pubs.acs.org/journal/ascecg
The Biorenery Research and Engineering Center, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan
Road, Taiyuan 030001, Peoples Republic of China
Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, Peoples Republic of China
*
S Supporting Information
KEYWORDS: Chemical recycling, Epoxy resin, Carbon ber, Selective CN bond cleavage
INTRODUCTION
In the past few decades, carbon ber reinforced epoxy resin
surface. The CEP can be dissolved in supercritical uids. For
example, thermosetting resin composites have been degraded in
composites (CFREP) have been widely used in the aeronautical supercritical water915 and supercritical alcohols16 including
eld, trac transformation industry, wind turbine eld, methanol,17 ethanol, n-propanol,18,19 and i-propanol.20,21
electronic industry, and sports or entertainment products Weirong Dang et al. recycled glass ber reinforced epoxy
because of their excellent physical and chemical properties. resin composites (GFREP) using a solution nitric acid.22,23 Juan
With the extensive application of CFREP, the leftover materials Li et al. recycled CFREP using hydrogen peroxide.24,25
in the manufacturing process and end-of-life waste products However, both high temperatures and strong oxidation led to
have caused environmental problems.1 The recycling of waste nonselective cleavage of the chemical bonds of CEP and
CFREP is highly desirable but challenging because cured epoxy produced a large amount of toxic gases. In addition to high
resin (CEP) with its three-dimensional network is both temperature and strong oxidation, other researchers degraded
insoluble and infusible.2 ber reinforced epoxy resin composites using expensive ionic
CFREP composites are composed of two parts, i.e., carbon liquid, which limits their large-scale application.26,27
bers (CFs) as core and CEP as coating. Traditional disposal Ideally, the recycling of CFs requires a selective cleavage of
routes such as landll and incineration are becoming specic bonds in CEP using an economical, high yielding, and
increasingly restricted because of environmental protection scalable system. The complexity of products and emission of
and legal restriction.3 The recycling of CFREP is usually toxic gases should be minimized. CEP contains several dierent
available by degrading the CEP coating, with as limited damage functionalities with dierent reactivities, i.e., benzene rings, C
of CFs as possible. In recent years, many recycling methods C bonds, CO bonds, and CN bonds. The selective cleavage
have been investigated, including mechanical, thermal, and of CN or CO bond could not only facilitate recycling of
chemical recycling methods.47 Among them, chemical CFs but also retain the valuable carbon skeleton of CEP. In our
recycling is the most promising since CFs can be recycled previous work, we demonstrated that metal ions in
from CFREP together with valuable building blocks of CEP all incompletely coordinating or weakly coordinating state enable
in the same process. the cleavage of CN and CO bonds in organic
Conventionally, chemical recycling of CFREP utilizes high
temperature, special solvents (e.g., supercritical uid8), or Received: August 27, 2015
strong oxidation (e.g., nitric acid or hydrogen peroxide) in Revised: October 9, 2015
order to cleave the chemical bonds of CEP from the CFs
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
acetic acid and the COH in CEP (1034 cm1) during the only 0.0049 wt %, which indicates that the aluminum salt was
degradation process. By comparison with CEP, the remarkable eectively separated and removed in the process. However, the
change of degradation products is observed by a reduction in total content of C, H, N, and O is only 87.36 wt %, so the
relative peak intensity of CN stretching vibration at 1183 remainder 13 wt % is attributed to Cl according to element
cm1, which indicates the cleavage of the CN bond during the balance. The recycled catalyst is mainly composed of C, H, O,
degradation reaction. Moreover, in the FT-IR spectrum of the and Al. There is a small amount of N. The Al content reaches
degradation products, the wide peak around 3226 cm1 implies up to 18.12 wt %. The total content of the ve elements (C, H,
that substantial NH bonds exist in the degradation products, O, N, Al) is 69.02 wt %, suggesting that the remaining 31 wt %
which also proves the cleavage of the CN bonds in CEP. By is the Cl element. These data show that the recycled catalysts
comparing with the ratio of the peak intensity of CH2 (2927 contain a mixture of aluminum acetate and aluminum chloride.
