Journal of Colloid and Interface Science 608 (2022) 142–157

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Journal of Colloid and Interface Science

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

Exploration on structural rules of highly efficient flame retardant

unsaturated polyester resins
Fukai Chu, Shuilai Qiu, Shenghe Zhang, Zhoumei Xu, Yifan Zhou, Xiaoyu Luo, Xin Jiang, Lei Song,
Weizhao Hu ⇑, Yuan Hu ⇑
State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026, PR China

g r a p h i c a l a b s t r a c t

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

Article history: Owing to the lack of research on structure-activity relationship and interaction mechanism between
Received 9 August 2021 unsaturated polyester resins (UPR) and flame retardants, it has been a big challenge to prepare high-
Revised 17 September 2021 efficiency flame retardants for UPR in industry. In this research, to explore structural rules of high-
Accepted 20 September 2021
efficiency flame retardants, several polymeric flame retardants were synthesized with varied main-
Available online 24 September 2021
chain, side-chain, phosphorus valence states and contents of flame retardant elements. The thermal sta-
bilities of flame retardants and UPR composites were firstly assessed. It has been found the interaction
Keywords:
existed between flame retardants and UPR, through transesterification reaction and b scission pathway
Structural rules
Highly efficient flame retardants
in polyester and polystyrene chains. With only 15 wt% of PCH3-S, UPR composites can reach V0 rating
Unsaturated polyester resins in UL-94. The PHRR and THR values can be maximumly decreased by 71.66 % and 77.67 %, with 20 wt
Thermal behavior % of PB-S. It has been found flame retardants with sulfone group and + 3 valence state of phosphorus
Interaction mechanism in molecular backbone can release SO2 and phosphorus containing compounds in gaseous phase, which
diluted fuel fragments and catalyzed H
and HO
radical removal. The mechanism for improved flame
retardancy of UPR composites with various polymeric flame retardants were discussed in detail. Some
general rules for highly efficient flame retardant UPR can be summarized: First, gaseous phase flame
retardant mechanism plays the major role in improvement of flame retardant performance of UPR com-
posites; Second, the combination of + 3 valence state of phosphorus structures, higher phosphorus con-
tents and sulfone groups effectively improves the flame retardant efficiency of flame retardants.
Ó 2021 Published by Elsevier Inc.

⇑ Corresponding authors.
E-mail addresses: hwz1988@ustc.edu.cn (W. Hu), yuanhu@ustc.edu.cn (Y. Hu).

