Composites Communications 40 (2023) 101589

Contents lists available at ScienceDirect

Composites Communications
journal homepage: www.elsevier.com/locate/coco

Preparing flame-retardant poly(phenylene oxide)/polyurea nanocomposite

foam with excellent heat-resistance and shape memory performance
Haomin Wang a, b, Jiangan You a, b, Man Tian a, b, Jian Qiu a, Haiping Xing a, Jian Xue a,
Zhiwei Jiang a, **, Tao Tang a, b, *
a
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China
b
University of Science and Technology of China, Anhui, 230026, China

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

Keywords: Superlight polymer foams with excellent heat resistance and flame retardancy are highly expected in many
Heat resistance application fields. However, the challenge for preparing polymer foams with the required performances by green
Microphase separation method needs to be overcome. Here, using “Plasticizing-Foaming-Reinforcing” (PFR) strategy, we combined poly
Polymer foam
(phenylene oxide) (PPO) and polyurea (PUA) to fabricate intrinsic fire-retardant PPO/PUA nanocomposite foam
Nanostructure
with excellent heat resistance and solvent resistance and shape memory. The supercritical CO2 (sc-CO2) foam
Shape memory
processing was realized at a much lower temperature, stemming from the fact that the monomer of PUA,
polymeric methylene diphenyldiisocyanate (PMDI), acted as a reactive plasticizer for PPO during the foaming
process, and the expansion ratio of the resultant PPO/PUA foams was greatly increased. The in-situ formation of
nanostructure in the cell wall during the crosslinking of PMDI takes place, in which the PUA is the dispersed
phase with 10–40 nm in the matrix of PPO. Compared to the PPO foam and PPO/polystyrene blend foam, the
PPO/PUA nanocomposite foam has excellent heat resistance and solvent resistance. Furthermore, the PPO/PUA
nanocomposite foam also has excellent shape memory performance at high temperature.

1. Introduction (phenylene oxide) (PPO) [5], whose processing temperature is close to

Polymer foams have been widely applied in the wind power, con­
struction, transportation, etc. [1–3], due to their lightweight, mechan­
ical properties, heat insulation and high strength characteristics.
Actually the performances of polymer foams depend on not only the cell
structure but also the composition and microstructure of the matrix
material [4]. However, the polymer foams widely used at present are
mainly based on common polymers, which has been difficult to meet the
growing demand for high-performance foams. Thanks to high glass
transition temperature (Tg) or melting point originating from the strong
chain interaction and high chain rigidity, engineering plastics can
withstand higher service temperatures than common polymers, which
will expand the application field of polymer foams. However, the pro­
cessing temperature of engineering plastics is high, which will not only
cause considerable energy waste during the processing stage, but also be
fatal to keep the performance for some polymers. For example, poly
its degradation temperature. Therefore, it is highly required to reduce
the processing temperature (such as foaming temperature) of engi­
neering plastics and improve their foaming performance for energy
conservation and further expanding the application range of engineering
plastics [6,7].
As an important engineering plastic, PPO shows good heat-resistance
(Tg – 210 ◦ C) and outstanding mechanical properties due to high rigidity
of chain structure [8]. Also PPO has a good fire retardant performance,
its limit oxygen index (LOI) is about 29.8%, and presenting
self-extinguishing behaviour in upward combustion under air. Unfor­
tunately, the melt flowability of PPO is poor due to the high melt vis­
cosity originating from its chain rigidity, which is difficult for melt
processing of PPO in the case without modification for reducing the melt
viscosity. In fact, PPO resin is often modified by adding some amounts of
polystyrene (PS) or high impact PS (HIPS) to decrease the viscosity and
increase the fluidity (processability) [9]. Because PS is miscible with

* Corresponding author. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, 130022, China.
** Corresponding author.
E-mail addresses: jiangzw@ciac.ac.cn (Z. Jiang), ttang@ciac.ac.cn (T. Tang).

