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Research paper

An efficient and mild recycling of waste melamine formaldehyde foams by

alkaline hydrolysis
Shaodi Wu a,b,1, Ning Zhang a,b,1, Chizhou Wang a,b, Xianglin Hou a,b, Jie Zhao a,b, Shiyu Jia a,b,
Jiancheng Zhao a,b, Xiaojing Cui c,*, Haibo Jin d,*, Tiansheng Deng a,b,*
a
Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China
b
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
c
Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan, Shanxi, 030008, China
d
Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology/College of New Materials and Chemical Engineering, Beijing
Institute of Petrochemical Technology, Beijing 102617, China
Received 8 September 2022; revised 12 October 2022; accepted 25 October 2022
Available online ▪ ▪ ▪

Abstract

Melamine formaldehyde foam (MFF) generates many poisonous chemicals through the traditional recycling methods for organic resin
wastes. Herein, a high MFF degradation ratio of ca. 97 wt% was achieved under the mild conditions (160
C) in a NaOH–H2O system with
ammelide and ammeline as the main degradation products. The alkaline solvent had an obvious corrosion effect for MFF, as indicated by
scanning electron microscopy (SEM). The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy
(FTIR), X-ray photoelectron spectroscopy (XPS), and 13C nuclear magnetic resonance (NMR). Besides, the MFF degradation products that have
the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of
melamine urea-formaldehyde resins (MUFs). Moreover, the degradation system demonstrated here showed the high degradation efficiency after
reusing for 7 times. The degradation process generated few harmful pollutants and no pre- or post-treatments were required, which proves its
feasibility in the safe removal or recovery of waste MFF.
© 2022 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communi-
cations Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Melamine formaldehyde foam; Degradation; Alkaline hydrolysis; Recycling

1. Introduction
Melamine formaldehyde foam (MFF) is made by micro-
wave foaming polymerization of melamine and formalde-
hyde [1,2]. It is a kind of thermosetting resin foam with high
porosity and fine three-dimensional network structure [3].
Due to its lightweight, heat preservation, flame retardant,
corrosion resistance, excellent ductility and so on, it has
been widely used in household cleaning, acoustic equipment,
* Corresponding authors.
E-mail addresses: cxjtyut@126.com (X. Cui), jinhaibo@bipt.edu.cn (H.
Jin), dts117@sxicc.ac.cn (T. Deng).
1
The authors contribute equally.
fire prevention materials and other fields in recent years [4].
With the rapid development of the construction industry, the
consumption amount of MFF is increasing at an amazing
speed. Consequently, a large number of waste MFFs is
accumulated and improperly disposed, which not only oc-
cupies the arable, but also pollutes the environment seriously
[5,6].
With the increasing attention to the environmental prob-
lems caused by thermosetting resin wastes, many explorations
are performed to dispose these resin wastes [7–9]. The tradi-
tional methods for treating resin wastes such as landfill and
incineration are forbidden, instead, the chemical recycling that
is considered as a sustainable method is being explored to
address this issue [10,11].