https://doi.org/10.1016/j.jcis.2021.09.124
0021-9797/Ó 2021 Published by Elsevier Inc.
F. Chu, S. Qiu, S. Zhang et al.
1. Introduction
The efficiency of low molecular flame retardants is decreased by
migration [1–3]. Polymeric flame retardants exhibit the advan-
tages of good migration resistance and matrix compatibility, as
well as wide processing temperature with high heat resistance
[4,5]. These characteristics improve the physical properties and
processing properties of materials [6]. Dihalophosphorus com-
pounds and diols are commonly used as monomers for polymeric
flame retardants. As-prepared polymeric flame retardants can
introduce many effective flame retardant elements and structural
units into the same molecules. At the same time, the flame-
retardant efficiency of polymeric flame retardants and uneven dis-
tribution and migration in the matrix are improved with structural
variations [7]. This firstly involves the changes in phosphorous
containing structures. Different phosphorous structures lead to
the difference of phosphorous valence state and contents of flame
retardant elements, which would further influence the flame retar-
dant efficiency [8]. However, there has no systematic analysis for
these effects, investigating the effect of structural variations on
thermal properties and flame retardant activities in detail. Also,
the mode of action for these structural variations has not been well
studied, which maybe vary from system to system [9]. The struc-
tural variations of polymeric flame retardants also involve the
combination of different flame retardant elements. In addition to
common elements such as phosphorus and nitrogen, sulfur con-
taining compounds in various forms have often serve as flame
retardant adjuvants [10,11]. Especially, sulfone group containing
compounds may release SO2 to gaseous phase, which is believed
to dilute the concentration of fuel fragments and catalyze flame-
propagating radicals removal reactions [12,13]. Meanwhile, the
generated sulfonic acids can also promote cationic crosslinking
and formation of carbonaceous layers in combustion process of
materials [14,15]. However, there is little analysis of the combined
action mechanism of phosphorus and sulfur elements, especially
for the phosphorus structures with different valence states.
Unsaturated polyester resin (UPR) is generally the linear poly-
mer with ester bonds and unsaturated double bonds, formed by
the condensation of unsaturated diacids and saturated diols. The
diluted solution of the resin in 30–40 % styrene crosslinking
monomer is cured by copolymerization to form thermosetting
resin with cross-linking structures [16,17]. Compared with other
thermosetting resins, UPR has low viscosity, moderate price, con-
venient processing and good formability at lower pressures and
temperatures. Meanwhile, owning to its high tensile strength,
light weight, chemical resistance and high insulation properties,
UPR composites are widely used in construction, chemical indus-
try, transportation, electrical [18,19]. However, both polyester and
polystyrene chains in the cured materials are highly flammable
[20]. At present, the flame-retardant UPR in industry is prepared
by adding a large number of commercial flame retardants, such
as 50 wt% of aluminium hydroxide or 30 wt% of ammonium
polyphosphate [21,22]. In these methods, the large amounts of
flame retardants, the poor compatibility and easy migration lead
to the decline of flame retardant efficiency and mechanical perfor-
mance [23,24]. An effective way to solve these problems is to pre-
pare effective flame retardants for UPR by designing reasonable
structures, improving the fire safety with low additive amounts.
However, for the high flammability of UPR, there is no specific
research on the design experience and conclusion of ideal flame
retardant structures. The structural variations may include the
main-chain/side-chain structures, the valence states of flame
retardant elements and the contents of these elements. The law
of structure-activity relationship between structures of flame
retardants and fire safety of UPR composites, is of great signifi-
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Journal of Colloid and Interface Science 608 (2022) 142–157
cance for the design and preparation of flame retardant UPR
materials in industry.
In this research, different polymeric flame retardants with dif-
ferent structures were prepared. Then, the effect of side chain/main
chain structures of flame retardants, phosphorus valence states,
combinations of flame retardant elements and elemental contents
on the fire safety performance of UPR composites were studied.
Finally, the general rules of effective flame retardancy for UPR
materials can be obtained, through the analysis of thermal decom-
position and combustion behaviors of materials, as well as the
flame retardant mechanism of different flame retardants.
2. Experimental
2.1. Materials
Phenyl dichlorophosphate, phenylphosphonic dichloride,
bisphenol A and bis(4-hydroxyphenyl) sulfone were bought from
Aldrich Chemical Co., Ltd (U.S.). Dichloromethane, chloroform,
methanol and trimethylamine were purchased from Sinopharm
Chemical Reagent Co., Ltd. Benzoyl peroxide (BPO) was also pro-
vided by Sinopharm Chemical Reagent Co., Ltd, which was recrys-
tallized through chloroform and methanol. Unsaturated polyester
resin (UPR, model 196) was bought from Hefei Chaoyu Chemical
Co., Ltd.
2.2. Synthesis of methylphosphonic dichloride
Methylphosphonic dichloride was prepared by the oxidizing
reaction of methyldichlorophosphine with high-purity oxygen
[25]. The detailed process was as follows: The dry high-purity oxy-
gen was continuously injected into a three-necked bottle contain-
ing 200 g of methyldichlorophosphine. Meanwhile, the system was
magnetically stirred at 35 ℃ for 24 h to produce methylphosphonic
dichloride crude products, which were then purified by vacuum
distillation at 100 ℃ (yields: 95%). Finally, the colorless transparent
liquid can be obtained. 1H and 31P NMR spectra of methylphospho-
nic dichloride were shown in Figure S1.
2.3. Synthesis of polymeric flame retardants
Various flame retardants were synthesized with phosphoryl
chloride compounds and diols. The synthetic route of polymeric
flame retardant additives was shown in Scheme 1. The products
with different reaction monomers, the yields, phosphorus contents
and sulfur contents were shown in Table 1. Take PCH3-S as an
example, bis(4-hydroxyphenyl) sulfone (0.11 mol, 27.53 g) and tri-
ethylamine (0.2 mol, 20.24 g) were firstly dispersed in 200 ml
dichloromethane. Then, the mixed solution of methylphosphonic
dichloride (0.1 mol, 13.29 g) and 50 ml dichloride were added
dropwise at room temperature. The system was heated to 60 °C
with magnetic stirring and condensation reflux for 24 h. After dry-
ing the dichloromethane in mixed system, the remaining solid
mixture were washed and filtered with diluted hydrochloric acid,
sodium bicarbonate, sodium chloride aqueous solutions and deion-
ized water several times to remove triethylamine hydrochloride.
Finally, the PCH3-S products can be obtained after vacuum drying
at 60 °C. PO-S, PB-S, PCH3-A, PO-A and PB-A were synthesized with
the same method.
2.4. Preparation of UPR composites
The formula of flame retardant UPR composites and the corre-
sponding flame retardant element contents were shown in Table 2.
F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Scheme 1. The synthetic route of polymeric flame retardant additives.

Table 1
The products with different reaction monomers, the yields, phosphorus contents and sulfur contents.

Products Dichloride Diols Yeilds (%) P (wt%) S (wt%)

PO-A Phenyl dichlorophosphate bisphenol A 85 8.45 /
PB-A Phenylphosphonic dichloride bisphenol A 87 8.84 /
PCH3-A Methylphosphonic dichloride bisphenol A 90 10.74 /
PO-S Phenyl dichlorophosphate bis(4-hydroxyphenyl) sulfone 86 7.98 8.26
PB-S Phenylphosphonic dichloride bis(4-hydroxyphenyl) sulfone 83 8.32 8.61
PCH3-S Methylphosphonic dichloride bis(4-hydroxyphenyl) sulfone 92 9.98 10.33

Table 2
The formula of flame retardant UPR composites and the corresponding flame retardant element contents.

Samples UPR (g) FR (g) BPO (g) P (wt%) S (wt%)

UPR 100 0 2.00 / /
UPR/PCH3-S 10% 90 10 1.80 1.00 1.03
UPR/PCH3-S 13% 87 13 1.74 1.30 1.34
UPR/PCH3-S 15% 85 15 1.70 1.50 1.55
UPR/PCH3-S 20% 80 20 1.60 2.00 2.07
UPR/PCH3-A 20% 80 20 1.60 2.15 /
UPR/PB-S 15% 85 15 1.70 1.25 1.29
UPR/PB-S 20% 80 20 1.60 1.66 1.72
UPR/PB-A 20% 80 20 1.60 1.77 /
UPR/PO-S 20% 80 20 1.60 1.60 1.65
UPR/PO-A 20% 80 20 1.60 1.69 /

The UPR composites were fabricated through adding various con-
tents of the synthesized flame retardants into UPR matrix. 2 wt%
BPO initiator was incorporated into the above mixture and stirred
uniformly, which was poured into Teflon mold after vacuum
degassing. After placing at 70 and 120 °C for 4 and 3 h respectively,
the flame retardant UPR composites can be obtained.
3. Results and discussion
3.1. Structural analysis of various flame retardants
The structures were characterized by FTIR and NMR, and the
detailed analysis was expressed in supplementary information.

