Research Article

pubs.acs.org/journal/ascecg

Chemical Recycling of Carbon Fiber Reinforced Epoxy Resin

Composites via Selective Cleavage of the CarbonNitrogen Bond
Yuqi Wang,, Xiaojing Cui, Hui Ge, Yongxing Yang, Yingxiong Wang, Ce Zhang,, Jingjing Li,
Tiansheng Deng,*, Zhangfeng Qin, and Xianglin Hou*,

The Biorenery Research and Engineering Center, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan
Road, Taiyuan 030001, Peoples Republic of China

University of Chinese Academy of Sciences, Beijing 100049, People Republic of China

Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, Peoples Republic of China
*
S Supporting Information

ABSTRACT: An ecient strategy is developed for chemical

recycling of cured epoxy resin (CEP) from its carbon ber
reinforced polymer composites (CFREP) using AlCl3/
CH3COOH as the degradation system. Acetic acid swells the
dense structures of CEP, facilitating the penetration of the
aluminum ion catalyst into the polymer matrix. The weakly
coordinating aluminum ions in CH3COOH solution selectively
cleave the CN bond while leaving the CC, CO (aryl alkyl
ether) bonds intact. This process recovers valuable oligomers
and carbon bers from CFREP.

KEYWORDS: Chemical recycling, Epoxy resin, Carbon ber, Selective CN bond cleavage

INTRODUCTION
In the past few decades, carbon ber reinforced epoxy resin
composites (CFREP) have been widely used in the aeronautical
eld, trac transformation industry, wind turbine eld,
electronic industry, and sports or entertainment products
because of their excellent physical and chemical properties.
With the extensive application of CFREP, the leftover materials
in the manufacturing process and end-of-life waste products
have caused environmental problems.1 The recycling of waste
CFREP is highly desirable but challenging because cured epoxy
resin (CEP) with its three-dimensional network is both
insoluble and infusible.2
CFREP composites are composed of two parts, i.e., carbon
bers (CFs) as core and CEP as coating. Traditional disposal
routes such as landll and incineration are becoming
increasingly restricted because of environmental protection
and legal restriction.3 The recycling of CFREP is usually
available by degrading the CEP coating, with as limited damage
of CFs as possible. In recent years, many recycling methods
have been investigated, including mechanical, thermal, and
chemical recycling methods.47 Among them, chemical
recycling is the most promising since CFs can be recycled
from CFREP together with valuable building blocks of CEP all
in the same process.
Conventionally, chemical recycling of CFREP utilizes high
temperature, special solvents (e.g., supercritical uid8), or
strong oxidation (e.g., nitric acid or hydrogen peroxide) in
order to cleave the chemical bonds of CEP from the CFs
surface. The CEP can be dissolved in supercritical uids. For
example, thermosetting resin composites have been degraded in
supercritical water915 and supercritical alcohols16 including
methanol,17 ethanol, n-propanol,18,19 and i-propanol.20,21
Weirong Dang et al. recycled glass ber reinforced epoxy
resin composites (GFREP) using a solution nitric acid.22,23 Juan
Li et al. recycled CFREP using hydrogen peroxide.24,25
However, both high temperatures and strong oxidation led to
nonselective cleavage of the chemical bonds of CEP and
produced a large amount of toxic gases. In addition to high
temperature and strong oxidation, other researchers degraded
ber reinforced epoxy resin composites using expensive ionic
liquid, which limits their large-scale application.26,27
Ideally, the recycling of CFs requires a selective cleavage of
specic bonds in CEP using an economical, high yielding, and
scalable system. The complexity of products and emission of
toxic gases should be minimized. CEP contains several dierent
functionalities with dierent reactivities, i.e., benzene rings, C
C bonds, CO bonds, and CN bonds. The selective cleavage
of CN or CO bond could not only facilitate recycling of
CFs but also retain the valuable carbon skeleton of CEP. In our
previous work, we demonstrated that metal ions in
incompletely coordinating or weakly coordinating state enable
the cleavage of CN and CO bonds in organic
Received: August 27, 2015
Revised: October 9, 2015

XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.5b00949

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Scheme 1. Selective CN Bond Cleavage of CEP in the Degradation Reaction

polymers.2830 Besides the catalyst, the selective degradation of

thermosetting resin is strongly dependent on the solvent. The
RESULTS AND DISCUSSION
Initially, the swelling behaviors of CEP were investigated using
solvent should eciently swell the thermosetting resin and various solvents. As shown in Figure 1, the CEP swelled best in
favor the transferring of the catalyst into the resin matrix.
Moreover, the catalytic cations should coordinate weakly with
the solvent molecules. In this way, the weakly coordinating ions
that enter the matrix of the swelled resin can coordinate with
the lone pair electrons of the heteroatom (O or N), facilitating
the selective cleavage of carbonheteroatom bonds (CO or
CN).
In this article, an economical and ecient catalytic system to
selectively cleave the CN bond rather than the CO and C
C bond is developed. In this way not only CFs can be recycled
but also the carbon skeleton structure of CEP, all in one
process (as shown in Scheme 1). CEP and its composites
CFREP were decomposed under mild conditions (180 C, 13
atm) using AlCl3/CH3COOH as the degradation system. The
compositions of degradation products were investigated by FT-
IR, NMR, and elemental analysis, from which a possible route
for decomposing CEP and its composites was proposed. The
selected epoxy resin is bisphenol A diglycidyl ether type epoxy
resin (DGEBA), which is a versatile epoxy resin. The selected
curing agent is 3,3-dimethyl-4,4-diaminodicyclohexylmethane Figure 1. Swelling property of CEP in various solvents at 180 C for 6
(DMDC), which is an intermediate temperature curing agent. h.
The curing process of CEP is shown in SI Scheme 1. To
selectively break the CN bond, a Lewis acid is required to
coordinate with the nitrogen lone electron pair. In this work, acetic acid, where its weight increase reached more than 56%.
AlCl3 is used as the Lewis acid catalyst for the selective cleavage On the contrary, the swelling ability of water was the least, and
of the CN bond in CEP. the weight increase of CEP was only about 3.8%. The swelling

abilities of alcohols were relatively low, and the swelling ratio of

EXPERIMENTAL SECTION
The degradation of CEP was carried out in a Teon-lined autoclave
with a content of 10 mL. In each experiment, a CEP strip (about 0.8 g,
10 mm 10 mm 2 mm of cuboid), AlCl3 (0.75 g), and acetic acid
(4.25 g) were added, and the degradation reaction was carried out
under the specied conditions. After the decomposition, the reaction
products were dissolved in acetone with the aid of ultrasound, while
the aluminum catalyst was separated by ltration, due to its insolubility
in acetone. The degradation products were obtained by removing
acetone using rotary evaporation at 45 C. The compositions of the
degradation products and recycled catalyst were characterized by FT-
IR, NMR, elemental analysis, and GPC. In the case of CFREP
degradation, about 1.5 g of CFREP was degraded under the
degradation condition described above. After the decomposition
reaction, the CFs were collected and washed 3 times with 10 mL of
acetone. The recycled CF properties and appearance were tested by a
monolament tensile machine, XPS, and SEM.
B DOI: 10.1021/acssuschemeng.5b00949
methanol, ethanol, n-propanol, and i-propanol is 18.79%,
20.85%, 16.16%, and 11.06%, respectively. The good swelling
ability facilitates the transferring of catalyst into the matrix of
epoxy resin. The solvent should, however, also dissolve the
catalyst and form weakly coordinating metal ions. Thus, the
acetic acid was selected as the solvent.
The degradation of CEP was performed in acetic acid with
various metal salts as the catalyst. The metal cations including
Al3+, Fe3+, Zn2+, Cu2+, and Mg2+ (Table 1, entries 15). AlCl3
showed superior ability for decomposing CEP relative to that of
the other tested metal ions. FeCl3, ZnCl2, CuCl2, and MgCl2
only had little catalytic eect for decomposing CEP. The
investigated anions include Cl, NO3, SO42, and CH3COO
(Table 1, entries 68). Cl was found to be better than other
anions for the catalytic eect of Al3+. Therefore, AlCl3 was
chosen as the catalyst.
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Table 1. Catalytic Eects of Various Cations or Anions on

