Composites Part B 233 (2022) 109647

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Novel glycerol-based polymerized flame retardants with combined

phosphorus structures for preparation of high performance unsaturated
polyester resin composites
Fukai Chu a, Shuilai Qiu a, Yifan Zhou a, Xia Zhou a, b, Wei Cai a, Yulu Zhu a, Lingxin He a, c,
Lei Song a, Weizhao Hu a, *
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui, 230026, PR China
b
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu, 210094, PR China
c
State Grid Anhui Electric Power Research Institute, Hefei, Anhui, 230601, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Owing to poor flame retardant efficiency and compatibility of traditional flame retardants, it is difficult to
Unsaturated polyester resin prepare unsaturated polyester resins (UPR) composites with excellent flame retardant properties. In this
Glycerol-based polymerized flame retardants research, novel glycerol-based polymeric flame retardants (PCH3PG, PBPG and POPG) were synthesized. The
Combined phosphorus structures
effect of different side chains, phosphorus contents and combined structures on flame retardancy efficiency of
Compatibility
UPR composites were explored. It has been found POPG was more conducive to improving char formation under
High performance
high temperatures than PCH3PG and PBPG. However, PCH3PG and PBPG exhibited better flame retardant effi­
ciency in flame retaradant UPR composites. Especially for UPR/PCH3PG, the flame retardant performance
increased rapidly with increasing PCH3PG contents. With only 15 wt% of PCH3PG in UPR, UPR/PCH3PG 15%
reached UL-94 V0 and 29% of LOI. When PCH3PG contents increased to 20 wt%, the LOI of UPR/PCH3PG 20%
increased to 30%, and PHRR and THR were reduced by 67.93% and 57.22%, compared with pure UPR. The
thermal degradation products and flame retardant mechanism in gaseous and condensed phase were studied. It
was found the most efficient PCH3PG was mainly played flame retardant effect in gaseous phase, supplemented
by the barrier effect of condensed phase. Additionally, the polymeric glycerol-based flame retardants exhibited
good compatibility with UPR matrix. This work explores the high-efficiency flame retardant structures with good
compatibility for UPR, promoting the wide application of UPR materials.

1. Introduction phosphorus-containing flame retardants, which are important compo­

Compared with halogen-containing flame retardant systems,
halogen-free phosphorus-containing systems present characteristics of
low smoke, low toxicity and non-polluting, which are the hotspots of
flame retardant polymer composites [1–4]. However, traditional
phosphorus-containing flame retardants cannot meet the application of
flame retardant materials in humid environments, due to the poor
thermal stability, poor water resistance, and poor compatibility with
polymer [5,6]. In recent years, the research has developed towards
polymeric flame retardants with macromolecular groups, to solve the
problem of migration caused by water in the actual application process
and improve the flame retardant efficiency [7,8]. In flame retardant
systems, char-forming agents are often used in combination with
nents affecting the flame retardant effect [9]. The most commonly used
char-forming agent is pentaerythritol [10,11]. By contrast, bio-based
glycerol exhibits better application prospects because of its environ­
mentally friendly nature [12]. However, the compounded compounds
with these small-molecule char-forming agents have poor flame retar­
dant efficiency and are easy to migrate out, due to poor heat resistance
and water solubility. To solve these problems, glycerol can be used as a
reaction platform to combine glycerol and phosphorus-containing
compounds through its hydroxyl group.
As an organophosphorus flame retardant with phosphaphenanthrene
structure, 9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) pre­
sents the advantages of phosphorus-containing flame retardants
[13–15]. Meanwhile, the high chemical stability and thermal stability of

* Corresponding author.
E-mail addresses: leisong@ustc.edu.cn (L. Song), hwz1988@ustc.edu.cn (W. Hu).