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F. Chu, S. Qiu, S. Zhang et al.
Table 3
The weight-average molecular weight (Mw), number-average molecular weight (Mn), degree of polymerization (DP) and of polymeric flame retardants and melting temperature
(Tm).
Samples Structures
PO-A
PB-A
PCH3-A
PO-S
PB-S
PCH3-S
GPC was used to evaluate the weight-average molecular weight
(Mw), number-average molecular weight (Mn) and degree of poly-
merization (DP) of polymeric flame retardants (Table 3). For flame
retardants with same pendant side groups, the use of bisphenol A
resulted in the significantly higher molecular weight and degree of
polymerization compared with that of bis(4-hydroxyphenyl) sul-
fone. The lower molecular weight and polymerization degree of
sulfone group containing flame retardant may be related to lower
solubility of bis(4-hydroxyphenyl) sulfone and condensation pro-
duct in dichloromethane. However, the varying molecular weights
of polymeric flame retardants exhibit little effect on the flame
retardant performance of polymer composites theoretically [26].
The change of molecular weight has neither effect on the content
of flame retardant elements such as phosphorus and sulfur, nor
the melting temperatures of flame retardants (Table 3). Thus, to
optimize the activity of phosphorus containing additives, different
polymeric flame retardants were synthesized and assessed in their
effects on thermal performance and flammability of UPR. The
effects of flame retardants were mainly discussed as below: The
structural variations in main-chain/side-chain, the change of phos-
phorus valence states and the corresponding change in flame retar-
dant element contents.
3.2. Thermal stability of flame retardants
TGA was used to study the effect of structural changes of poly-
meric flame retardants on their thermal stability (Fig. 1), and some
important parameters such as the temperatures at weight loss of 5
and 10 wt% (T5% and T10%), the temperatures at maximum weight
loss rate (Tmax) and residues at 800 °C (Yc) were summarized in
Table S2. Compared with one degradation peak in DTG curves of
flame retardants under inert atmosphere, two degradation peaks
(Tmax1 and Tmax2) appeared under air condition, owning to the
degradation of polymer chain and further oxidation of char resi-
dues in condensed phase. Meanwhile, the Yc under N2 was twice
more than that under air atmosphere, indicating the thermal sta-
bilities of flame retardants under air were significantly lower than
that in inert atmosphere, due to the strong thermal oxygen degra-
dation reaction.
Under the same atmosphere, the thermal properties of flame
retardants were different due to the structural changes of main
chain and side chain. Under air condition, the range of T5% and
Journal of Colloid and Interface Science 608 (2022) 142–157
Mn Mw DP Tm (℃)
215.89
49,772 84,158 230
206.62
60,529 108,977 311
221.14
13,454 50,591 175
217.93
10,422 10,802 28
221.28
13,063 13,203 35
200.20
9560 10,982 32
T10% of all polymeric flame retardant additives was between 300
and 400 °C. Among them, PB-A showed the largest T5%, T10% and
Tmax1, which were 387, 416 and 475 °C, respectively. The Yc of
PO-A, PB-A and PCH3-A were 9.64, 9.81 and 6.09 wt%, while that
of PO-S, PB-S and PCH3-S were 14.96, 8.81 and 11.09 wt%. This
indicated sulfone in main-chain of synthesized flame retardants
presented higher char residues than that with isopropylidene.
Meanwhile, compared to PB-S and PCH3-S, PO-S showed the high-
est Tmax2 (624 °C) and Yc (14.96 wt%), indicating the pendant phe-
noxy in side-chain was most conductive to the charring capacity of
flame retardants.
Under N2 condition, the thermal behavior of the flame retar-
dants showed the similar trend to that under air. The T5% and
T10% ranged from 350 to 450 °C under N2 condition, which higher
than that under air. Alao, PB-A exhibited the largest T10% (477 °C)
and Tmax1 (533 °C). Meanwhile, compared with the Yc of 22.86,
19.95 and 13.78 wt% for PO-A, PB-A and PCH3-A, the Yc of PO-S,
PB-S and PCH3-S was increased to 36.65, 32.30 and 28.38 wt%,
which also confirmed that sulfone containing structure was more
conducive to increasing the charring capacity. Compared the flame
retardants with same main chain but different side chain, PO-A and
PO-S showed the higher Yc, also indicating the better charring
capacity of phenoxy structures. Additionally, the contents of phos-
phorus and sulfur in PO-S were obviously less than that of PB-S and
PCH3-S (Table 1). The results indicated the charring capacity of
flame retardants were not necessarily related to the content of
flame retardant elements, but to their specific structure and corre-
sponding phosphorus valence state, which would be further dis-
cussed in gaseous and condensed phase analysis.
3.3. Thermal degradation of flame retardants
TGA-FTIR was used to analyze the pyrolysis gaseous products of
different flame retardants [27–30]. Fig. 2 showed the FTIR spectra
of pyrolysis products of PCH3-S and PCH3-A at different tempera-
tures. For PCH3-S, the characteristic peaks at 2345 and 673 cm1
were ascribed to CO2, and peaks at 2180 and 1627 cm1 were
ascribed to CO and aromatic compounds, respectively [31]. Mean-
while, the characteristic peaks at 1290–1400 cm1 indicated the
sulfone group in PCH3-S generated SO2 during pyrolysis process .
SO2 peak showed a relatively weak intensity at 250 °C, became
obvious at 420 °C, and increased rapidly at 440 °C. Due to the
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F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Fig. 1. The thermal behaiors were analyzed by TGA and DTG curves under air and N2 atmosphere.