https://doi.org/10.1016/j.coco.2023.101589
Received 27 February 2023; Received in revised form 3 April 2023; Accepted 3 April 2023
Available online 5 April 2023
2452-2139/© 2023 Elsevier Ltd. All rights reserved.
H. Wang et al.
PPO [10], the addition of PS reduces not only the melt viscosity of PPO
but also the Tg of PPO (the decrement of Tg depending on the content of
PS in the PPO/PS blend), which will lead to the reduction of
heat-resistance performance of the resultant blends (compared to pure
PPO). Meanwhile, the addition of PS is not very efficient to reduce the
melt viscosity of PPO owing to macromolecular feature of PS [11], so
more PS will be needed to promote the fluidity of PPO, resulting in the
obvious reduction of heat resistance and flame retardancy. According to
the above results, it is highly expected to establish a method for reducing
melt viscosity of PPO during the foaming process while maintaining
good heat resistance performance in the service period.
Compared to the addition of polymer, the addition of small mole­
cules as plasticizer will be more efficient in reducing melt viscosity of
engineering plastic during the foaming process. However, how to keep
the high performance of plasticized polymers during the service period
is a critical issue. In our previous work [12], we proposed a “Plasti­
cizing-Foaming-Reinforcing” (PFR) strategy to develop new high per­
formance poly(vinyl chloride)/polyurea (PVC/PUA) blend foams. The
key factor in this strategy is that the monomer of PUA was used as a
reactive plasticizer to reduce the melt viscosity of polymers during the
foaming process, and then the reaction induction phase separation takes
place in the cell wall during the curing, and the reactive plasticizer
becomes gradually the dispersed phase of crosslinked PUA to in-situ
form the sea-island nanostructure.
In this study, we prepare fire-retardant PPO foam with superlight and
outstanding heat-resistance performance. The crosslinking monomer
(polymeric methylene diphenyldiisocyanate: PMDI) of polyurea (PUA)
is used as a plasticizer to reduce the melt viscosity of PPO, and after
foaming, the PMDI were initiated to polymerize and crosslink by
introducing water. As a result, the PMDI becomes the PUA phase
dispersed in the PPO matrix, and the cell walls appear in-situ microphase
separation nanostructure, which dramatically promote heat resistance
of the resultant foams and endow excellent solvent resistance and shape
memory properties. The effect of added PMDI on the expansion ratio,
cell structure and performances of PPO/PUA nanocomposite foams were
studied.
2. Experimental section
2.1. Materials
Polyphenylene ether（PPO, LXR040）resin was purchased from
Nantong Xingchen Synthetic Material Co., LTD. Polymeric methylene
diphenyldiisocyanate (PMDI, M20S, NCO content: 31.5 wt%) from BASF
was used as the monomer of PUA.
2.2. Preparation of PPO/PUA nanocomposite foams
The preparation process of PPO/PUA nanocomposite foams is as
follow. The first step is the mixing process of PMDI and PPO at 190 ◦ C for
7 min by XSS-300 mixer, in which PMDI and PPO are mixed in different
weight ratio (5:5, 6:4, 7:3, respectively) and named PPO/PMDI-50,
PPO/PMDI-40, PPO/PMDI-30 respectively, and then tableted at
200 ◦ C for 5 min to obtain PPO/PMDI blend sheet material (25 mm × 25
mm × 3 mm). Then the sheet samples are treated in a high-pressure
foam kettle at a certain temperature for 1 h under supercritical CO2
(sc-CO2), following rapidly release the pressure to obtain the foam
samples. Finally, the obtained foam samples were placed in a water
vapor oven at 85 ◦ C for crosslinking reaction to acquire PPO/PUA
nanocomposite foams.
2.3. Characterization
The samples before and after curing were tested by Fourier transform
infrared spectroscopy (FTIR), and the test instrument was VERTEX70
Fourier variable infrared spectrometer.
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Composites Communications 40 (2023) 101589
Scanning electron microscopy (SEM, XL30 ESEM, PHILLIPS) was