cm1) to CH3 (2961 cm1) in CEP, the decrease of this ratio In order to make the proportion of elements more intuitive, the
in the degradation products indicates that the CN bonds original data are transformed into mole ratio (see SI Table 2).
connected to the cyclohexyl in the curing agent unit were The ratio of C to N of degradation products remains
cleaved. The above results illustrate that the weakly unchanged relative to raw material, but the content of H and
coordinating aluminum ions enable the cleavage of the CN O increases after degradation. The unchanged carbon nitrogen
bond without breaking the COC bond of aryl alkyl ethers of ratio indicates the cleavage of the CN bond, which connects
CEP. In the spectrum of the recycled catalyst (Figure 2c), the with the cyclohexyl group of the curing agent because cleavage
signals of 1586 and 1474 cm1 are the asymmetric and of the other CN bond will lead to nitrogen loss. There exist
symmetric stretching vibrations of COO, which indicate the some Cl ions left in degradation products, but the Al content is
catalysts are partially transformed into aluminum acetate during close to 0, which suggests that the Cl atom may substitute the
the degradation reaction. H atom of the phenyl group during the degradation reaction.
The carbon skeleton structures of CEP and degradation As shown in Table 3, the degradation products are mainly
products were analyzed by solid state NMR (see Figure 3). In composed of organic components. Thus, the molecular weight
the NMR spectra, the peaks of CEP at 157, 143, 127, and 114 and its distribution were investigated using the GPC method
ppm in Figure 3a belong to the carbon signals of the benzene (see SI Table 3). The weight-average molecular weight (Mw)
ring. The peaks of the benzene ring in the degradation product of degradation products is 2396 g/mol, which is nearly twice
appear at 157, 143, 129, and 114 as seen in Figure 3b. This that of the uncured epoxy resin (UEP). The number-average
shows that the structure of the benzene ring remains intact in molecular weight (Mn) of degradation products is 1635 g/mol,
the recycled degradation products. Furthermore, the peak at and the polydispersity index (PDI) of degradation products is
157 ppm remains unchanged, indicating the existence of the 1.46. The GPC data show that the Mn and Mw of degradation
aryl alkyl ether (COC) in the degradation products. For products are larger relative to UEP, which indicates that the
CEP, the peak at 42 ppm is designated to quaternary carbon of degradation products should be the oligomers (UEP unit which
bisphenol A, and the peak at 70 ppm belongs to the carbons of is connected by the N atom).
glycidyl ether. Both of them remain unchanged in the The main destination of this work is selective cleavage of the
degradation process. The peaks between 32 and 34 ppm in carbon heteroatom bond so that the degradation products can
CEP are the signals of the cyclohexyl in the curing agent unit; be reused in resin manufacturing. The FT-IR data show that the
however, these peaks in the degradation products narrow down COC bond keeps intact, whereas the CN bond is cleaved.
to a limit range between 32 and 33 ppm. The peaks between 32 Furthermore, the FI-IR data also show that the CN bond of
and 34 ppm decreased obviously in the degradation products, the curing agent was cleaved in the degradation process, which
suggesting that the CN bonds connected to the cyclohexyl can be veried by the relative decrease of the CH2 peak
group were cleaved. The structure of the degradation products intensity. The NMR data, including solid state NMR, 1H NMR,
13
were also explored by 1H NMR, 13C NMR, DEPT 135, and C NMR, DEPT 135, and DEPT 90 indicate that the carbon
DEPT 90 (SI Figures 2 and 3). It was found that the signals skeleton structure of the resin remains intact. On the basis of
from the benzene ring and the glycidyl ether unit are found in these results, we propose a possible decomposition catalytic
the degradation products, which illustrates that the cleavage mechanism of CEP in the AlCl3/CH3COOH degradation
takes place between carbon and heteroatom during degradation system (see Scheme 2). The weakly coordinating aluminum
reaction. The 13C-NMR spectra of uncured epoxy resin (UPR) ions coordinate the isolated electron pair of the nitrogen atoms.