Fig. 2. FTIR curves of gaseous pyrolysis products at different temperatures through TGA-FTIR test: (a) PCH3-S and (b) PCH3-A.

phosphorus-containing structures in PCH3-S, P@O and PAO groups
containing gaseous products appeared at 1261 and 1168 cm1
respectively[32], where the peak intensity was obvious at 400 °C,
and increased significantly with the increase of temperatures. In
contrast, the FTIR spectrum of PCH3-A has no characteristic peak
of SO2 at the same position, but also appeared characteristic peaks
of CO2 (2348 and 663 cm1), CO (2179 cm1), aromatic compounds
(1596 and 1492 cm1), P@O (1261 cm1) and PO (1178 cm1).
Meanwhile, the stretching vibration peaks of hydrocarbyl appeared
at 2850–3160 cm1 in high temperature stage, which was attribu-
ted to the pyrolysis of isopropylidene group in PCH3-A.
TGA-MS was used to further analyze the pyrolysis products of
PCH3-S and PCH3-A. Fig. 3 was the total ion current chromatogram
(TIC) of PCH3-S and PCH3-A in N2 atmosphere. The temperature for
maximum TIC intensity of PCH3-S was obviously lower than that of
PCH3-A, which was consistent with the DTG results in Fig. 1. The
difference in main chain structures between PCH3-S and PCH3-A
caused obvious changes in pyrolysis products in TGA-MS. Fig. 4
showed the mass spectra of PCH3-S at different temperatures in
the TIC. At 250 ℃, there appeared fragmentation of phenol (m/
z = 94), phosphorus-containing substances (m/z = 141, 173, 174,
249 and 250) and sulfur-containing materials (m/z = 235 and
236) [33]. As temperatures rose, the phosphorus and sulfur-
containing compounds with larger molecular weights were further
cracked to aromatic products such as phenol and benzene (m/
z = 78). At 350 °C, higher molecular weight phosphorus and

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F. Chu, S. Qiu, S. Zhang et al.
Fig. 3. The TIC curves of PCH3-S and PCH3-A in unit mass.
sulfur-containing compounds would be further cracked into frag-
ments with m/z = 47, 48 and 64, which were mainly small mole-
cule fragments such as PO
, HPO and SO2. The relative intensities
of these small molecules in mass spectrum were gradually
increased, and significant at 400–500 °C. However, as the temper-
ature further increased, the relative intensities gradually
decreased. Fig. 5 showed the mass spectra of PCH3-A at different
temperatures in the TIC chart. Compared with PCH3-S, PCH3-A pro-
duced more products during the pyrolysis process with isopropy-
lene structures in main chain. At 250 ℃, the fragments (m/z = 76,
91 and 104) were mainly aromatic compounds, while the frag-
ments at m/z = 141 and 250 were mainly phosphorus-containing
substances. As temperatures rose to 350 °C, the fragments at m/
z = 94, 119 and 134 were mainly phenol and other aromatic sub-
stances, due to the combination of hydrocarbyl radicals generated
from isopropylene structures. When the temperature further
increased, the phosphorus-containing material at m/z = 250 gradu-
ally disappeared, and fragments mainly composed of PO
and PO2