https://doi.org/10.1016/j.compositesb.2022.109647
Received 17 October 2021; Received in revised form 30 November 2021; Accepted 11 January 2022
Available online 14 January 2022
1359-8368/© 2022 Published by Elsevier Ltd.
F. Chu et al.
Fig. 1. Synthesize of phosphorus-containing glycol.
the biphenyl structure in DOPO give P–C bond excellent chemical sta­
bility, which makes its flame retardancy better than traditional organic
phosphate flame retardants [14]. At the same time, in order to further
broaden the application field, DOPO can be used as a reaction starting
material to synthesize many derivatives and further improve its flame
retardant efficiency [16–18]. The formation of DOPO derivatives is
usually through the reaction between the active P–H bond and the
alkenyl, carbonyl, imino, epoxy, etc. Additionally, the combination of
different phosphorus structures in flame retardants greatly improves the
flame retardant performance of polymers. For example, Jiang et al.
successfully synthesized a reactive flame retardant (DHP) which con­
tained multi-phosphorus valence structures, to improve the problems of
easy migration and low efficiency of traditional additive flame re­
tardants [19]. DHP was introduced into molecular chain skeleton of
polymers to prepare flame retardant composites. The results showed the
multi-phosphorus valence structures in DHP not only inhibited the
release of combustible pyrolysis products, but also captured free radicals
in gaseous phase to stop the combustion. Also, DHP can catalyze the
production of thermally stable char layers in condensed phase. Zhang
Fig. 2. Synthetic route of PBPG, POPG and PCH3PG.
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Composites Part B 233 (2022) 109647
et al. synthesized a novel DOPO-PEPA flame retardant through the
Atherton-Todd reaction between DOPO and pentaerythritol phosphate
alcohol (PEPA), which was incorporated it into epoxy resin as an addi­
tive flame retardant [20]. The study found that the synergistic effect of
different phosphorus structures in DOPO-PEPA was more conducive to
the improvement of flame retardant performance of epoxy than use of
DOPO or PEPA alone. Bai et al., synthesized star-shaped triazine group
containing DOPO derivative (TRIPOD-DOPO). The UPR composites can
reached V0 rating 30.5% of LOI with 30 wt% of TRIPOD-DOPO [21,22].
These results showed that the combination of different flame retardant
structures can combine gaseous phase and condensed phase mecha­
nisms, providing a promising flame retardant method for polymers and
stimulating the exploration of high-efficiency flame retardant structures
[23–26].
Due to low cost and excellent molding process, unsaturated polyester
resin (UPR) has been widely used in the fields of urban construction, rail
transit and wind power development, etc [27–29]. However, the use of
reactive styrene diluent makes the cured UPR contain both polyester and
polystyrene segments. Both molecular segments exhibit extremely
F. Chu et al. Composites Part B 233 (2022) 109647

flammable characteristics, which severely limits the wide application of Table 1

UPR [30]. In previous research, the flame retardant performance of UPR The composition of different UPR composites and contents of corresponding
are often improved through the addition of large amounts of traditional phosphorus elements.
flame retardants, such as ammonium polyphosphate, aluminum hypo­ Samples UPR (g) Flame BPO (g) P (%)
phosphite, and aluminum hydroxide [31–33]. However, these studies Retardant (g)
have not designed flame retardants with suitable structures based on the UPR 100 0 2.00 0
composition and structural characteristics of UPR. Meanwhile, the poor UPR/PCH3PG 13% 87 13 1.74 2.20
compatibility of traditional flame retardants has further reduced their UPR/PCH3PG 15% 85 15 1.70 2.54
UPR/PCH3PG 20% 80 20 1.60 3.38
flame retardant efficiency [21]. Thus, to improve the flame retardant
UPR/PBPG 15% 85 15 1.70 2.17
efficiency and the dispersion of the flame retardant in UPR, it is neces­ UPR/PBPG 20% 80 20 1.60 2.89
sary to analyze the structural law of compatible high-efficiency flame UPR/POPG 15% 85 15 1.70 2.09
retardants. In this research, a novel DOPO-based diol (PG) was first UPR/POPG 20% 80 20 1.60 2.79
prepared by the Atherton-Todd reaction between glycerol and DOPO.
Then, three polymeric glycerol-based flame retardants (PCH3PG, PBPG
PCH3PG was same as PBEG, and all three synthetic flame retardants are
and POPG) were synthesized with varied side chains, phosphorus con­
viscous liquids.
tents and combined flame retardant structures. Thus, the effect of
different flame retardant structures on properties of UPR composites can
be explored. The flame retardant performance and mechanism of flame 2.3. Fabrication of UPR composites
retaradant UPR compsites were analyzed. Additionally, the dispersion
and compatibility of flame retardants and the mechanical properties of The composition of different UPR composites and contents of cor­
UPR composites were studied. responding phosphorus elements are shown in Table 1. Different
amounts of PBPG, POPG and PCH3PG were introduced to UPR matrix.
2. Experimental Then the BPO initiator accounting for 2 wt% of UPR matrix was added
and stirred uniformly. After vacuum degassing, the mixture was poured
2.1. Materials into the polytetrafluoroethylene mold, curing at 70 and 120 ◦ C for 4 and
3 h respectively. Taking PCH3PG as example, the flame retardant UPR
Glycerol, 10H-9-Oxa-10-phosphaphenanthrene 10-oxide (DOPO), composites was named UPR/PCH3PG x%, where x% was the proportion
triethylamine, dichloromethane and carbon tetrachloride were pur­ of PCH3PG in UPR composites.
chased from Aladdin Chemical Reagent Co., Ltd (China). Phenyl
dichlorophosphate and phenylphosphonic dichloride were purchased 2.4. Characterization
from Sinopharm Chemical Reagent Co., Ltd (China). The preparation of
methylphosphonic dichloride was according to previous literatures [7, The characterization methods were shown in supplementary
34]. Unsaturated polyester resin (UPR) was purchased from Hefei information.
Chaoyu Chemical Co., Ltd (China). Benzoyl peroxide (BPO) was used as
initiator of curing reaction and purchased from Sinopharm Chemical 3. Results and discussion
Reagent Co., Ltd (China). BPO was recrystallized with chloroform and
methanol before use. 3.1. Structural analysis and processing performance