used to observe the cell wall, cell edge, and cell structure of PPO/PUA
foams. Then, the image processing software (Nano Measurer) was used
to calculate the average cell density and cell diameter of the foam with
different proportions and densities. The expansion rate of the foam can
be measured by the drainage method. Atomic force microscope (AFM,
Bruker Dimension Icon) was applied to observe the morphology of cell
wall in the PPO/PUA nanocomposites. The thin film of PPO/PUA
nanocomposite was used as the model of the cell wall of the nano­
composite foam, which is subjected to the same treatment process as the
preparation of PPO/PUA nanocomposite foams.
Dynamic mechanical analysis (DMA) was used to test the loss
tangent (tan δ) and storage moldulus (G’) of the samples, and the in­
strument was DMA+450, 01 db Metravib, France. DMA adopts tensile
mode, and the sample size for testing was 40 mm × 10 mm × 3 mm, of
which the density of the foam sample was 100–200 kg/m3. The oscil­
lation frequency during the test was 1 Hz, the heating rate is 5 ◦ C/min.
For comparing the heat resistance of the foams with different compo­
sition at high temperatures, the foam samples were placed in a 250 ◦ C
oven for 10 min, and then the volume change before and after treatment
was measured.
Thermogravimetric analysis (TGA, TA STD Q600 thermal analyzer)
was used to measure thermal degradation temperature and residual
content of the samples in a nitrogen atmosphere. The test temperature
range was from room temperature to 700 ◦ C, the heating rate was 10 ◦ C/
min. The foam samples with dimensions of 150 mm × 50 mm × 13 mm
were prepared for horizontal combustion test (PSH-2, Nanjing Jiangning
Analytical Instrument Co., LTD), and the test standard was GB 8332-
2008. The LOI value of the samples was tested using HC-2C oxygen
index meter (Nanjing, China) according to the test standard ASTM
D2863-9.
Solvent resistance for the samples was evaluated using good solvents
of PPO resin, such as toluene, chloroform and other organic solvents.
The PPO/PUA foam samples were soaked in the solvents for 24 h to
observe its mass retention rate.
3. Results and discussion
The first stage for the process for preparing PPO/PUA nanocomposite
foam is the addition of PMDI into PPO to plasticize PPO. The DMA
measurements were used to characterize PPO/PMDI blends. As shown in
Fig. 1a, the Tg of pure PPO sample is 220 ◦ C, and the Tg dramatically
decreases after adding PMDI. When the content of PMDI is 30 wt% and
50 wt%, the Tg decreases to 140 ◦ C and 95 ◦ C, respectively. These results
show that the PMDI are efficient plasticizer of PPO. This is because
before curing, the added PMDI will enter the gap of PPO chains to in­
crease the free volume between macromolecular chains, play a plasti­
cizing role, and reduce the Tg of PPO.
Fig. 1b shows FTIR spectra of PPO/PMDI = 60/40 blend before and
after the curing by introducing water. The vibration peak at 2275 cm− 1
comes from –NCO group of PMDI. After curing, the vibration peak at
2275 cm− 1 almost vanished, showing that the foam cured completely
through the crosslinking reaction between –NCO group and water
molecule. Some new characteristic peaks appeared in the PPO/PUA
nanocomposite foams, for example, –NH in amide group (3370 cm− 1)
and C– – O in amide group (1665 cm− 1), meaning the formation of urea
structure in the PPO/PUA nanocomposite foams [4].
Fig. 1c shows the tan δ curves of PPO/PUA nanocomposite foams
with the testing temperature. Compared to the PPO/PMDI blends
(Fig. 1a), the Tg of PPO/PUA nanocomposite foams rises to 225 ◦ C after
curing, in spite of the content of PMDI, implying that the obtained
nanocomposite foams have good heat-resistance. The change of micro­
structure with the curing time in the thin film of PPO/PMDI (60/40)
blend was presented in Fig. S1. Fig. 1d shows AFM image for the film of
PPO/PUA-40 nanocomposite after curing. It can be seen that the sea-
island nanostructure is formed in the film of PPO/PUA after curing, in
H. Wang et al. Composites Communications 40 (2023) 101589