(m/z = 47 and 63) appeared [33].
RT-FTIR was used to analyze the condensed phase of PCH3-A
and PCH3-S. As shown in Fig. 6, though the RT-FTIR spectra of
PCH3-A and PCH3-S were similar, they exhibited their own charac-
teristic peaks with different main chain structures. For example,
the CAH peaks appeared at 2900–3000 cm1 for PCH3-A and the
S@O peak appeared at 1320 cm1 for PCH3-S. Moreover, these
two characteristic peaks disappeared at about 400 and 450 °C,
which corresponded to temperatures where hydrocarbons and
SO2 appeared in pyrolysis gaseous products of PCH3-A and PCH3-
S. The PAO (1210 cm1), PAOAPh (920 cm1) and P@O
(568 cm1) disappear at 400 °C, which also corresponded to tem-
peratures at which phosphorus-containing compounds appeared
in pyrolysis gaseous products [34]. Since sulfonic acid can be gen-
erated from the thermal degradation of sulfone group in condensed
phase, the PCH3-S still exhibited the S@O signal (1150 cm1) at
high temperature [35]. To analyze effects of differences in
phosphorus-containing structures on pyrolysis products of poly-
meric flame retardant, TGA-FTIR and TGA-MS technology were also
used to analyze the thermal degradation process of PB-S and PO-S.
The detailed analysis was shown in supplementary information.
3.4. Thermal stability of UPR composites
The TGA and DTG were also used to analyze different flame
retardant UPR composites in air and N2 [36–38]. As shown in
Fig. 7, Table S3-S4, the thermal stability of UPR composites under
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Journal of Colloid and Interface Science 608 (2022) 142–157
N2 was generally higher than that under air atmosphere. Mean-
while, compared to one thermal degradation stage under N2, there
appeared two thermal degradation stages under air conditions, due
to the oxidation reaction. Moreover, the Yc under N2 was higher
than that under air atmosphere for the same UPR composites.
Under air atmosphere, the Yc of UPR/PCH3-A 20% and UPR/PCH3-
S 20% were 0.43 and 0.74 wt%, respectively. Under N2, the Yc of
UPR/PCH3-A 20% and UPR/PCH3-S 20% were 6.41 and 12.78 wt%,
respectively. The results indicated sulfone containing PCH3-S was
more conducive to charring capacity of UPR in thermal decomposi-
tion process than the PCH3-A.
Meanwhile, the difference in side chains of flame retardants
would also affect the charring capacity of UPR composites in high
temperature. Under air atmosphere, the Yc of UPR/PCH3-S 20%
and UPR/PB-S 20% were 0.74 and 0.84 wt%, and the Yc of UPR/
PO-S 20% increased to 2.14 wt%. Under N2, the Yc of UPR/PCH3-S
20% and UPR/PB-S 20% were 6.41 and 8.85 wt%, while 12.78 wt%
for UPR/PO-S 20%. These results indicated PO-S was more con-
ducive to the formation of char residues of UPR composites, com-
pared with flame retardants with the same main chain structures
(PCH3-S and PB-S). This was consistent with the Yc of flame retar-
dants, indicating the phenoxy structure in side chain was more
conducive to the char formation of UPR.
Additionally, it has been found an interesting phenomenon
from Table S3 and S4. All values of T5%, T10%, Tmax and Yc for flame
retardants were higher than that of pure UPR. However, when
these polymeric flame retardants were added in UPR matrix to pre-
pare UPR composites, the T5% and T10% of composites were signifi-
cantly lower than pure UPR. This indicated that the addition of
flame retardants in UPR broadened the temperature range of ther-
mal degradation of UPR composites. This was observed more
clearly by the comparison of TGA and DTG curves obtained by
experiment and theoretical calculation (Figure S9). For all compos-
ites, the pyrolysis process of UPR composites calculated by linear
proportion was between flame retardants and pure UPR, and the
results obtained by experiment was prior to that of pure UPR under
both air and N2 atmosphere. These results indicated an interaction
between polymeric flame retardants and UPR matrix during the
thermal decomposition of composites, rather than a simple linear
sum. Moreover, as shown by the arrow in Figure S9, the experi-
mental curves presented small peaks of thermal degradation rate
before Tmax1 compared with the calculated curves, also confirming
the interaction between flame retardants and URP during degrada-
tion process. This peak may be the weight loss caused by transes-
terification reaction between UPR matrix and flame retardants
(Fig. 8) [39,40]. This reaction was confirmed in the section of con-
densed phase analysis below.
3.5. Flame retardant performance of UPR composites
The flame retardant performance of UPR composites with poly-
meric flame retardants were assessed by UL-94 test, and the corre-
sponding results were listed in Table 4. Compared with no rating of
pure UPR, the flame retardant rating of UPR composites with flame
retardants changed with the structures of flame retardants. With
same pendant side chain, flame retardants with isopropylidene in
main chain (PCH3-A, PB-A, PO-A) brought poor flame retardant
results for UPR composites. The UPR composites showed no rating
even at 20 wt% of addition. With sulfone group in main chain, both
UPR/PCH3-S 15% and UPR/PB-S 20% composites reached V0 rating,
indicating sulfone group in polymeric flame retardants can effec-
tively promote the fire safety performance of URP.
Meanwhile, differences in side chains would also affect the effi-
ciency of polymeric flame retardants. With pendant phenoxy
group, PO-S presented the worst flame retardant efficiency and
UPR/PO-S 20% composites had no rating in UL-94; With phenyl
F. Chu, S. Qiu, S. Zhang et al.
Fig. 4. The mass spectra of PCH3-S at different temperatures in TIC curves.
group, 15 wt% and 20 wt% of PB-S allowed UPR composites to reach
V2 and V0 rating; For PCH3-S, the addition of 13 wt% and 15 wt%
made UPR composites reach V1 and V0, respectively. Thus, PCH3-
S enabled URP to exhibit the best flame retardant performance,
mainly related to the higher phosphorus and sulfur contents of
UPR/PCH3-S composites at the same amount.
However, the content of flame retardant elements was not the
only factor affecting flame retardant performance of UPR compos-
ites. For example, it has been found that UPR/PCH3-S 15% can reach
higher V0 rating at lower contents of phosphorus and sulfur ele-
ments, through the comparison of UPR/PCH3-S 15% and UPR/PO-S
20% composites. This indicated phosphorous containing structures
in polymeric flame retardants and their corresponding phospho-
rous valence states can also affect the flame retardant efficiency.
Cone calorimeter was also used to analyze the heat release
behaviors of UPR composites with different polymeric flame retar-
dants during combustion process (Fig. 9 and Table S5) [41–44].
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Journal of Colloid and Interface Science 608 (2022) 142–157
Compared with pure UPR, both peak of heat release rate (PHRR)
and total heat release (THR) of UPR composites with polymeric
flame retardants experienced obvious reduction. Meanwhile, com-
pared with isopropylidene containing flame retardants (PCH3-A,
PB-A, PO-A), the decrease of PHRR and THR of UPR composites
was more obvious with sulfone group (PCH3-S, PB-S, PO-S), indicat-
ing sulfone was conducive to inhibiting heat release. With the
same addition contents and main chain structures, the flame retar-
dant efficiency of + 3 valence state phosphorus structure was bet-
ter than + 5 valence structure. Among them, the PHRR and THR
of UPR composites were decreased by 69.73% and 71.48% with
20 wt% of PCH3-S, compared with pure UPR; The PHRR and THR
were maximumly decreased by 71.66 % and 77.67 % with 20 wt%
of PB-S. The great inhibition of PCH3-S and PB-S on heat release
was mutually confirmed with best flame retardant performance
in UL-94 tests. Fire generation index (FGI) is the ratio between
PHRR and tPHRR, which was applied to evaluate the fire safety per-
F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Fig. 5. The mass spectra of PCH3-A at different temperatures in TIC curves.