2.2. Synthesize of PBPG, POPG and PCH3PG
The synthesis of PBPG, POPG and PCH3PG was by substitution re­
action between dichloro compounds (phenylphosphonic dichloride,
phenyl dichlorophosphate and methylphosphonic dichloride) and
phosphorus-containing glycol (PG), respectively. Firstly, PG was syn­
thesized with DOPO and glycerol through Atherton-Todd reaction
(Fig. 1). DOPO (0.05 mol, 10.81 g) and triethylamine (0.05 mol, 5.06 g)
were dissolved in 100 mL of dichloromethane at room temperature,
following by addition of glycerol (0.05 mol, 4.60 g) under magnetic
stirring. Then, CCl4 (0.05 mol, 7.69 g) was added dropwise at 0 ◦ C, and
the system was stirred magnetically for 24 h at 60 ◦ C with condensate
reflux. After that, the reaction solution was extracted and separated
several times with HCl and saturated NaCl solution to remove triethyl­
amine hydrochloride. After drying with anhydrous sodium sulfate for
several hours, dichloromethane was removd by a rotary evaporator. The
light yellow viscous liquid product was obtained after vacuum drying at
50 ◦ C for 24 h.
The synthetic routes of PBPG, POPG and PCH3PG was shown in
Fig. 2. Taking PBPG as example, PG (0.11 mol, 33.69 g) was mixed with
dichloromethane (250 ml). Meanwhile, triethylamine (0.2 mol, 20.24 g)
was added into above solution. Then, phenylphosphonic dichloride (0.1
mol, 19.50 g) was added dropwise to the above mixtures. The system
was heated at 70 ◦ C for 6 h under magnetic stirring and condensing
reflux. After removing triethylamine hydrochloride, the filtrate was
extracted with diluted HCl, NaHCO3, NaCl solution and deionized. After
removing dichloromethane with a rotary evaporator, the PBPG product
was obtained after drying at 50 ◦ C for 24 h. The synthesis of POPG and
To clearly characterize the chemical structure of PG before and after
reaction, 1H and 31P NMR were firstly used to analyze glycerol and
DOPO. As shown in Fig. S1, the signal at 8.79 ppm in 1H NMR spectrum
of DOPO was due to P–H, while the peaks between 7.12 and 8.21 ppm
were from benzene ring structures. There was only one signal at 14.33
ppm in 31P NMR, indicating the high purity of DOPO [35]. Glycerol
exhibited peak of hydroxyl at 4.46 ppm, while the characteristic peak at
3.20–3.48 ppm was attributed to C–H [36]. After Atherton-Todd reac­
tion, peaks at 3.51–4.33 ppm in 1H NMR spectrum of PG were from
glycerol, and peaks between 7.08 and 8.04 ppm were from aromatic ring
of DOPO. For 31P NMR spectrum, the peak of PG significantly changed
compared with DOPO. Compared with single peak of DOPO at 14.33
ppm, two peaks at 10.92 and 9.48 ppm appeared in PG spectrum,
proving the reaction between DOPO and glycerol. The appearance of
two characteristic peaks of PG was caused by the reaction of DOPO with
hydroxyl groups at different positions in glycerol. Meanwhile, 1H NMR
was also used to analyze structures of PBPG, POPG and PCH3PG (Fig. 3).
In 1H NMR spectrum of PCH3PG, peaks at 1.03–1.76 ppm were from
methyl group in methylphosphonyl structure, and signals at 2.95–5.03
ppm corresponded to the methylene hydrogen and tertiary hydrogen
atom in PG. Meanwhile, characteristic peaks of aromatic ring structure
in appeared at 6.78–8.14 ppm. Compared with PCH3PG, the 1H NMR
spectra of PBPG and POPG were different, due to changes in
phosphorus-containing structures. The aromatic ring peaks of phos­
phorous containing side group and DOPO structures in PBPG and POPG
appeared in 6.76–8.41 and 6.47–8.60 ppm, respectively. Additionally, a
small amount of impurities such as dichloromethane and triethylamine
existed in products. However, these substances would volatilize during

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F. Chu et al. Composites Part B 233 (2022) 109647

Fig. 3. 1H NMR spectra of PBPG, PCH3PG and POPG.