and curing agent after the degradation were also investigated The carboxylate oxygen of acetic acid, then attack the now
(SI Figures 4 and 5). This shows that the carbon skeleton of more electrophilic tertiary carbon, which leads to the cleavage
UPR and curing agent remains intact. This result further of the bond between the tertiary carbon and the nitrogen. This
indicates the cleavage of tertiary carbon nitrogen bonds. In the results in the formation of the ester and the secondary amine.
NMR spectrum of the recycled catalyst, the peak at 179 ppm is However, the degradation of CFREP may be dierent from
the signal of carbonyl of carboxylate, and the peak at 25 ppm is that of CEP because of the existence of CFs. The eect of
the signal of methyl. As shown in the 27Al-NMR spectra (SI reaction time on recycling of CFREP was studied, and the
Figure 6), the recycled catalyst is mainly ve-coordinated morphology of the recycled CFs was observed using SEM (see
aluminum or six-coordinated aluminum. These results indicate SI Figure 7). The surface of CFs was still covered by CEP after
that the recycled catalyst is mainly aluminum acetate. reacting for 1 h in the 15 wt % AlCl3/CH3COOH degradation
Elemental analysis was employed to obtain the element system at 180 C, but cracks appeared on the surface. When the
components of degradation products and recycled catalyst reaction time extended to 2 h, most of the surface of CFs was
(Table 3). The CEP is mainly made of the elements C, H, N, observed. Cleaner CFs were obtained after reaction for 3 h. To
and O. These four elements account for 99.84 wt % of CEP. guarantee the complete degradation, the chemical recycling of
The degradation products are also mainly composed of C, H, CFREP was carried out in the optimal conditions for CEP (15
N, and O. The aluminum content of degradation products is wt % AlCl3/CH3COOH, 180 C, 6 h). Figure 4 shows that the
D DOI: 10.1021/acssuschemeng.5b00949
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article
Scheme 2. Possible Decomposition Catalytic Mechanism of considerably larger compared with the C 1s peaks. The surface
CEP in the AlCl3/CH3COOH Degradation System 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-
Figure 4. Pictures of (a) CFREP and (b) recycled CFs, and SEM meng.5b00949.
images of (c) virgin CFs and (d) recycled CFs. Reaction conditions:
degradation system AlCl3/CH3COOH and AlCl3 mass fraction 15 wt Synthesis process of CEP; eective separation of
%, 180 C, and 6 h. degradation products and catalyst; NMR character-
izations; elemental analysis (mole ratio) and molecular
weight of products; characterizations of recycled CFs;
CFREP decomposed completely, and the CFs were recycled. comparison of various recycling methods in recycling
Clean CFs were obtained after removing the CEP from CFREP (PDF)
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 AUTHOR INFORMATION
virgin CFs, there existed some spots in the surface of recycled Corresponding Authors
CFs. These spots are the incompletely degraded CEP. The *(T.D.) E-mail: dts117@sxicc.ac.cn.
tensile strength of the recycled CFs was investigated using a *(X.H.) E-mail: houxianglin@sxicc.ac.cn.
monolament tensile test (see SI Table 4). The tensile strength Notes
of recycled CFs is 2871.96 MPa, which is 97.77% that of virgin
The authors declare no competing nancial interest.
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 ACKNOWLEDGMENTS
strength of the recycled CFs. This work was supported by Scientic and technological project
The surface functional group compositions determined by of Shanxi Province (20130322005-01). We thank Associate
XPS are shown in SI Figure 8. In the XPS analysis of the Professor Christian Marcus Pedersen for help with preparing
recovered carbon ber ((a3) in SI Figure 8a), the O 1s peak is the manuscript.
E DOI: 10.1021/acssuschemeng.5b00949
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article
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