Fig. 6. RT-FTIR curves were used to analyze the change of condensed phase products with increasing temperatures: (a) PCH3-A and (b) PCH3-S.

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Fig. 7. The TGA and DTG curves of UPR composties under air and N2 atmosphere.

Fig. 8. Schematic diagram of transesterification reaction between UPR matrix and polymeric flame retardant.

Table 4 3.6. Thermal degradation of UPR composites

The results of UL-94 for UPR composites, and the corresponding contents of P and S
elements.
TGA-FTIR was also used to analyze the gaseous products of UPR
Samples UL-94 P (wt%) S (wt%) composites. Fig. 10 showed the FTIR spectra of pyrolysis volatiles
UPR No / / of pure UPR at different temperatures and many similar peaks
UPR/PCH3-S 10% No 1.00 1.03 were observed in infrared spectra of pyrolysis gaseous products,
UPR/PCH3-S 13% V1 1.30 1.34 such as hydrocarbon (3081 cm1), CO2 (2304 cm1), CO
UPR/PCH3-S 15% V0 1.50 1.55
(2175 cm1) and aromatic compounds (1494 and 910 cm1) [45–
UPR/PCH3-S 20% V0 2.00 2.07
UPR/PCH3-A 20% No 2.15 / 48]. Meanwhile, the characteristic peak of carbonyl compounds
UPR/PB-S 15% V2 1.25 1.29 at 1752 cm1 was attributed to the presence of ester groups in
UPR/PB-S 20% V0 1.66 1.72 UPR materials. The peak intensity of gaseous products increased
UPR/PB-A 20% No 1.77 /
rapidly from 400 ℃, reached the maximum at 460 °C, and then
UPR/PO-S 20% No 1.60 1.65
UPR/PO-A 20% No 1.69 / gradually decreased.
The FTIR spectra of pyrolysis volatiles of UPR/PCH3-S 20 %和
formance of UPR composites. A lower FGI value indicates the UPR/PCH3-A 20% showed similar peaks to pure UPR (Fig. 11).
higher fire safety performance. Compared with 5.47 kW/(m2
s) of Meanwhie, some new characteristic peaks appeared the structural
pure UPR, the FGI of UPR composites with polymeric flame retar- difference of flame retardants. For UPR/PCH3-S 20%, the character-
dants decreased. Particularly, the FGI of UPR/PCH3-S 20% decreased istic peak of SO2 appeared at 1357 cm1 from thermal degradaiton
to 2.41 kW/(m2
s), experiencing a 55.94 % reduction compared of sulfone structures in the PCH3-S flame retardant. As reported in
with pure UPR. All these results indicated the good flame retardant literatures, SO2 can dilute the concentration of combustible gas-
performance of UPR composites, provided by the combination of eous products and generated the following H
and HO
radical elim-
+ 3 valence state phosphorus structure and sulfone group in flame ination reactions, thereby affecting the pyrolysis and combustion
retardants. behavior of UPR composites [13].

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F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Fig. 9. (a) HRR and (b) THR curves of UPR composites with various polymeric flame retardants.

SO2 H
!HOSO

HOSO
H
!SO2 H2

Fig. 10. FTIR curves of gaseous pyrolysis products at different temperatures
through TGA-FTIR test for pure UPR.
HOSO
HO
!SO2 H2 O
The FTIR spectra of UPR/PCH3-S 20% and UPR/PCH3-A 20% also
showed characteristic peaks of P@O (1243 cm1) and PAO
(1130 cm1). Phosphorus-containing compounds were cracked
and generated PO
and PO2
free radicals, which can also capture
H
and HO
free radicals, further affecting the pyrolysis and com-
bustion behavior of UPR composites [49]. TGA-FTIR was also used
to analyze the effect of difference in phosphorus structure on gas-
eous products of UPR materials. The FTIR spectra of gaseous pyrol-
ysis products of UPR/PB-S 20% and UPR/PO-S 20% were similar to
those of UPR/PCH3-S 20%. There were also hydrocarbons, CO2, CO,
carbonyl compounds, aromatic compounds, SO2 and phosphorus-
containing compounds.
For polyester segments in UPR materials, the transesterification
reaction between flame retardants and polyester chains not only
occured before thermal decomposition process, but also during
thermal degradation of UPR composites (Fig. 12a). This was mainly
because the formation of low molecular weight ester-based com-
pounds during the thermal degradation of polyester segments
[34,45], which further underwent the transesterification reaction

Fig. 11. FTIR curves of gaseous pyrolysis products for (a) UPR/PCH3-S 20% and (b) UPR/PCH3-A 20%.