https://doi.org/10.1016/j.gee.2022.10.008
2468-0257/© 2022 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co.,
Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
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2 S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx
There exist several common methods for recycling the
thermosetting resins [5,6,10]. In the first method, waste plas-
tics are mechanically pulverized and reused as fillers in the
field of construction materials [12–14]. This method is simple
and convenient, but the dust pollution and low-value-added
process limits its application. The second method is the high-
temperature pyrolysis, in which the recovery of pyrolysis oil
and gas was mainly concerned [8,15,16]. However, the
complexity of product distribution added the difficulty to the
separation and utilization processes, which limits the sus-
tainable applications of this method. Besides, the triazine ring
structure contained in MFF will be cleaved via a non-selective
way in the pyrolysis process (>200
C), and consequently a
large number of toxic gases and liquids including hydrocyanic
acid will be inevitably generated [17,18]. In many cases, the
pyrolysis of macromolecular compounds generally generates
numerous pollutants, which increase the cost for the separation
and purification processes to meet the discharge standards
[8,19,20]. The third one is the chemical recovery, in which the
resin is degraded to the specific monomers or oligomers by the
selective bond cleavage under the mild conditions [4,21,22].
Controllable chemical recovery promotes the directed trans-
formation of thermosetting plastics [23,24]. Furthermore, the
moderate reaction conditions and the clear and simplified
product distribution makes it a sustainable and economical
method [25,26].
Our research group earlier proposed a simple and effective
acidolysis method to cleave the specific C–N bonds [27], and
the valuable C and N alternated-aromatic ring (CNAR) units
in dense melamine–formaldehyde resins (MFRs) can be
recovered using methanesulfonic acid (MSA)–tetrahydrofuran
(THF)–10 wt% H2O system under the acidic conditions [1].
It will be high desirable to combine the chemical recycling of
resin into the monomers and the synthesis of monomers into
new resins. In such case, the process cost will be largely
reduced. However, this remains as a big challenge in catal-
ysis, and no reports have been found. In fact, MFF has
already a large number of loose pores, which allows its
contact with the catalyst in solution without the swelling of
its body. Hence, a greener and more efficient alkaline hy-
drolysis system was proposed to degrade MFF [28,29]. We
noticed that in a certain concentration of NaOH–H2O system,
MFF can be converted to the chemical intermediates such as
ammelide and ammeline after 4 h at 160
C, which can be
further reused in the synthesis of new melamine urea-form-
aldehyde resin (MUFs) materials [30]. In addition, the inor-
ganic alkaline catalyst is stable and non-volatile, showing no
loss in the degradation process; meanwhile, it is less corro-
sive to the equipment.
Inspired by these findings, the NaOH–H2O solution was
developed in this work to degrade MFF into the monomers of
ammelide and ammeline in the aqueous system with NaOH as
the catalyst, followed by their synthesis into MUFs in the
alkaline system. The NaOH–H2O system showed high
degradation degree after reusing for 7 times (Fig. S1, Sup-
porting Information), which shows its promosing future in the
industrial.
Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
2. Experimental section
2.1. Chemicals and materials
All chemicals used were commercially available, such as
sodium hydroxide (NaOH), sodium carbonate (Na2CO3), so-
dium bicarbonate (NaHCO3), potassium hydroxide (KOH),
formaldehyde solution (37 wt.%) were purchased from Sino-
pharm Chemicals Reagent Co., Ltd. Deuterium oxide (D2O,
99.9% atom D) was purchased from Macklin. Acetone (AR).
Ethanol absolute (AR) was bought from Beichen Fangzheng
Chemical Reagent Co. Ltd (Tianjin, China). All the reagents
were analytic purity grade and were used without further pu-
rification. Melamine formaldehyde foam (MFF) was provided
by Puyang Greencos New Material Technology Co. Ltd.
2.2. Degradation of MFF
0.15 g of MFF pieces and 0.5 g catalyst in 4.5 g aqueous
solution were added into a Teflon-lined autoclave with a vol-
ume of 10 mL. The degradation reaction was carried out at
160
C. The undegraded MFF fragments were insoluble in the
alkaline system, which can be directly filtered after the reac-
tion. Ammelide and ammeline were precipitated after adding
ethanol to the filtrate. Finally, the precipitated degradation
products were dried in the oven at 80
C for 12 h. The mixture
of ethanol and alkaline filtrate were separated by distillation,
and both ethanol and the alkaline systems was recycled.
The degradation ratio of MFF could be calculated via the
following equation:
W0  W1
Degradation ratio ðRd ; %Þ ¼  100%
W0
where, W0 and W1 were the masses of raw MFF and MFF
residue after degradation, respectively. Degradation products
are mainly monomers of triazine rings, which are difficult to
dissolve in ethanol. White powder can be precipitated by
adding ethanol into the degradation solution, and the products
can be obtained after repeated washing and drying. The con-
centration of degradation products in D2O were quantified by
NMR analysis using the internal standard. The internal stan-
dard reagent in NMR was fumaric acid, which was dissolved
in D2O quantitatively. Specifically, by comparing their peak
integrals to that of internal standard in the spectra, the masses
of degradation products were calculated.
2.3. Synthesis of MUFs from the degradation products of
MFF
MUFs were synthesized by the standard procedure using
variable amounts of purified urea and formaldehyde solutions,
where 50 or 100% of melamine was replaced by the degra-
dation products of MFF.
The molar ratio of formaldehyde to urea is 1.2. Urea was
added by 7: 2:1 mass ratio in 3 times in sequence. Formal-
dehyde solution (37 wt%) was poured into three-way flask,
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S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx 3

and heated to 55
C in oil bath. The pH of the reaction solution Table 1

was adjusted to 7.0–8.0 with 5% NaOH and ammonia mixture. The catalytic decomposition of MFF.a