Table 2
The phosphorus contents, weight average molecular weight (Mw), number
average molecular weight (Mn), and degree of polymerization (DP) of PBPG,
POPG and PCH3PG.
Samples Structures P (wt%) Mn Mw DP

PBPG 14.46 5447 6097 14

POPG 13.94 5546 6980 16

Fig. 4. TGA and DTG curves of PBPG, POPG and PCH3PG in N2 atmosphere.

PCH3PG 16.91 4357 5332 14

curing reactivity of flame retardant UPR composites can be ascribed to
– C and the increased viscosity of resins
the reduced density of reactive C–
(Fig. S2b). Meanwhile, the crosslinking density and glass transition
temperature (Tg) were therefore reduced, and the specific analysis was
shown in Fig. S3 and Table S1.

the preparation process of UPR, thus not affecting the properties of

materials.
The synthesized flame retardants were viscous liquid with a certain
fluidity, due to a certain degree of polymerization. The number average
molecular weight (Mn), weight average molecular weight (Mw), and
degree of polymerization (DP) of PBPG, P CH3PG and POPG were
measured by GPC. The DP of PBPG, POPG and PCH3PG flame retardants
were 14, 16, and 14, respectively. Additionally, the phosphorus contents
of PBPG, POPG and PCH3PG were 14.46, 13.94and 16.91% respectively
(Table 2), which was mainly due to changes in phosphorus-containing
dichloride compounds. The increased phosphorus contents of flame re­
tardants improved flame retardant efficiency. However, the difference
in phosphorus-containing structure not only changed the phosphorus
contents of flame retardants, but also changed the side chain structures,
which also influence the properties of UPR composites.
The effects of synthesized flame retardants on the reactivity and
viscosity of UPR should be considered [37,38]. Non-isothermal DSC
curves were used to analyze the curing reactivity. As shown in Fig. S2a,
compared with pure UPR, the temperature at exothermic peaks (Tp) of
UPR/PCH3PG increased with the increasing contents of PCH3PG. This
result indicated the decreased curing reactivity with the introduction of
flame retardants. However, the Tp of UPR/PCH3PG 20%, UPR/PBPG
20% and UPR/POPG 20% had no obvious difference. The decreased
3.2. Thermal stabilities
TGA was utilized to analyze thermal degradation of flame retardants
with different phosphorus-containing structures in N2 atmosphere
(Fig. 4 and Table S2). The Tmax (temperature at maximum thermal
degradation rate) and Yc (char yields at 800 ◦ C) of PBPG were 364 ◦ C
and 9.36%, the Tmax and Yc of POPG were 365 ◦ C and 17.06%, and the
Tmax and Yc of PCH3PG were 369 ◦ C and 4.67%. These results indicated
the thermal stability of flame retardants at high temperature stage was
affected by phosphorus-containing dichloride compounds. Comparing
PBEG and PCH3PG, although PCH3PG had higher phosphorus contents,
the Tmax of PCH3PG and PBPG were similar, and even the Yc of PBPG was
higher. This indicated the phenylphosphoryl structure of PBPG exhibi­
ted higher char-forming efficiency due to thermally stable benzene ring
in side chain, compared with the methylphosphonyl structure in
PCH3PG. Compared with PBEG and PCH3PG, even though POPG had
lowest phosphorus contents, its Yc was greatly increased. This indicated
there was no necessary relationship between phosphorus contents and
Yc for different phosphorus-containing flame retardants.
The thermal stability of pure UPR, UPR/PBPG, UPR/PCH3PG and
UPR/POPG composites under air and N2 atmospheres was also studied
by TGA and DTG (Fig. 5) [39]. Some important data such as phosphorus
contents in UPR composites, T5%, T10%, Tmax and Yc were summarized in

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F. Chu et al. Composites Part B 233 (2022) 109647

Fig. 5. TGA and DTG curves of pure UPR, UPR/PBPG, UPR/PCH3PG and UPR/POPG composites in N2 and air atmosphere.