151
F. Chu, S. Qiu, S. Zhang et al.
Fig. 12. (a) The transesterification reaction during degradation process of polyester chain; (b) The thermal degradation of polystyrene proceeded through b scission pathway.
and generated small molecular substances, thereby accelerating
the pyrolysis of UPR composites. Also, flame retardants would also
advance the pyrolysis of polystyrene segments in UPR. The
phosphorus-containing radicals generated by the pyrolysis of
flame retardants extract hydrogen from the skeleton of polystyrene
segments to produce stable polystyrene free radicals [50–52].
Then, the polystyrene segments were pyrolyzed by b-breaking
method (Fig. 12b). The interaction between flame retardants and
UPR matrix was achieved by transesterification of different ester
groups and degradation enhancement effect of phosphorus con-
taining free radicals. Such interaction acted on polyester and poly-
styrene segments respectively, enhancing the degradation of UPR
composite and broaden the temperature range of thermal
degradation.
The digital pictures showed the carbon residues of UPR compos-
ites after cone calorimetric (Fig. 13). Compared with a small
amount of residues of pure UPR, the residues of UPR/PCH3-S com-
posites did not increase obiously. Meanwhile, comparing UPR/
PCH3-S 20%-UPR/PCH3-A 20%, UPR/PB-S 20%-UPR/PB-A 20%, and
UPR/PO-S 20%-UPR/PO-A 20%, different structures in main chains
had no obvious effect on macroscopic morphology of char residues
of UPR materials. However, it can be found UPR/PO-S 20% retained
more residues, comparing UPR/PCH3-S 20%, UPR/PB-S 20% and
UPR/PO-S 20%, indicating the phenoxy phosphorus structure
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Journal of Colloid and Interface Science 608 (2022) 142–157
with + 5 valence state of phosphorus can enhance the charring
capacity of UPR composites. SEM was used to observe the micro-
morphologies of UPR materials after combustion (Fig. 14). In con-
trast, although the quality of carbon layers of UPR/PCH3-S was
slightly better than pure UPR, there were still many cracks. Com-
pared with UPR/PCH3-S 20%, UPR/PCH3-A 20% had no pores in
the carbon layers. The carbon layers UPR/PB-S 20% were frag-
mented and cracked, but the micro-morphology of UPR/PB-A 20%
was relatively complete. Meanwhile, carbon residues of UPR/PO-S
20% were dense and complete, which can effectively inhibit the
transfer of heat, pyrolysis products and oxygen from condensed
phase flame retardant mechanism. It was worth noting that even
though PCH3-S and PB-S flame retardants had better flame retar-
dant effeciency, but the integrity of the carbon layers were not as
good as UPR/PO-S 20%. This result indicated higher flame retardant
properties of PCH3-S and PB-S flame retardant UPR materials were
more from aseous phase effect of flame retardants.
RT-FTIR was used to analyze products in condensed phase dur-
ing the thermal decomposition of UPR composites, analyzing the
interaction between UPR matrix and flame retardants. Though
RT-FTIR of UPR composites was similar to pure UPR (Fig. 15a),
there appeared some new changes caused by the flame retardants.
For example, the peak at 920 cm1 was ascribed to the PAO
stretching vibration in PAOAPh structure (Fig. 15b-e). For UPR
F. Chu, S. Qiu, S. Zhang et al.
Fig. 13. The digital pictures of carbon residues of UPR composites after combustion.
composites with sulfone group containing flame retardants, the
S@O stretching vibration band appeared at 1150 cm1 (Fig. 15b-
d). These characteristic peaks changed with the increasing temper-
atures. Due to the degradation of sulfone group and resulting
release of SO2, the S@O peak got weaker but not going away at high
temperatures, indicating the remaining of S@O in condensed
phase. This was consistent with the above analysis on thermal
degradation of flame retardants, where sulfone group generated
SO2 for radical capture reaction in gaseous phase and also played
catalytic charring effect with the formation of sulfonic acid in con-
densed phase. The PAO stretching peak in PAOAPh also decreased
gradually, which started at 300 ℃. However, no thermal degrada-
tion of flame retardants was observed at this temperature. This
indicated the change of internal structure of UPR composites, and
the transesterification reaction was likely to occur at this time
(Fig. 8). Nor has PAO characteristic peak completely disappeared
in condensed phase, indicating the phosphorous-containing groups
participated in condensed reaction process during the thermal
degradation of UPR composites. Additionally, XPS was used to con-
firm the existance of phosphorous and sulfur elements in char resi-
dues of UPR composites after combustion (Figure S11 and
Table S6).
3.7. Mechanism analysis
The weights of UPR composites during combustion were also
recorded by cone calorimeter. Fig. 16a and b showed the curves
of weight loss and weight loss rate, respectively. Compared to pure
UPR, the final char residues of flame retardant UPR composites
increased. However, the increase varied with the structure and
contents of flame retardants. UPR/PO-S 20% had the highest char
residues, because generation of strong acid from the degradation
153
Journal of Colloid and Interface Science 608 (2022) 142–157
of + 5 valence state of phosphorus and sulfone group, which would
further catalyze the formation of carbon layers. The char residues
of UPR composites with PCH3-S and PB-S flame retardants exhib-
ited the limited increase. Especially, when contents of PCH3-S
increased from 10 wt% to 20 wt%, the final char residues did not
increase significantly. This result indicated the degradation prod-
ucts of + 3 valance state of phosphorus sturctures mainly existed
in gaseous phase, improving flame retardant performance of UPR
composite by free radical capture reaction. Meanwhile, compared
with pure UPR, the peak of maximum degradation rate of UPR
composites appeared earlier, which was also consistent with the
thermal behavior of UPR composites. The relationship between
THR and final weight loss of UPR composites was depicted in
Fig. 16c. For UPR composites with PCH3-A, PB-A and PO-A, their
THR and weight loss were larger than composites with sulfone
containing flame retardants, indicating that the worse flame retar-
dant efficiency of isopropylidene containing flame retardants.
Meanwhile, the weight loss of UPR composites with PCH3-A, PB-
A and PO-A showed little difference, indicating the single use of
phosphorus structures cannot effectively change the charring
capacity of UPR composites during combustion. For UPR compos-
ites with PCH3-S, PB-S and PO-S, the THR showed little different
with similar weight loss. This indicated the combination of phos-
phorous structure and sulfone group promoted charring capacity
of flame retardants. Among them, PO-S brought minimum weight
loss with similar THR, confirming it was mainly condensed phase
flame retardant mechanism; PCH3-S caused the highest weight loss
with similar THR, indicating flame retardant mechanism in gaseous
phase; And PB-S had obvious effect in both gaseous phase and solid
phase.
In a word, the effect of different polymeric flame retardants on
flame retardant performance of UPR was influenced by structural
F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Fig. 14. The SEM pictures of carbon layers of UPR composites after combustion.