Fig. 1. (a) tan δ curves of PPO and PPO/PMDI blends with the testing temperature; (b) FTIR spectra of PPO/PMDI-60/40 blends before and after curing; (c) tan δ
curves of PPO/PUA nanocomposite foams with the testing temperature; (d) AFM image (Adhesion mode) for the film of PPO/PUA-40 nanocomposite.

Fig. 2. A schematic drawing for curing process including chemical reaction of converting PMDI into PUA.

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H. Wang et al.
which the PMDI becomes gradually the crosslinked network, forming
the dispersed PUA phase (the red dashed line area) with 10–40 nm in the
PPO matrix. Fig. 2 shows a schematic drawing for curing process
including chemical reaction of converting PMDI into PUA. It can be seen
that there is benzene ring in chemical structures of both PPO and PUA.
We think that there is π-π interaction between PPO and PUA, which is
the reason for the formation of nanoscale dispersed PUA phase in the
PPO matrix.
Fig. 3 shows the structural parameters of PPO/PUA nanocomposite
foams. From Fig. 3a, it can be seen that the foaming temperature range
dramatically reduces in the case of PPO/PMDI blends comparing with
the pure PPO, and the expansion ratio is increased with the content of
PMDI. The foaming pressure does not show a strong effect on the
expansion ratio of PPO/PUA foams (Fig. 3b). The cell density and cell
size present strong dependence on the foaming temperature, and the cell
size rises with the foaming temperature, but the cell density decreases
(Fig. 3d). Fig. 3c shows SEM image of cellular structure in the PPO/PUA-
40 nanocomposite foams.
The DMA was used to evaluate the PPO/PUA nanocomposite foam.
The influence of the composition on storage modulus (E′ ) curves of PPO/
PMDI blend and PPO/PUA nanocomposite foams with the temperature
was shown in Fig. S2. Here the storage modulus (E′ ) of the sample at a
tested temperature was divided by its storage modulus at room tem­
perature (E0’) to obtain the normalized modulus (E’/E0’) to eliminate
the influence of the density of the foamed samples. As shown in Fig. 4a,
the plot of complex modulus with the testing temperature shows that the
temperature for the quick drop of complex modulus in the case of PPO/
PUA nanocomposite foams is higher than in the case of pure PPO foam,
meaning that the PPO/PUA nanocomposite foams have excellent heat-
resistance performance due to the in-situ formation of nanostructure
in the cell wall. Comparing the photographs of the PPO/PUA foam
Fig. 3. The structural parameters of PPO/PUA nanocomposite foams: (a) The plot of expansion ratio with the foaming temperature; (b) The plot of expansion ratio
with the foaming pressure; (c) SEM image for cellular structure of PPO/PUA-40 nanocomposite foams; (d) The plot of cell size with the foaming temperature for PPO/
PUA-40 nanocomposite foams.
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Composites Communications 40 (2023) 101589
sample before and after heating at 250 ◦ C for 10 min (Fig. 4b), it can be
seen that PPO/PUA nanocomposite foam has a good shape retention
during the heat treatment, showing the good ability for keeping the
shape. The solvent resistance for PPO/PUA nanocomposite samples was
evaluated using toluene (good solvent of PPO resin) as solvent to soak
the samples for 24 h to observe its mass retention rate. As shown in
Fig. 4c, although the mass retention rate of PPO is less than 20 wt%, all
the PPO/PUA nanocomposite foams show very small mass loss. Similar
results can be observed in other solvents, such as THF, DMF, chloroform
and so on, meaning that the obtained nanocomposite foams have
excellent solvent resistance.
Shape memory polymers are the materials that can fix one temporary
shape and subsequently recover to its permanent shape upon stimula­
tion, such as heating [13]. In this work, the formation of sea-island
microphase separation structure in the cell wall endows PPO/PUA
nanocomposite foams to possess shape memory performance, which
provide a potential for some applications [13,14]. Generally, shape
memory polymers need to have fixed phase and reversible phase for
resisting temporary deformation and restore their original shape under
some external stimuli [12,13]. Here crosslinked PUA can act as fixed
phase, PPO can act as reversible phase. For demonstrating shape
memory performance of the obtained foams, we placed PPO/PUA foam
samples with a size of 80 mm × 10 mm × 5 mm in a muffle furnace at
270 ◦ C for 30 s. After the sample was softened, the sample was bent to
90◦ , and then the sample was cooled to room temperature. At last the
sample was placed in the muffle furnace again, the sample deformed and
completely recovered its original shape after a certain period of time.
Fig. 4d shows the whole process of shape memory test of PPO/PUA-40
nanocomposite foam. The foam sample strip with the permanent
shape (S1) can be heated to 270 ◦ C to construct a new temporary shape
(S2), and then cooled to room temperature for 5 min to maintain the
H. Wang et al. Composites Communications 40 (2023) 101589

Fig. 4. Heat resistance performance of PPO/PUA nanocomposite foams: (a) The plot of complex modulus with the testing temperature from the DMA measurements;
(b) The photograph of the PPO/PUA-40 foamed samples before and after heating at 250 ◦ C for 10 min; (c) The mass retention rate of PPO/PUA foams after soaking in
toluene for 24 h at room temperature; (d) Shape recovery process of PPO/PUA-40 nanocomposite foam: (S1) the original shape of the sample; (S2) Deformation at
270 ◦ C and shape fixing at 25 ◦ C; (S1) Shape recovery at 270 ◦ C.