the Degradation Reaction of CEPa
entry catalyst degradation ratio/wt %b
1 AlCl3 84.21
2 FeCl3 swollen
3 ZnCl2 swollen
4 CuCl2 swollen
5 MgCl2 swollen
6 Al(NO3)3 swollen
7 Al2(SO4)3 swollen
8 Al(CH3COO)3 swollen
a
Acetic acid as solvent. Reaction conditions: catalyst mass fraction10
wt %, 180 C, 6 h. bThe calculation formula of the degradation ratio is
Dr = (m1 m2)/m1 100%, where Dr is degradation ratio, m1 is the
initial quality of CEP before degradation, and m2 is the remaining
quality of CEP after degradation.

In the AlCl3/CH3COOH degradation system, the eects of Figure 2. FT-IR spectra of (a) CEP, (b) degradation products, and (c)
AlCl3 concentration, reaction temperature, and reaction time recycled catalyst.
on the degradation behaviors of CEP were investigated (Table
2). CEP decomposed completely with the minimum AlCl3

Table 2. Inuence of Catalyst Mass Fraction, Temperature,

and Time on Degradation of CEPa
mass fraction temperature time degradation ratio
entry (wt %)b (C) (h) (wt %)c
1 15 180 6 100
2 10 180 6 84.21
3 5 180 6 swollen
4 15 170 6 79.17
5 15 160 6 37.75
6 15 180 5 92.74
7 15 180 4 74.18
8 15 180 3 22.13
a
React in the AlCl3/CH3COOH degradation system. bMass fraction
of AlCl3 in the degradation system. cThe calculation formula of the
degradation ratio is Dr = (m1 m2)/m1 100%, where Dr is the Figure 3. Solid state NMR of (a) CEP, (b) degradation products, and
degradation ratio, m1 is the initial quality of CEP before degradation, (c) recycled catalyst.
and m2 is the remaining quality of drying CEP after degradation.
Table 3. Elemental Analysis of CEP, Degradation Products,
and Recycled Catalysta
mass fraction being 15 wt % at 180 C for 6 h (Table 2, entries
13). CEP decomposition into oligomers increased from sample C (%) H (%) N (%) O (%) Al (%)
37.75% to 100% in 15 wt % AlCl3/CH3COOH, when the CEP 73.99 8.79 2.85 14.21
reaction temperature was raised from 160 to 180 C (Table 2, degradation products 59.75 7.38 2.27 17.96 0.0049
entries 45). The decomposition time had a signicant eect recycled catalyst 18.12 4.80 0.11 27.87 18.12
on the degradation of CEP because the degradation process a
The content of Al is characterized by ICP.
gradually takes places from the outer surface into the resin
interior. It took 6 h to degrade CEP completely (entries 68).
Thus, the optimal degrading conditions of CEP were The signal at 1248 cm1 in CEP is ascribed to the stretching
determined to be 15 wt % AlCl3 in acetic acid at 180 C for vibration of COC, while the signal of COC in the
6 h. After the degradation, the degradation products in the degradation products appears at 1240 cm1. The peak of aryl
reaction mixture were separated and weighted (see SI Figure 1 alkyl ethers (COC) appears in the spectrum of recycled
and SI Table 1). The recovery ratio of degradation products degradation products, indicating the conservation of aryl alkyl
was up to 97.43 wt %. The compositions of separated products ethers. The peak at 1743 cm1, found in the degradation
were analyzed by FT-IR (Figure 2), solid state NMR (Figure products, belongs to the CO stretching vibration of ester
3), and elemental analysis (Table 3). bond. The ester bond forms from the esterication reaction
The FT-IR spectra of raw materials (CEP) and degradation between acetic acid and the COH of diglycidyl ether unit,
products are shown in Figure 2a and b. The peaks of 1607, rather than the cleavage of aryl alkyl ether bond because the
1510, and 1458 cm1 in raw materials belong to the stretching carbonyl of aromatic ester will appear in higher wavenumber
vibration of benzene ring. The peaks of the benzene ring in than 1743 cm1, due to the conjugation with the benzene ring.
degradation products appear in 1600, 1506, and 1458 cm1, The obvious decrease in peak intensity at 1045 cm1 (COH
which indicates that the benzene ring structure remains intact. of diglycidyl ether unit) in Figure 2b implies a condensation of
