@PCTP-8 EP@PCTP-8
25
SPR (m2/s)

TSP (m2)
0.15 20

15
0.10
10
0.05 5

0
0.00
-5
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Time (s) Time (s)

(e) EP
(f) 1.0
4.5 EP@PCTP-8
EP@PCTP-6
0.8
FGI (kW/m2s)

FPI (m2s/kW)

3.0 0.6

EP@PCTP-4 0.4
EP@PCTP-6 EP@PCTP-8 EP@PCTP-4
1.5
0.2 EP

0.0 0.0
Sample Sample

Fig. 6. (a) HRR, (b) THR, (c) SPR, (d) TSP, (e) FGI and (f) FPI results of EP and EP@PCTP

composites.
Table 3 Cone calorimeter data of EP and EP@PCTP composites.
TTI P-HRR THR TSP av-CO av-CO2 Residue
Sample
(s) (kW·m−2) (MJ·m−2) (m2) (kg·kg−1) (kg·kg−1) (wt%)

EP 136 847.6 106.7 33.7 0.0498 1.0763 10.8

EP@PCTP-4 106 378.1 72.9 29.5 0.0602 1.0557 22.7

EP@PCTP-6 191 249.3 40.3 25.1 0.0443 0.7022 25.2

EP@PCTP-8 192 227.1 33.3 19.4 0.0409 0.6135 28.5

16 / 33
 It is well known that the most casualties in a fire accident are always caused by the smoke

and toxic gases released in a burning building. Hence, the smoke emission behavior of a material

must be taken into serious consideration. The SPR and TSP curves (Fig. 6c and 6d) show that the

SPR and TSP values of pure EP are much higher than those of EP@PCTP composites. The TSP

values of EP@PCTP composites reduced appreciably from 33.7 to 19.4 m2 with the increase of

PCTP content, indicating the excellent smoke suppression property of PCTP to the EP matrix. The

results could be ascribed to the catalytic charring effect of PCTP, which delayed the diffusion of

pyrolysis components and protected the unburned substances inside from exposing to the fire [63].

Moreover, the emissions of CO and CO2 (Fig. S3a and S3b) were significantly suppressed with

the incorporation of PCTP, which further confirmed the excellent performance of PCTP on

harmful gases suppression.

Table 4 Cone calorimeter data of different FRs for EP matrix.

FR The decrease rate (%)

Heat flux
FRs content P-HRR THR TSP Reference
(kW·m−2)
(phr) (kW·m−2) (MJ·m−2) (m2)

BPFA 9.9 47 29 48 50 [51]

HAP-DOPO 10.3 57 / / 50 [64]

BPA-BPP 9.9 60 11 31 35 [65]

BPS-BPP 9.9 46 15 71 35 [66]

PCTP 8.7 73 69 42 35 This work

Fire growth index (FGI) and fire performance index (FPI) are two important derivative

parameters from cone calorimeter test in order to evaluate the flame retardancy of materials. FGI

was defined as the proportion of P-HRR and time to P-HRR (t-PHRR), the higher the value, the

faster the fire spreads [67, 68]. As shown in Fig. 6e, the FGI values of EP@PCTP composites

were much lower than that of pure EP. FPI was calculated from the proportion of TTI and P-HRR,

which correlated well with the result of large-scale experiments in the case of fire safety. FPI is in

negative correlation to the fire hazard, the lower the value of FPI, the quicker the flashover starts

[20]. As depicted in Fig. 6f, it was obviously that FPI improved with the increase of PCTP, which

further corroborated the remarkable property of PCTP in reducing the fire risk of EP matrix.

17 / 33
3.5 Flame retardant mechanism

3.5.1 Morphology and structure of char residues

Fig. 7. Digital photographs of the char residues from top view and side view for (a, e) EP, (b, f)

EP@PCTP-4, (c, g) EP@PCTP-6 and (d, h) EP@PCTP-8 after cone calorimeter test.

The char residues of polymer materials after combustion could provide some significant

information about the flame retardant mechanism. Fig. 7 exhibits the char residue images of EP

and EP@PCTP composites captured from different perspectives. As illustrated, neat EP presented

a badly fragmentary state and almost burned out. However, with the incorporation of PCTP, a

series of residual chars with a larger size and an increased thickness could be observed. The char

layers became more compact, with higher coherence and integrality for EP@PCTP-6 and

EP@PCTP-8. The phenomenon was attributed to the catalytic charring effect and intumescent

effect of PCTP, which could in turn slow down the heat flux and suppress the fire propagation.