Fig. 15. RT-FTIR was used to analyze the change of condensed phase products with increasing temperatures: (a) pure UPR, (b) UPR/PCH3-S 20%, (c) UPR/PO-S 20%, (d) UPR/PB-
S 20% and (e) UPR/ PCH3-A 20%.

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F. Chu, S. Qiu, S. Zhang et al. Journal of Colloid and Interface Science 608 (2022) 142–157

Fig. 16. The curves of (a) weight loss and (b) weight loss rate; (c) The relationship between THR and final weight loss of UPR composites.

variations. Firstly, these structural changes caused difference in
contents of flame retardant elements. Generally, the higher the ele-
ment content, the higher the flame retardant performance. This
increase improved the catalytic charring of phosphoric acid,
pyrophosphoric acid and sulfonic acid, as well as the radical cap-
ture and fuel dilution efficiency of phosphorus containing free rad-
icals and SO2. The schematic diagram was shown in Fig. 17, taking
PCH3-S as an example. Secondly, the variations in structures and
elemental valence states of flame retardants can affect the effi-
ciency of catalytic charring and free radical capture. For example,
even though the phosphorus content was lowest in flame retar-
dants with pendant phenoxy in side chains, it had the highest char-
ring capacity; Moreover, although flame retardant element
contents in UPR/PCH3-S 15% composites were lower than UPR/
PO-S 20%, its exhibited better fire safety in UL-94. Thus, the methyl
phosphoryl structure and sulfone group in polymeric flame retar-
dant brought the best flame retardant performance for UPR com-
posites, through the reasonable combined strategies of higher
phouphorus contents, sulfone group and + 3 valence state phos-
phorus structures.
4. Conclusions
To explore the effects of structural variations on activity of
flame retardants and prepare high fire safety UPR composite, dif-
ferent polymeric flame retardants were synthesized. The effects
of flame retardants were mainly discussed in structural variations
in main-chain/side-chain, phosphorus valence states and flame
retardant element contents. FTIR, NMR and GPC were used to eval-

Fig. 17. The schematic diagram for flame retardant mechanism of PCH3-S.

155
F. Chu, S. Qiu, S. Zhang et al.
uate structures of these polymeric flame retardants. There existed
interactions between polymeric flame retardants and UPR matrix,
through the transesterification reaction and b scission pathway
in polyester and polystyrene chains, respectively. The effect of
structural variations on flame retardant performance of UPR com-
posites were also studied. With 15 wt% of PCH3-S, the UPR compos-
ites can reach V0 rating. The PHRR and THR values can be
decreased by 71.66 % and 77.67 % with 20 wt% of PB-S. Through
gaseous and condensed phase analysis, it found that flame retar-
dants with sulfone group and + 3 valence state of phosphorus ele-
ments in molecular backbone can release SO2 and phosphorus
containing compounds in gaseous phase, which diluted the fuel
fragments and catalyzed H
and HO
radical removal reactions.
The flame retardants with sulfone in main chain and + 5 valence
state of phosphorus elements presented higher charring capacity
in condensed phase, owning to the formation of carbonaceous lay-
ers through sulfonic acid, phosphoric acid and pyrophosphoric acid
entities. Finally, some structural rules of highly efficient flame
retardants for UPR composites can be obtained. Firstly, compared
with + 5 phosphorus valence structure, +3 phosphorus valence
structure is more conducive to the improvement of flame retar-
dancy of UPR. Even with lower phosphorus contents in modified
UPR, the UL-94 rating of UPR composites with + 3 phosphorus
valence structure is still higher than the flame-retardant UPR
with + 5 phosphorus valence structure. Secondly, the combination
of phosphorus structures and sulfone groups can effectively pro-
mote the flame retardant efficiency. Additionally, compared with
condensed phase mechanism, the gaseous phase mechanism plays
the major role in improvement of flame retardant performance of
UPR composites.
CRediT authorship contribution statement
Fukai Chu: Conceptualization, Writing – original draft. Shuilai
Qiu: Methodology. Shenghe Zhang: Writing – review & editing.
Zhoumei Xu: Visualization. Yifan Zhou: Visualization. Xiaoyu
Luo: Validation. Xin Jiang: Resources. Lei Song: Supervision. Weiz-
hao Hu: Project administration. Yuan Hu: Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The research was financially supported by the National Natural
Science Foundation of China (No. 51991352, No. 51874266 and No.
51973203), the Fellowship of China Postdoctoral Science Founda-
tion (No. 2021TQ0316), and the Fundamental Research Funds for
the Central Universities (WK2320000043 and WK2320000044).
Appendix A. Supplementary material
Characterizations; NMR analysis of methylphosphonic dichlo-
ride; FTIR and NMR of synthesized flame retardants; Thermal
degradation of PB-S and PO-S; Table S1-S5; Fiugre S1-S10. Supple-
mentary data to this article can be found online at https://doi.org/
10.1016/j.jcis.2021.09.124.
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