thermal stability of composites under high-temperature stage [42]. In

Table 3
comparison with pure UPR, the increasing contents of PCH3PG, PBPG
The phosphorus contents, UL-94, LOI and cone calorimeter results of UPR
and POPG obviously enhanced the high-temperature charring capacity
composites.
of UPR composites in both N2 and air atmosphere. Meanwhile, though
Samples P UL- LOI PHRR THR tPHRR FGI
UPR/PBPG 20% had higher phosphorus contents compared to
(%) 94 (%) (kW/ (MJ/ (s) (kW/
m2) m2) (m2⋅s))
UPR/POPG 20%, (POPG 2.79 wt%, PBPG 2.89 wt%), its Yc were lower.
This indicated the charring capacity of flame retardant UPR composites
UPR 0 No 23.5 859.31 90.76 148 5.81
did not only depend on phosphorus contents, but also the difference in
± 0.2
UPR/ 2.20 No 28 ± 352.14 44.94 154 2.29 flame retardant structures.
PCH3PG 0.1
13%
UPR/ 2.54 V0 29 ± 289.91 41.80 157 1.85 3.3. Flame retardant performance
PCH3PG 0.3
15% UL-94 and LOI were firstly utilized to characterize flame retardant
UPR/ 3.38 V0 30 ± 275.60 38.83 159 1.73
PCH3PG 0.2
properties of pure UPR, UPR/PBPG, UPR/PCH3PG and UPR/POPG
20% composites. Table 3 showed the results and corresponding phosphorus
UPR/ 2.17 V2 27 ± 267.12 37.58 150 1.78 contents of UPR composites. The flame retardant performance was
PBPG 0.5 depended on flame retardants contents and structures. As contents of
15%
PCH3PG rising, the flame retardant performance of UPR/PCH3PG com­
UPR/ 2.89 V0 28 ± 295.85 38.15 153 1.93
PBPG 0.2 posites increased rapidly. UPR/PCH3PG 15% reached V0 rating in UL-94
20% test, and phosphorus contents of UPR composite was only 2.54%. With
UPR/ 2.09 No 26.5 283.18 36.33 145 1.95 PCH3PG contents rising, LOI value of UPR composites increased signif­
POPG ± 0.3 icantly. The LOI of UPR/PCH3PG 13% increased from 23.5% of pure
15%
UPR/ 2.79 V0 27.5 282.65 35.44 152 1.86
UPR to 28%. When PCH3PG increased to 20 wt%, the LOI of UPR/
POPG ± 0.2 PCH3PG 20% was further increased to 30%, due to increased phos­
20% phorus contents. Compared with UL-94 V0 rating of UPR/PCH3PG 15%,
UPR/PBPG 15% and UPR/POPG 15% can not reach same flame retar­
dant rating. Meanwhile, compared with UPR/PCH3PG 15%, the LOI of
Table S3. Glycerol-based polymeric flame retardants made UPR com­
UPR/PBPG 20% and UPR/POPG 20% was lower, with higer flame
posites degrade earlier than pure UPR in both N2 and air atmospheres,
retardant contents and phosphorus contents. This indicated the flame
due to the unstable P–O species in flame retardants. Meanwhile, some
retardant performacne of UPR composites not only depended on phos­
reactions between flame retardants and polyester segments, such as
phorus contents, but also on the corresponding flame retardant struc­
hydrolysis, phenololysis and transesterification, would also reduce the
tures. In this work, the methyl phosphorus structure in PCH3PG was
thermal stability of UPR composites at low temperature stage [40,41].
more helpful for improvement of flame retardant performance than
These reactions lead to generation of small molecular segments and
phenyl and phenoxy side group structures.
decreased thermal stability. However, this premature degradation
The heat release behavior of UPR composites was analyzed by cone
facilliated to the catalytic charring in condensed phase and enhanced
calorimeter combustion test [43–46]. The HRR and THR curves of pure

Fig. 6. (a) HRR and (b) THR curves of pure UPR, UPR/PCH3PG, UPR/PBPG and UPR/POPG composites.