SEM images of the external char residues (Fig. 8a-d) show that pure EP presented a

discontinuous appearance along with numerous cracks and open holes on the surface, which was

beneficial for the emission of combustible volatiles from the inside of the substrate and the

exposure of EP matrix to the heat flow outside, thus causing the higher HRR and TSP values. On

the contrary, it was apparent that the external char surface got smoother and denser after the

addition of PCTP. Interestingly, plenty of unbroken and intumescent bubbles could be captured

from the char surface of EP@PCTP-8, which signified the enhanced thermal resistance of the char

layer [22]. For the inner structure of the char residues (Fig. 8e-h), a similar change was found.

Destructive cracks existed in the interior char residue of pure EP, which would promote the heat-
18 / 33
and oxygen-exchanges inside the EP substrate. On the contrary, with the incorporation of PCTP

into the EP matrix, the holes and cracks became smaller, more continuous and intumescent

surfaces appeared in the interior char residues. The char layers with better integrity and enhanced

thermal stability thereby could play as an effective shield to prevent the further pyrolysis of the

underlying substrate, to delay the heat and mass transfer, and meanwhile to isolate the oxygen

needed in combustion [69, 70].

The vibrations of disordered carbon (D-band) and sp2-hybridized carbon or graphitic carbon

(G-band) can be detected at around 1365 and 1600 cm−1, respectively, in the LRS spectra (Fig.

8i-l). Generally, the intensity proportion of the D and G bands (ID/IG) reflects the graphitization

degree of char, a lower value reveals a higher graphitization degree and a better shield effect [71,

72]. Apparently, pure EP presented the highest ID/IG value (2.83), whereas the corresponding ID/IG

values of EP@PCTP composites reduced with the introducing of PCTP. The EP@PCTP-8 sample

showed the lowest ID/IG value (2.41) among all the samples, indicating the formation of the char

residue with the highest graphitization degree and the most stable property, which was in

accordance with the conclusion from the SEM image.

The chemical components of the char residues were further examined by EDS and FTIR

experiments to investigate the charring behavior of PCTP. According to the EDS result in Fig. 8m,

the phosphorus content in the char layer of EP@PCTP-8 was 16.28 wt%, while the nitrogen

content was 5.28 wt%. The decreased mass ratio of N/P (from 4.39 to 0.32) for EP@PCTP-8

suggested that the nitrogenous groups such as triazine units in the composite were decomposed

and transformed into the gaseous products while burning. In the corresponding FTIR spectrum

(Fig. 8n), the broad peak detected at 3431 cm−1 was derived from the stretching vibrations of O-H

and N-H bonds, which came from the phosphoric or polyphosphoric acid, amino compounds or

water [73]. The peaks at 1150 and 866 cm−1 could be ascribed to the stretching vibrations of P=N

and P–N groups in the phosphazene structure. The absorptions around 960 and 1121 cm−1 were

assigned to the vibrations of P-O-P and P-O-CAr bonds, indicating the existence of the crosslinked

phosphorous oxides in the char layers [74-76]. These results confirmed the catalytic effect and

char-forming ability of PCTP during the combustion and revealed its flame-retardant mechanism

in condensed phase. However, the triazine groups could not be observed in the FTIR spectrum, it

19 / 33
was possible that the triazine units degraded at high temperature and produced nitrogenous

nonflammable gases such as N2 or NO2 in the combustion process [39, 77-79], thus functioned

with dilution effect in gaseous phase.

Fig. 8. SEM images of the external char residues of (a) EP, (b) EP@PCTP-4, (c) EP@PCTP-6, (d)

EP@PCTP-8; and interior char residues of (e) EP, (f) EP@PCTP-4, (g) EP@PCTP-6, (h)

EP@PCTP-8 ; Raman spectra of the char residues of (i) EP, (j) EP@PCTP-4, (k) EP@PCTP-6, (l)

EP@PCTP-8; (m) EDS and (n) FTIR spectra of the char residues of EP@PCTP-8.