After the first urea part was added, the temperature of the Entry System Catalyst/wt.% Time/h TEMP/ C Rd/%
reaction solution was slowly raised to 85
C and kept for 1 NaOH 5 4 160 63.1
45 min. Then add proper amount of formic acid solution to 2 NaOH 10 4 160 97.2
adjust the pH to 5.0–5.5, and add the second urea part and 3 NaOH 15 4 160 98.3
4 NaOH 20 4 160 98.4
10 wt% melamine. Stop heating and cool down slightly to 5 NaOH 30 4 160 98.8
80
C until the solution becomes milky white; add the third 6 KOH 10 4 160 92.8
part of urea, stir for 30 min at a constant temperature. Adjust 7 Ca(OH)2 10 4 160 1.4
the pH value to 7.5–8.5 with 5% NaOH and ammonia solution, 8 Na2CO3 10 4 160 11.6
add ammonium chloride as curing agent and continue to stir 9 Na2CO3 30 12 180 24.2
10 NaHCO3 10 4 160 3.7
thoroughly for 15 min. 11 NaHCO3 30 12 180 6.4
12 HCl 10 2 180 97.6
2.4. Characterizations 13 MSA 10 1.5 180 98.4
14 ZnCl2 10 12 180 0
To explore the chemical structure of the degradation 15 AlCl3 10 12 180 0
16 MgCl2 10 12 180 0
products, NMR data were collected on an AVANCE IIITM 17 CaCl2 10 12 180 0
(Bruker, Switzerland) spectrometer (400 MHz). To explore the 18 CuCl2 10 12 180 0
changes of functional group in the degradation process, FT-IR 19 MnCl2 10 12 180 0
spectra were monitored by Vertex 80 V (VRUKER, Germany) 20 NaCl 10 12 180 0
spectrometer in the change of 4000–400 cm1 wavenumber 21 LiCl 10 12 180 0
with a resolution of 4 cm1, and 40 times scan were accu- a
Reaction condition: Teflon-lined reactor. Quality of MFF (0.15 g),
mulated to form 1 spectrum. The covalent states of C, N, O catalytic-aqueous solution (5 g, catalyst purity: 99%).
were investigated by X-ray photoelectron spectroscopy (XPS)
(an AXIS ULTRA DLD spectrometer with Al-Ka X-ray ratio of more than 97% (Entry 1–5). Hydrochloric acid (HCl)
resource (hv ¼ 1486.6 eV)). The morphology of degradation and MSA were also efficiently catalyze the degradation of
product was characterized by a scanning electron microscopy MFF, showing the degradation ratio of 97.6% and 98.4%,
(SEM, JSM-7900F, Japan). respectively (Entry 12, 13). Considering the volatile feature of
acid reagents, it is not conducive to the industrial production.
3. Results and discussion In addition, HCl will combine with ammonium ions in the
solution to generate ammonium chloride (NH4Cl) during the
3.1. Comparison of different catalysts reaction, which will be consumed as the reaction proceeds.
The catalytic effects of Lewis acid catalysts were also inves-
The study on the hydrolytic property of cured resins mainly tigated (Entry 14–21). The results showed that they had
focuses on the activation of chemical links in the resin neglectable catalytic activity towards the degradation of MFF.
network. The degradation of MFRs could be achieved by
acidolysis accelerated at a certain temperature and under the 3.2. The corrosion effect of alkaline system on the MFF
strong acidic condition. Different from the dense MFRs, MFF surface
has large amounts of pores in structure, which is beneficial to
the fast diffusion of solvent. THF that can swell the resin in To investigate the effect of the system for the degradation
other studies is not necessary for the degradation of MFF [27]. of MFF, the surface morphology transformations of MFF
In addition, the oxidation of acidolysis process is strong, during the degradation process was explored by SEM (Fig. 1).
which may lead to the complex distribution of degradation The surface of virgin MFF was flat without irregular cracks.
products. Therefore, alkaline hydrolysis will be feasible due to After 30 min, some rough spots appeared on the smooth sur-
its mild conditions, and the degradation products in this case face of MFF. As the reaction proceeded, the surface of MFF
can be directly used for the production of new MUFs. became rough and uneven, accompanied by the appearance of
The performances of various acidic or basic catalysts were tiny holes. As the time increased, the surface layer of MFF
explored, as listed in Table 1. When the strong alkalis began to exfoliate and the small holes became denser. As the
including NaOH (Entry 2) and KOH (Entry 6) were used as reaction time was prolonged to 4 h, the holes and gullies on the
the catalyst, the depolymerization of MFF could be achieved surface became larger, which made the surface rougher. The
at a certain concentration of alkali. MFF was partly decom- volume of MFF body did not increase significantly during the
posed in the weak alkaline solvent system (Entry 7, 8, and 10), degradation process, but its surface morphology changed
and it did not fully depolymerize with the increase of catalyst greatly. Therefore, the corrosion effect of solvent plays an
concentration, reaction time and temperature (Entry 9 and11). important role in the alkaline hydrolysis system.
This result indicated that the alkalinity of catalyst is a key MFF has an open-cellular morphology, which facilitates the
factor for decomposing MFF. It is found that NaOH rapid and full contact of itself with both the solvent and catalyst
(10 wt.%)-H2O solution can achieve a MFF depolymerization [3]. The alkaline system eroded the surface of MFF and caused

Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
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4 S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx
Fig. 1. SEM images amplified 5000 times of virgin MFF (a) and materials after 30min (b), 1 h (c), 2 h (d), 3 h (e), 4 h (f) of degradation (Reaction conditions: the
Teflon-lined reactor, 120
C, MFF 0.15 g, NaOH (10 wt.%)-H2O system).
the fracture in some skeleton of MFF, which further promoted
the transfer of solvent into the interior of resin (Fig. S2, Sup-
porting Information). With the extension of reaction time, the
MFF framework continued to fracture along with the intense
corrosion effect. The fragmentation structure made the rate of
degradation faster and faster. This may explain why MFF is
more prone to alkaline hydrolysis than the dense resin.
3.3. The degradation of MFF under different
temperatures and times
The degradation reaction of thermosetting resins generally
involves the diffusion of the solvent and the catalyst into the resin,
followed by the cleavage of the specific bonds in the resin. For the
dense resins, the degradation rate is greatly affected by the
swelling process, in which the volume of resin will be expanded
obviously and then the degradation reaction will occur on the
surface and in the body of resin simultaneously [26,31]. And for
MFF, the vesicular structure enabled the fast diffusion of solvent,
and thus, the rate of whole degradation process depends primarily
on the rate of degradation reaction.
The conversion rates of MFF were tested under different
temperatures (Fig. S3). When the reaction temperature was
below 100
C, the reaction rate was slow and the final conversion
rate of MFF was less than 70%. With the increase of temperature,
the reaction rate and final conversion ratio increased gradually.
When the temperature reached 140
C, the final conversion rate
of MFF was close to 97% after 6 h of reaction. With the further
increasing in the temperature, the conversion rate of MFF
reached nearly 95% after 4 h under 160
C. As the triazine ring
structure of MFF is not stable at above 200
C, it might produce
toxic gas after the disordered bond breaking. Hence, the reaction
temperature was controlled no higher than 180
C. In the
following experimental characterization, the optimal reaction
conditions were 160
C and 4 h in the Teflon-lined reactor.
Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
3.4. Analysis of degradation products
The degradation products of MFF were characterized by
13
C NMR. The typical 13C NMR spectrum from the residues
of hydrolyzed solutions was shown in Fig. 2a, the obvious
chemical shifts were observed for the signals ca.171 ppm after
degradation at 160
C. The peak of C on the CNAR connected
with –NH2 showed signal at this region, and the small dif-
ference between 171.11 ppm and 171.12 ppm indicated the
presence of ammelide and ammeline. Besides, the C on the
CNAR linked to –OH showed a strong signal at position
168.35 ppm. These NMR spectra implied that the C–N bonds
outside CNAR were partly cleaved, while the C–N bonds of
the CNAR were retained. In order to verify the above assig-
nations for signals, cyanuric acid was added into the above
solution, which caused the significant enhancement of signal
at 167.47 ppm (Fig. 2b). The further addition of melamine led
to an enhanced signal at 166.76 ppm (Fig. 2c). These results
indicated that part of the amino group outside the CNAR was
replaced by the hydroxyl group, and finally degradation
products were mainly composed of ammelide and ammeline.
The selective cleavage of bonds in MFF was further veri-
fied by IR (Fig. S4). The vibration at 1373 cm1 and
1623 cm1in the CNAR of MFF was decreased after 4 h.
Correspondingly, the peak appeared at 1495 cm1 and
1678 cm1 indicated the offset of C¼N bond, which caused by
changes in the environment outside the CNAR. Compared
with the IR spectrum of standard cyanuric acid, it was found
that –OH group attached to the CNAR at 1036 cm1 and
1088 cm1 was formed gradually after 2 h. Besides, the signal
of the –NH2 group attached to the CNAR at 1211 cm1 was
also decreased. The IR spectra also showed that part of the
–NH2 outside the CNAR was replaced by the –OH group,
which verified the presence of ammelide and ammeline as the
products.
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S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx 5