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F. Chu et al.
Fig. 7. The pyrolysis fragment distribution of PCH3PG at different temperatures.
UPR, UPR/PCH3PG, UPR/PBPG and UPR/PBPG composites were shown
in Fig. 6, and some important information were listed in Table 3. The
peak value of HRR curves (PHRR) and THR of UPR composites were
significantly reduced by glyceryl polymerized flame retardants,
compared with pure UPR. With the increasing of PCH3PG, PHRR and
THR of UPR/PCH3PG composites gradually decreased. For
UPR/PCH3PG 13%, the PHRR and THR were reduced by 59.02% and
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Composites Part B 233 (2022) 109647
50.48% respectively, in comparison with pure UPR. When PCH3PG
contents was increased to 20 wt%, PHRR and THR of UPR/PCH3PG 20%
were maximumly decreased by 67.93% and 57.22%, compared with
pure UPR. For PBPG and POPG, the PHRR of UPR/PBPG 20% and
UPR/POPG 20% were reduced by 65.57% and 67.11%, which was
slightly lower than UPR/PCH3PG 20%. The fire growth index (FGI) was
used to assess the fire hazards of pure UPR, UPR/PCH3PG, UPR/PBPG
F. Chu et al. Composites Part B 233 (2022) 109647

Fig. 8. The pyrolysis fragment distribution of PBPG at different temperatures.

and UPR/PBPG composites, and higher FGI value indicated higher fire
hazards [47]. With PCH3PG contents of increasing, FGI values of
UPR/PCH3PG decreased gradually. The FGI of UPR/PCH3PG 13,
UPR/PCH3PG 15% and UPR/PCH3PG 20% were 2.29, 1.85 and 1.73
kW/(m2.s), reducing 58.14%, 66.18% and 68.37% compared with pure
UPR. Meanwhile, FGI values of UPR/PBPG 20% and UPR/POPG 20%
were reduced by 64.72% and 66.00% respectively, compared with pure
UPR. These results indicated UPR/PCH3PG exhibited highest fire safety
performance.
3.4. Gaseous phase analysis
The pyrolysis products of flame retardants at different pyrolysis
temperatures were analyzed by TGA-MS. Due to the unstable P–O

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F. Chu et al.
Fig. 9. The pyrolysis fragment distribution of POPG at different temperatures.
groups in glycerol-based polymerized flame retardants, the flame re­
tardants were first pyrolyzed and broken at P–O bond to generate three
parts: phosphate structure, DOPO and glycerol structure. Meanwhile, for
glycerol-based polymerized flame retardants combining different phos­
phorus structures, the pyrolysis products in gaseous phase was more
complicated because of DOPO containing glycol monomers in synthetic
route. As shown in Figs. 7–9, The types of pyrolysis fragments of
PCH3PG, PBPG and POPG in TGA-MS were similar with each other. The
pyrolysis species at m/z = 89 and 91 were originated from glycerol. The
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Composites Part B 233 (2022) 109647
pyrolysis fragments at m/z = 47, 63 and 139 were mainly attributed to
cleavage of phosphorus-containing compounds [48,49]. The fragments
at m/z = 77, 78, 94, 168, 169 and 170 were mainly attributable to ar­
omatic compounds. According to the temperature and time sequence of
pyrolysis fragments, the schematic diagram of possible pyrolysis process
of PCH3PG, PBPG and POPG was shown in Fig. 10 [50].
TGA-FTIR technology was operated to investigate pyrolysis products
of pure UPR, UPR/PBPG, UPR/PCH3PG and UPR/POPG composites
[51–54]. As shown in Fig. S4, FTIR spectra showed gaseous products of
F. Chu et al. Composites Part B 233 (2022) 109647

Fig. 10. The schematic diagram of possible pyrolysis process of glycerol-based polymerized flame retardants.

Fig. 11. Digital pictures of carbon residues for pure UPR, UPR/PCH3PG, UPR/PBPG and UPR/POPG composites after cone calorimter.

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F. Chu et al. Composites Part B 233 (2022) 109647

Fig. 12. SEM images of carbon residues of pure UPR, UPR/PCH3PG, UPR/PBPG and UPR/POPG composites after cone calorimter.

Fig. 13. RT-FTIR spectra of products in condensed phase for (a) pure UPR, (b) UPR/PCH3PG 20%, (c) UPR/PBPG 20% and (d) UPR/POPG 20% composites at
different temperatures.

pure UPR, UPR/PCH3PG 20%, UPR/PBEG 20% and UPR/POEG 20% at
different temperatures. The peaks of FTIR spectra of pyrolysis for all
composites at different pyrolysis temperatures were relatively similar.
There appeared CO2 peak at 2310 cm− 1, CO peak at 2180 cm− 1,
carbonyl compounds peak at 1762 cm− 1 and aromatic compounds peak
at 910 cm− 1 for all composites [55,56]. However, no obvious signal
peaks of phosphorus-containing species appeared, due to the sensitivity
of test instrument and the interference of other adjacent characteristic
peaks. Compared with pure UPR, UPR/PCH3PG 20% and UPR/PBPG
20%, the peak intensity in pyrolysis infrared spectra of UPR/POPG 20%
decreased rapidly after 400 ◦ C, indicating POPG exhibited better
inhibitory effect on release of gaseous pyrolysis products.
3.5. Condensed phase analysis
Fig. 11 showed digital pictures of char residues of pure UPR, UPR/
PCH3PG, UPR/PBPG and UPR/POPG composites after cone calorimter
test. Though the addition of PCH3PG increased char yeilds after com­
bustion of UPR composites, the increase in its addition did not signifi­
cantly change char yeilds. However, from SEM image of carbon residue
for UPR/PCH3PG, as PCH3PG content increased, the microstructure
cracks of the carbon residue decreased and the structure was gradually