3.5.2 Evolved gases analysis

The development and spread of the blaze can be significantly influenced by the gasified

pyrolysis volatiles generated during the combustion process. Therefore, the thermal pyrolysis

behaviors of EP and EP@PCTP composites were analyzed through TG-FTIR technique to further

find out the flame retardant mechanism of PCTP in gaseous phase. Fig. S4 presents the 3D

TG-FTIR and FTIR spectra of volatile products from pure EP and EP@PCTP-8 obtained at the
20 / 33
maximum degradation rate. Generally, the FTIR signals of some typical pyrolysis volatiles could

be clearly detected at wavenumbers of 3500-3850, 2750-3200, 2250-2400, 1700-1900, 1200-1600

and 600-1000 cm−1. Significant diminutions in pronounced peaks of toxic gaseous volatiles could

be easily observed between pure EP and EP@PCTP-8. Fig. 9a and 9b depict the FTIR spectra of

the volatile products for EP and EP@PCTP-8 at different temperatures. Signals from primary

pyrolysis volatiles located at 3650, 2970, 2360 and 2190, 1740, 1510 and 1260 cm−1 in the spectra

were assigned to the absorption of -OH (H2O or phenol), hydrocarbons, CO2 and CO, carbonyl

compounds, aromatic compounds containing aromatic rings or aromatic ethers, respectively [80].

It seemed that the FTIR spectra of EP@PCTP-8 were analogous to that of pure EP. However, the

volatile products of EP@PCTP-8 turned up slightly earlier than that of pure EP during the

pyrolysis process, indicating the catalytic effect of PCTP in the EP matrix.

(a) H2O or Phenol Hydrocarbons CO2 Carbonyl compounds

Aromatic compounds (b) H2O or Phenol Hydrocarbons CO2 Carbonyl compounds
Aromatic compounds
800°C
800°C
600°C 600°C
Absorbance

Absorbance

500°C 500°C
450°C 450°C
430°C 430°C
420°C 420°C
CO CO
400°C 400°C
360°C 360°C
300°C 300°C
250°C 250°C

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 9. FTIR spectra of the volatile products for (a) EP and (b) EP@PCTP-8 at different

temperatures.

(a) Gram-Schmidt EP
EP@PCTP-8
(b) H2O or Phenol
EP
EP@PCTP-8
(c) Hydrocarbons
EP
EP@PCTP-8
Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min) Time (min)

(d) CO EP (e) Carbonyl compounds EP

EP@PCTP-8
(f) Aromatic compounds
EP
EP@PCTP-8
EP@PCTP-8
Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min) Time (min)

21 / 33
 Fig. 10. Absorbance curves of several typical volatile products against time of

EP and EP@PCTP-8.

In order to further elucidate the effect of PCTP on the amount of gasified pyrolysis volatiles

released during the heating program, the intensities of primary volatile products mentioned above

versus time for EP and EP@PCTP-8 are given in Fig. 10. It was apparent in Fig. 10a that the total

volatile products were reduced with the incorporation of PCTP. In addition, the maximum

absorbance intensities for EP@PCTP-8 were significantly weaken compared with those of pure

EP with respect to volatiles such as H2O/Phenol, hydrocarbons, CO, carbonyl compounds and

aromatic compounds (Fig. 10b-f). It is generally accepted that hydrocarbons and aromatic

compounds are flammable volatiles, thus the decrease of these volatile products generated would

be propitious to the suppression of smoke and heat release during the combustion. Moreover, the

intensity of CO diminished greatly, indicating the effect of PCTP on gaseous toxicity suppression,

which was coincided with the result of cone calorimeter test.

3.5.3 Proposed flame retardant mechanism

Scheme 2. Schematic illustration of the possible chemical structure evolution and flame retardant

22 / 33
 mechanism for PCTP in the EP matrix.

Based on the analysis above, the possible chemical structure evolution and flame retardant

mechanism for PCTP in the EP matrix were proposed and illustrated in Scheme 2. As a triazine

polymer with phosphazene units embedded, PCTP functioned both in condensed and gaseous

phases. On the one hand, PCTP could produce phosphorus based compounds such as phosphoric

or polyphosphoric acid and crosslinked phosphorous oxides, which work together with the

nitrogenous carbon generated during the combustion to promote the formation of the compact and

integral char layers, which could in turn cut off the heat flux and oxygen in the air, thus

suppressed the fire propagation of EP matrix. In addition, due to the barrier effect of the char

layers, the diffusion of pyrolysis volatiles was delayed and led to the decreased smoke release. On

the other hand, the nitrogenous nonflammable gases such as N2 or NO2 originated from the

triazine groups in PCTP could also work in gaseous phase, the dilution effect further contributed

to the reduced fire hazard of EP matrix.