Fig. 2. The 13C NMR spectrum (a) of the decomposed products of MFRs, after adding cyanuric acid (b) and melamine (c). Samples were prepared in D2O
(Teflon-lined reactor 160
C, 4 h, NaOH (10 wt.%)-H2O system).

Interestingly, compared with the raw MFF materials, the
peak intensity of the C–O–C bond at 1040 cm1 obviously
disappeared after 2 h, indicating that the cleavage of the C–O
bond was easier than the C–N bonds. The peaks between 2750
and 2900 cm1 suggested the –CH2 groups, the peak of –NH
at 2969 cm1 was evident, and the enhanced peaks in the
range of 3200–3400 cm1 implied the presence of OH, NH
and NH2 groups. To our surprise, the signal of carbonyl
appeared at 1676 cm1 after 4 h of reaction, which facilitated
the subsequent exploration of the recycling of products.
3.5. Mechanism of MFF alkaline hydrolysis
The changes of surface functional groups of MFF at
different reaction time were verified by XPS. After 2 h of
reaction, the peak intensity of sp2C in CNAR was basically
unchanged (Fig. 3b) compared with raw material MFF
(Fig. 3a). The signal of sp2N in CNAR was increased, while
the –NH2 functional group outside the CNAR was signifi-
cantly reduced (Fig. 3d and e). It indicated that the structure
outside the CNAR ring has changed. At the same time, the
peak intensity of C–O–C changed, and the proportion of –OH
began to rise (Fig. 3g and h), illustrating that there were
constantly –OH groups attached to the MFF body during the
hydrolysis process. As the reaction time was prolonged, the
content of sp2C in CNAR was increased (Fig. 3c) and the C–
O–C was dropped to a very low level (Fig. 3i), which showed
that the three-dimensional chain structure of MFF was
destroyed. In addition, the peaks for sp2N in CNAR (Fig. 3f)
and –OH outside the CNAR were further increased (Fig. 3i),
indicating that the –NH2 groups outside the CNAR were
constantly replaced by –OH groups. Interestingly, the signal of
C¼O group was increased in the beginning and then
decreased. It suggested that the generated formaldehyde was
instable in the alkaline hydrolysis system.
The molar ratios of different functional groups on the
surface of MFF were also calculated by XPS (Table S1). As
the reaction progresses, the relative content of C–O–C dropped
from 95.62% to 2.60%, which indicated the disintegration of
the three-dimensional structure of MFF. The relative content
of sp2N increased from 51.13% to 93.16%, while the content
of sp3N decreased from 48.87% to 6.84%. At the same time,
the relative content of –OH increased from 0 to 92.78%, which
was further verified the –NH2 groups outside the CNAR were
party replaced by –OH groups.
Based on the results of product identification, the degra-
dation mechanism of MFF was proposed, as illustrated in
Scheme 1 and 2. The hydroxide ions attracted the hydrogen
ions on nitrogen atoms, making nitrogen atoms negatively
charged and the adjacent carbon atoms positively charged.
Hydrogen and oxygen atoms of H2O in the solution combined
with nitrogen and carbon atoms, respectively, breaking the
sp3C- sp3N bond outside the CNAR ring. After the continuous
degradation of MFF, the macromolecular network structure
was broken into many ring monomers that were similar to
melamine. In such case, the hydroxyl groups of H2O mole-
cules were gradually introduced into the outer side of the
CNAR monomer to form ammelide and ammeline. The ratio
of degradation products was calculated from their corre-
sponding peak areas in 1H NMR spectrum. The calculated

Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
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6 S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx

Fig. 3. XPS spectra of C-functional groups: virgin MFF (a), MFF after 2 h of degradation (b), and MFF after 4 h of degradation (c). XPS spectra of N-functional
groups: virgin MFF (d), MFF after 2 h of degradation (e), and MFF after 4 h of degradation (f). XPS spectra of N-functional groups: virgin MFF (g), MFF after 2 h
of degradation (h), and MFF after 4 h of degradation (i) (Reaction conditions: the Teflon-lined reactor, 120
C, MFF 0.15 g, NaOH (10 wt.%)-H2O system).