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F. Chu et al. Composites Part B 233 (2022) 109647

cm− 1, carbonyl compound at 1739 cm− 1, C–O–C (1268 and 1126 cm− 1)
and aromatic compounds (1446, 741 and 700 cm− 1) [57]. However,
some differences can be found in peak positions of UPR/PCH3PG,
UPR/PBPG and UPR/POPG composites, compared with pure UPR.
Especially, there appeared new peaks at 920 cm− 1 for UPR/PCH3PG,
UPR/PBPG and UPR/POPG, which corresponded to P–O stretching vi­
bration [58]. This indicated some phosphorus elements remained in
condensed products in thermal degradation process of UPR/PCH3PG,
UPR/PBPG and UPR/POPG. These phosphorus-containing compounds
stimulated the production of carbon layers, thereby preventing heat
release.
XPS was applied for the analysis of element composition in carbon
layers after cone calorimter. As shown in Fig. 14 and Table 4, compared
with pure UPR, there all existed phosphorus elements in carbon residues
of UPR/PCH3PG 20%, UPR/PBPG 20% and UPR/POPG 20%. This result
corresponded to the RT-FTIR detection results, indicating the presence
of phosphorus in the condensed phase. However, UPR/PCH3PG 20%,
UPR/PBPG 20% and UPR/POPG 20% exhibited 0.50, 0.74 and 2.85 at%
of phosphorus contents in char residues respectively, due to different
flame retardant mechanism from varied flame retardant structures. The
Fig. 14. XPS results of char residues after cone calorimeter for pure UPR, UPR/
PCH3PG 20%, UPR/PBPG 20% and UPR/POPG 20% composites. lower phosphorus contents in char residues of UPR/PCH3PG 20% and
UPR/PBPG 20% indicated PCH3PG and PBPG mainly played flame
retardant action in gaseous phase. By contrast, the phosphorus contents
Table 4 in char residues of UPR/POPG 20% increased obviously, indicating
The element composition of char residues for pure UPR, UPR/PCH3PG 20%, POPG mainly played flame retardant effect in condensed phase. Mean­
UPR/PBPG 20% and UPR/POPG 20% composites after cone calorimter tested by while, it has been found that UPR/PCH3PG and UPR/PBPG composites
XPS spectra. performed better flame retardant properties compared with that of UPR/
Samples C (at.%) O (at.%) P (at.%) POPG composites, which indicated flame retardant mechanism in
UPR 85.22 14.08 /
gaseous phase was more helpful to improve flame retardant properties of
UPR/PCH3PG 20% 87.34 11.07 0.50 UPR composies.
UPR/PBPG 20% 85.21 12.85 0.74
UPR/POPG 20% 77.42 17.86 2.85
3.6. Compatibility and mechanical properties
completed. (Fig. 12). The use of PBPG and POPG also increased the char
yeilds of UPR composites after combustion. From SEM images of UPR/ Fig. 15a showed the transparency of pure UPR and flame retardant
PBPG and UPR/POPG, it can be seen the microstructure of carbon layers UPR samples in 3 mm the compatibility ckness. It can be seen from the
experienced a transition from multiple cracks to complete morphologies figure that all words can be clearly seen through the sample, indicating
without cracks with increasing contents of flame retardants. This phe­ all composites exhibited good transparency in the visible light region.
nomenon was similar with that of UPR/PCH3PG. This transparency was ascribed to the good between these three flame
To further analyze the composition of condensed phase products, RT- retardants and polymer matrix. To analyze the mechanical performance
FTIR was used to pure UPR, UPR/PCH3PG, UPR/PBPG and UPR/POPG of UPR composites, the tensile strength and impact strength were tested.
composites at different pyrolysis temperatures (Fig. 13). The charac­ The tensile strength and impact strength of flame retardant UPR com­
teristic peaks of condensed phase products of UPR/PCH3PG, UPR/PBPG posites were slightly reduced compared with pure UPR (Fig. 15b), due to
and UPR/POPG were similar with that of pure UPR. There appeared decrease curing activity and crosslinking density. However, the tensile
characteristic peaks of hydroxyl at 3448 cm− 1, hydrocarbon at 2940 strength and impact strength of different flame retardant UPR compos­
ites showed little difference, indicating the difference in side-chain

Fig. 15. (a) The transparency of pure UPR and flame retardant UPR samples in 3 mm thickness; (b) Tensile and impact strengths of UPR composites.