temporary shape. When reheated to 270 ◦ C, the sample shape returns to

Table 1
its permanent shape (S1).
Fire retardancy of PPO/PUA nanocomposite foams.
The flame-retardant properties of PPO/PUA foam samples were
measured to evaluate the fire safety performance, including limiting Samples Composition Density (g/ LOI UL94 Horizontal
(wt/wt) cm3) (%) burning
oxygen index (LOI) and horizontal combustion rating. The test standard
was GB 8332-2008 for horizontal combustion test of cellular plastics. PPO 100/0 0.17 28.5 V1 HF-1
PPO/ 70/30 0.14 27.5 V1 HF-1
For all the tested samples, there was not addition of flame retardants, so
PUA-30
intrinsic flame-retardant performance was compared. From Table 1, it PPO/ 60/40 0.11 25.5 V1 HF-1
can be seen that the PPO foam with the density of 0.17 g/cm3 presents PUA-40
the LOI of 28.5% and the HF-1 level in the standard horizontal burning PPO/ 60/40 0.04 24.5 NR HF-1
testing, showing a good intrinsic flame-retardant performance. The PUA-40
PPO/PS 70/30 0.12 22 NR HBF
presence of PUA in the PPO/PUA foams slightly reduced the LOI value
PPO/PS 60/40 0.06 21 NR HBF
(24.5–27.5%), but the HF-1 level in the standard horizontal burning
testing was kept (Table 1), in spite of varying composition and the
density of the foams. Fig. S3 shows the pictures of the PPO/PUA-40 foam resistance and solvent resistance, comparing with the PPO/PS foams.
sample (as an example) at different combustion time during the testing. More specifically, the PPO/PUA nanocomposite foam prepared by this
It can be seen that the fire spread very slowly and did not burn to 25 mm method also has excellent shape memory performance at high temper­
line (the red line on the surface of the samples), showing intrinsic flame- ature. This study provides a simple and green method to prepare high-
retardant performance. When the density of PPO/PUA nanocomposite performance rigid PPO-based foams.
foams is higher than 0.10 g/cm3, the foam samples can reach UL94 V1
grade. As control, for PPO/PS blend foams, the LOI is lower than 22%, CRediT authorship contribution statement
and the horizontal combustion rating only arrives HBF or NR level.
Haomin Wang: Writing – original draft, Completing experiments
4. Conclusion and writing paper. Jiangan You: data cutarion, Formal analysis,
Providing a part of experimental data and analysis about the mecha­
In this work, using PMDI as a reactive plasticizer for PPO, we have nism. Man Tian: data cutarion, Providing a part of experimental data.
successfully fabricate intrinsic fire-retardant PPO/PUA nanocomposite Jian Qiu: Discussion about the results. Haiping Xing: Discussion about
foam with excellent heat resistance, solvent-resistance and shape the results. Jian Xue: data cutarion, Providing a part of experimental
memory through sc-CO2 foam processing. Compared to pure PPO, the data. Zhiwei Jiang: Superviser, Discussion about the results. Tao Tang:
foaming process was realized in the PPO/PMDI at much lower temper­ Superviser, Revised paper, Funding acquisition, and, Formal analysis,
ature due to the presence of PMDI acting as a reactive plasticizer for About the mechanism.
PPO, and the expansion ratio of the resultant PPO/PUA nanocomposite
foams was also increased. The crosslinking reaction via the diffusion of Declaration of competing interest
water resulted in the in-situ formation of microphase separation nano­
structure in the cellular wall of the resultant foams, in which the PUA is The authors declare that they have no known competing financial
the dispersed phase with 10–40 nm in the matrix of PPO. This special interests or personal relationships that could have appeared to influence
nanostructure endows the PPO/PUA nanocomposite foam excellent heat the work reported in this paper.

5
H. Wang et al.
Data availability
Data will be made available on request.
Acknowledgements
The financial supports from National Natural Science Foundation of
China (52233004, and 51991353) and the Ministry of Science and
Technology of China (2021YFB3702800) are greatly appreciated.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.coco.2023.101589.
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