ratios of ammelide and ammeline were 28.2% and 71.8%,
respectively (Fig. S7).
3.6. Comparison of original and recycled MUFs
To verify the feasibility of the hydrolytic process, the
degradation products of MFF was used to make new MUFs
(the new UF resins were named as recycled MUFs).
According to the FT-IR analysis (Fig. 4), the peaks at
1689 cm1 and 1657 cm1 were assigned to the characteristic
absorptions of C¼O and C–N of amido bonds in MUFs. The
signal of C¼N bond was obviously enhanced after adding
melamine or degradation products, indicating the presence of
CNAR in MUF. At the same time, the signal peak of the –NH2
group attached to the CNAR at 1197 cm1 was increased. This
finding illustrated that the recycled MUFs had the similar

Scheme 1. Schematic presentation of recycling of MFF by alkaline hydrolysis into ammelide and ammeline, followed by their synthesis of new MUFs materials.

Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
 + MODEL

S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx 7

Scheme 2. Possible reaction pathways of MFF degradation.

chemical structure to the original MUFs. In addition, the
signals at 750 cm1, 811 cm1 and 1045 cm1 represented
–OH, –NH and –CH2OH, respectively.
Thermogravimetric analysis (Fig. S5) showed that both
normal urea-formaldehyde resins (UF) and MUFs’ starting
gravimetric temperature (Ta) and final temperature (Tb) were
in the range of 220
C–330
C. UF reached its maximum
weight loss rate at ca. 261
C, while MUF reached its
maximum weightlessness velocity at ca. 282
C. TGA results
showed that the introduction of CNAR increased the initial
decomposition temperature of the material. The deviation of
the maximum weight loss rate indicated that the thermal sta-
bility of the material was further improved. The glass transi-
tion temperature (Tg) of resin was measured by DSC. As
shown in Fig. S6, the obvious glass transition was occurred in
the temperature range of 230–250
C. With the introduction of
melamine or degradation products, the Tg of MUFs was
increased compared with that of UF. The change of Tg may
lead to the change of thermogravimetric rate, which also
indicated that the generation of new chemical cross-linking
favored the thermal stability of resin. In addition, the me-
chanical performance test results (Table S2 in the ESI) show
that the normal UF had good ductility with elongation at break
of 42.79%. When either melamine or the degradation products
were added, the ductility of MUFs was decreased, whereas the
tensile strength of MUFs was largely enhanced to a value
higher than 3.8 MPa. This result indicated that the introduction
of CNAR greatly improved the rigidity of the MUFs material.

Fig. 4. FT-IR spectra of normal UF, original and recycled MUFs.

Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
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 + MODEL
8 S. Wu et al. / Green Energy & Environment xxx (xxxx) xxx
With the addition of either melamine or the degradation
products, the tensile yield stress was also improved, reaching
more than 2.3 MPa. These two values were three times higher
than that of the normal UF (0.75 MPa).
4. Conclusions
We report a green and effective NaOH (10 wt.%)-H2O
system to recycle the waste MFFs under mild conditions
(160
C). The alkaline system exhibited the high corrosion
effect on the MFF surface, which accelerated the collapse of
three-dimensional network structure in MFF. The main
degradation products including ammelide and ammeline could
be directly re-used to fabricate new MUFs, which was deriving
from the synthesized resin functioned the same as an original
MUFs. Besides its effectiveness, the alkaline solution has su-
perior reusability. This work proved the feasibility of using
alkaline hydrolysis to recycle waste MFF, which showed many
advantages such as environmentally friendly, easy process
operating and relative low production cost over the other
previous methods.
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
This work was supported by the National Natural Science
Foundation of China (No. 21774139), China, Key Research and
Development Program of Shanxi Province, China (No,
202102040201009), special fund of Beijing Key Laboratory of
Clean Fuels and Efficient Catalytic Emission Reduction Tech-
nology and the Fund for Shanxi “1331 Project”. Thanks to
Ningbo Kejiang Culture Sci. & Tech. Development Co., Ltd. For
the help in schematic drawing.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.gee.2022.10.008.
Please cite this article as: S. Wu et al., An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis, Green Energy &
Environment, https://doi.org/10.1016/j.gee.2022.10.008
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