11
F. Chu et al.
Fig. 16. (a–d) SEM and (e–h) SEM-EDS images of fractured surface for pure UPR, UPR/PCH3PG 20%, UPR/PBPG 20% and UPR/POPG 20%.
structures of PCH3PG, PBPG and POPG flame retardants exhibited little
influence on mechanical performance of UPR composites.
SEM images and SEM-EDS images of the fractured surface after
impact test were shown in Fig. 16. Compared with the smooth surface
morphology of pure UPR (Fig. 16a), there were some wrinkles on frac­
tured surface of UPR/PCH3PG 20%, UPR/PBPG 20% and UPR/POPG
20% composites (Fig. 16b–d). Meanwhile, phosphorus elements can be
found on fractured surfaces of flame retardant UPR composites in SEM-
EDS image. In the comparison of phosphorus content, UPR/PCH3PG
20% exhibited the highest phosphorus contents, while UPR/POPG 20%
had the lowest phosphorus content (Fig. 16e–h). This was consistent
with the theoretical calculation of the phosphorus contents of UPR/
PCH3PG 20%, UPR/PBPG 20% and UPR/POPG 20% composites in
Table 1. Fig. S5 showed the SEM-Mapping image of fractured surface of
UPR composites. On fractured surface of UPR/PCH3PG 20%, UPR/PBPG
20% and UPR/POPG 20%, the phosphorus elements were uniformly
distributed, which further indicated these three flame retardants present
good dispersibility and compatibility in UPR matrix.
4. Conclusion
To enhance the flame retardant efficiency and compatibility of flame
retardants in UPR composites, novel polymeric glycerol-based flame
retardants with combined flame retardant structures were synthesized.
A novel DOPO-based diol (PG) was first prepared by the Atherton-Todd
reaction between glycerol and DOPO. Then, PCH3PG, PBPG and POPG
were synthesized and incorporated in flame retardant UPR composites.
NMR and GPC were firstly used for the structure characterization of
three flame retardants. In the analysis of thermal stabilities, it can be
found POPG was more helpful to improve char yeilds under high tem­
peratures than PCH3PG and PBPG. However, PCH3PG and PBPG
contributed more to the improvement of flame retardant properties.
Especially for PCH3PG, the flame retardant performance of UPR/
PCH3PG increased rapidly with its increasing contents. When 15 wt% of
PCH3PG was added and the phosphorus content of UPR/PCH3PG 15%
was only 2.54 wt%, the composies reached V0 in UL-94 test and 29% of
LOI value. When PCH3PG contents were increased to 20 wt%, the LOI of
UPR/PCH3PG 20% was increased to 30%. Meanwhile, PHRR and THR of
UPR/PCH3PG 20% experienced maximum 67.93% and 57.22% reduc­
tion, compared with pure UPR. TGA-MS and TGA-FTIR were applied to
analyze the gaseous products and gaseous phase mechanism. Mean­
while, RT-FTIR, SEM and XPS were used to analyze flame retardant
12
Composites Part B 233 (2022) 109647
mechanism condensed phase. It was found the most efficient PCH3PG
was mainly played a flame retardant effect in gaseous phase, supple­
mented by the barrier effect of condensed phase. Additionally, the
polymeric glycerol-based flame retardants exhibited good compatibility
with UPR matrix. This work explores the high-efficiency flame retardant
structures with good compatibility for UPR, and promotes the wide
application of UPR materials.
CRediT authorship contribution statement
Fukai Chu: Conceptualization, Writing – original draft, Funding
acquisition. Shuilai Qiu: Methodology. Yifan Zhou: Writing – review &
editing. Xia Zhou: Visualization. Wei Cai: Visualization. Yulu Zhu:
Validation. Lingxin He: Resources. Lei Song: Supervision, Funding
acquisition. Weizhao Hu: Project administration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The research was financially supported by the Fellowship of China
Postdoctoral Science Foundation (No. 2021TQ0316), the National Nat­
ural Science Foundation of China (No. 51991352, No. 51973203 and
No. 51874266), and the Fundamental Research Funds for the Central
Universities (WK2320000043 and WK2320000044).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compositesb.2022.109647.
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