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acetic acid and the COH in CEP (1034 cm1) during the
degradation process. By comparison with CEP, the remarkable
change of degradation products is observed by a reduction in
relative peak intensity of CN stretching vibration at 1183
cm1, which indicates the cleavage of the CN bond during the
degradation reaction. Moreover, in the FT-IR spectrum of the
degradation products, the wide peak around 3226 cm1 implies
that substantial NH bonds exist in the degradation products,
which also proves the cleavage of the CN bonds in CEP. By
comparing with the ratio of the peak intensity of CH2 (2927
cm1) to CH3 (2961 cm1) in CEP, the decrease of this ratio
in the degradation products indicates that the CN bonds
connected to the cyclohexyl in the curing agent unit were
cleaved. The above results illustrate that the weakly
coordinating aluminum ions enable the cleavage of the CN
bond without breaking the COC bond of aryl alkyl ethers of
CEP. In the spectrum of the recycled catalyst (Figure 2c), the
signals of 1586 and 1474 cm1 are the asymmetric and
symmetric stretching vibrations of COO, which indicate the
catalysts are partially transformed into aluminum acetate during
the degradation reaction.
The carbon skeleton structures of CEP and degradation
products were analyzed by solid state NMR (see Figure 3). In
the NMR spectra, the peaks of CEP at 157, 143, 127, and 114
ppm in Figure 3a belong to the carbon signals of the benzene
ring. The peaks of the benzene ring in the degradation product
appear at 157, 143, 129, and 114 as seen in Figure 3b. This
shows that the structure of the benzene ring remains intact in
the recycled degradation products. Furthermore, the peak at
157 ppm remains unchanged, indicating the existence of the
aryl alkyl ether (COC) in the degradation products. For
CEP, the peak at 42 ppm is designated to quaternary carbon of
bisphenol A, and the peak at 70 ppm belongs to the carbons of
glycidyl ether. Both of them remain unchanged in the
degradation process. The peaks between 32 and 34 ppm in
CEP are the signals of the cyclohexyl in the curing agent unit;
however, these peaks in the degradation products narrow down
to a limit range between 32 and 33 ppm. The peaks between 32
and 34 ppm decreased obviously in the degradation products,
suggesting that the CN bonds connected to the cyclohexyl
group were cleaved. The structure of the degradation products
were also explored by 1H NMR, 13C NMR, DEPT 135, and
DEPT 90 (SI Figures 2 and 3). It was found that the signals
from the benzene ring and the glycidyl ether unit are found in
the degradation products, which illustrates that the cleavage
takes place between carbon and heteroatom during degradation
reaction. The 13C-NMR spectra of uncured epoxy resin (UPR)
and curing agent after the degradation were also investigated
(SI Figures 4 and 5). This shows that the carbon skeleton of
UPR and curing agent remains intact. This result further
indicates the cleavage of tertiary carbon nitrogen bonds. In the
NMR spectrum of the recycled catalyst, the peak at 179 ppm is
the signal of carbonyl of carboxylate, and the peak at 25 ppm is
the signal of methyl. As shown in the 27Al-NMR spectra (SI
Figure 6), the recycled catalyst is mainly ve-coordinated
aluminum or six-coordinated aluminum. These results indicate
that the recycled catalyst is mainly aluminum acetate.
Elemental analysis was employed to obtain the element
components of degradation products and recycled catalyst
(Table 3). The CEP is mainly made of the elements C, H, N,
and O. These four elements account for 99.84 wt % of CEP.
The degradation products are also mainly composed of C, H,
N, and O. The aluminum content of degradation products is
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only 0.0049 wt %, which indicates that the aluminum salt was