3.6 Moisture resistance

Some FRs are moisture sensitive due to their inherent hydrophilicity, which could limit their

applications in electronic fields [40, 81]. Table 5 indicates that the WAP increased over time for

all samples. However, EP@PCTP composites showed suppressed WAP, and the water absorption

decreased with the increase of PCTP, demonstrating that PCTP could improve the moisture

resistance of EP matrix effectively, which might be resulted from the hyper-crosslinked structure

and the triazine units in the skeleton of PCTP [82].

3.7 Mechanical properties of EP@PCTP composites

The influence of a flame retardant on the mechanical properties of cured EP materials is a

vital factor to evaluate its practical application performance. Table 5 summarizes the data of EP

and EP@PCTP composites after tensile and flexural tests. It can be seen that PCTP had little

influence on the tensile strength and flexural strength of EP@PCTP composites, indicating the

good compatibilities of PCTP in the EP matrix. In addition, the tensile modulus and flexural

modulus increased with the incorporation of PCTP, which could be ascribed to the presence of

rigid structures in PCTP. Fig. S5 shows the SEM images of the tensile fractured surfaces of EP

and EP@PCTP composites. It was notable that the fractured surface of pure EP presented a fairly

23 / 33
 smooth morphology (Fig. S5a), while the surfaces of EP@PCTP composites were quite rough and

small crinkles could be observed (Fig. S5b-d), which implied the strong interfacial interaction

between PCTP and EP matrix. Moreover, the EDS-mappings of P and N elements on the fractured

surface of EP@PCTP-8 (Fig. S5e, S5f) indicated that PCTP had been dispersed uniformly in the

EP matrix.

Table 5 Water absorption and mechanical properties of EP and EP@PCTP composites.

WAP at 70 °C Tensile Elongation Tensile Flexural Flexural

Sample (%) strength at break modulus strength modulus

12 h 24 h 48 h (MPa) (%) (GPa) (MPa) (GPa)

EP 0.23 0.32 0.65 63.7±2.4 11.2±2.0 1.07±0.05 115.1±7.8 3.55±0.19

EP@PCTP-4 0.14 0.27 0.60 70.9±1.5 8.8±0.3 1.10±0.09 119.8±3.7 3.61±0.20

EP@PCTP-6 0.11 0.19 0.53 68.6±1.2 8.5±0.2 1.15±0.03 121.0±4.2 3.77±0.23

EP@PCTP-8 0.08 0.15 0.47 64.3±1.7 7.8±0.2 1.18±0.04 114.6±1.2 3.90±0.10

4. Conclusions

In this work, a novel polyphosphazene covalent triazine polymer, PCTP, was successfully

synthesized through the trimerization reaction of aromatic nitriles substituted HCCP. The

phosphorus/nitrogen based PCTP endowed EP thermosets excellent flame retardancy and smoke

suppression property. The TGA analysis indicated that EP composites with different PCTP content

exhibited an increased thermal resistance and charring property compared with the pure EP. The

compact char residues generated could play as a barrier to prohibit the heat and mass transfers and

cut off the oxygen supply in the air during the combustion, thus contributed to a large decrease in

P-HRR, THR and TSP values. Meanwhile, the triazine units could also decompose into

nonflammable volatiles to dilute the ignitable gases during the burning. The LOI values increased

dramatically from 22.3% to 28.0% when the content of PCTP moved from 0 to 8.7 phr. The EP

composites passed the UL-94 V-0 rating when 6.4 phr PCTP was added. Moreover, the

incorporation of PCTP decreased the water absorption, and also brought good compatibility and

strong interfacial interaction to EP matrix, thus the Tg values and mechanical properties of

EP@PCTP composites were barely influenced, demonstrating its potential practical applications.

5. Declarations of interest

24 / 33
 None.

Acknowledgment

The authors acknowledge the financial support from Shanghai Brightfield Chemicals Co. Ltd.,

China. The authors wish to thank Associate Prof. Dr. Yun Ding and Prof. Dr. Aiguo Hu for their

kindly assistance.

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Highlights
 Polyphosphazene covalent triazine polymer (PCTP) as a flame retardant was
synthesized.
 PCTP significantly decreased the fire hazard of epoxy resin (EP).
 PCTP functioned both in condensed and gaseous phases.
 PCTP effectively enhanced the water resistance of EP.
 The Tg values and mechanical properties of EP@PCTP composites were barely
influenced.

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