eectively separated and removed in the process. However, the
total content of C, H, N, and O is only 87.36 wt %, so the
remainder 13 wt % is attributed to Cl according to element
balance. The recycled catalyst is mainly composed of C, H, O,
and Al. There is a small amount of N. The Al content reaches
up to 18.12 wt %. The total content of the ve elements (C, H,
O, N, Al) is 69.02 wt %, suggesting that the remaining 31 wt %
is the Cl element. These data show that the recycled catalysts
contain a mixture of aluminum acetate and aluminum chloride.
In order to make the proportion of elements more intuitive, the
original data are transformed into mole ratio (see SI Table 2).
The ratio of C to N of degradation products remains
unchanged relative to raw material, but the content of H and
O increases after degradation. The unchanged carbon nitrogen
ratio indicates the cleavage of the CN bond, which connects
with the cyclohexyl group of the curing agent because cleavage
of the other CN bond will lead to nitrogen loss. There exist
some Cl ions left in degradation products, but the Al content is
close to 0, which suggests that the Cl atom may substitute the
H atom of the phenyl group during the degradation reaction.
As shown in Table 3, the degradation products are mainly
composed of organic components. Thus, the molecular weight
and its distribution were investigated using the GPC method
(see SI Table 3). The weight-average molecular weight (Mw)
of degradation products is 2396 g/mol, which is nearly twice
that of the uncured epoxy resin (UEP). The number-average
molecular weight (Mn) of degradation products is 1635 g/mol,
and the polydispersity index (PDI) of degradation products is
1.46. The GPC data show that the Mn and Mw of degradation
products are larger relative to UEP, which indicates that the
degradation products should be the oligomers (UEP unit which
is connected by the N atom).
The main destination of this work is selective cleavage of the
carbon heteroatom bond so that the degradation products can
be reused in resin manufacturing. The FT-IR data show that the
COC bond keeps intact, whereas the CN bond is cleaved.
Furthermore, the FI-IR data also show that the CN bond of
the curing agent was cleaved in the degradation process, which
can be veried by the relative decrease of the CH2 peak
intensity. The NMR data, including solid state NMR, 1H NMR,
13
C NMR, DEPT 135, and DEPT 90 indicate that the carbon
skeleton structure of the resin remains intact. On the basis of
these results, we propose a possible decomposition catalytic
mechanism of CEP in the AlCl3/CH3COOH degradation
system (see Scheme 2). The weakly coordinating aluminum
ions coordinate the isolated electron pair of the nitrogen atoms.
The carboxylate oxygen of acetic acid, then attack the now
more electrophilic tertiary carbon, which leads to the cleavage
of the bond between the tertiary carbon and the nitrogen. This
results in the formation of the ester and the secondary amine.
However, the degradation of CFREP may be dierent from
that of CEP because of the existence of CFs. The eect of
reaction time on recycling of CFREP was studied, and the
morphology of the recycled CFs was observed using SEM (see
SI Figure 7). The surface of CFs was still covered by CEP after
reacting for 1 h in the 15 wt % AlCl3/CH3COOH degradation
system at 180 C, but cracks appeared on the surface. When the
reaction time extended to 2 h, most of the surface of CFs was
observed. Cleaner CFs were obtained after reaction for 3 h. To
guarantee the complete degradation, the chemical recycling of
CFREP was carried out in the optimal conditions for CEP (15
wt % AlCl3/CH3COOH, 180 C, 6 h). Figure 4 shows that the
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Scheme 2. Possible Decomposition Catalytic Mechanism of
CEP in the AlCl3/CH3COOH Degradation System
Figure 4. Pictures of (a) CFREP and (b) recycled CFs, and SEM
images of (c) virgin CFs and (d) recycled CFs. Reaction conditions:
degradation system AlCl3/CH3COOH and AlCl3 mass fraction 15 wt
%, 180 C, and 6 h.
CFREP decomposed completely, and the CFs were recycled.
Clean CFs were obtained after removing the CEP from
CFREP, as shown in Figure 4a and b. SEM was employed to
further study the surface morphology of the recycled CFs (see
Figure 4c and d). As compared with the very clean surface of
virgin CFs, there existed some spots in the surface of recycled
CFs. These spots are the incompletely degraded CEP. The
tensile strength of the recycled CFs was investigated using a
monolament tensile test (see SI Table 4). The tensile strength
of recycled CFs is 2871.96 MPa, which is 97.77% that of virgin
CFs. The tensile modulus of recycled CFs is 168.46, which is
98.07% that of virgin CFs. These results conrm that the
degradation system has insignicant impact on the tensile
strength of the recycled CFs.
The surface functional group compositions determined by
XPS are shown in SI Figure 8. In the XPS analysis of the
recovered carbon ber ((a3) in SI Figure 8a), the O 1s peak is
E DOI: 10.1021/acssuschemeng.5b00949
Research Article
considerably larger compared with the C 1s peaks. The surface
elemental composition is shown in SI Table 5. As shown in SI
Table 5, the carbon content decreases about 10%, and the
oxygen content increases about 10% after degradation in the
AlCl3/CH3COOH system. To clarify the functional groups on
the surface of the recycled carbon bers, C 1s spectra are curve-
tted (see SI Figure 8b, c, and d). The notable change of the
recycled CF surface is the appearance of the CO bond
(289.05 eV), which may be important for reuse of the recycled
CFs. The O 1s peak-tting curves are shown in SI Figure 9, and
the percentage of oxygenated functional group is shown in SI
Table 6. The COH group decreased about 38%, and the
increase of the CO group is about 26%. Especially, the new
group OCO appears, and its content reached up to about
11% in the recycled CFs surface. The above result shows that
the AlCl3/CH3COOH degradation method is superior to that
of other degradation methods, for example, thermal decom-
position or supercritical liquids (see SI Table 7).
CONCLUSIONS
In conclusion, chemical recycling of CFREP has successfully
been realized via a selective cleavage of a tertiary carbon
nitrogen bond using AlCl3/CH3COOH as the degradation
system. The tertiary carbon nitrogen bond cleavage was
evidenced by FT-IR, NMR, elemental analysis, and GPC.
These characterizations also showed that the CC and CO
bond remained intact. Under the optimal degradation
conditions (15 wt %, 180 C, 6 h), the recovery yield of
CEP reaches up to 97.43 wt %, and the clean CFs recovered
conserved about 97.77% of their tensile strength compared with
that of virgin CFs. Especially, oligomers of CEP can be
preserved and recycled, which facilitates their reuse in resin
manufacturing. This promising novel strategy is an environ-
mentally benign and economically feasible method for chemical
recycling of the CFREP composite.
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.5b00949.
Synthesis process of CEP; eective separation of
degradation products and catalyst; NMR character-
izations; elemental analysis (mole ratio) and molecular
weight of products; characterizations of recycled CFs;
comparison of various recycling methods in recycling
CFREP (PDF)
AUTHOR INFORMATION
Corresponding Authors
*(T.D.) E-mail: dts117@sxicc.ac.cn.
*(X.H.) E-mail: houxianglin@sxicc.ac.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work was supported by Scientic and technological project
of Shanxi Province (20130322005-01). We thank Associate
Professor Christian Marcus Pedersen for help with preparing
the manuscript.
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F DOI: 10.1021/acssuschemeng.5b00949
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX