Materials and Design 172 (2019) 107774

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Materials and Design

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Self-healing of cross-linked PU via dual-dynamic covalent bonds of a

Schiff base from cystine and vanillin
Sang-Hyub Lee 1, Se-Ra Shin 1, Dai-Soo Lee ⁎
Department of Semiconductor and Chemical Engineering, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, Chonbuk 54896, Republic of Korea

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Schiff base was synthesized from

vanillin and cystine, and employed as a
cross-linker of polyurethane.
• Dual dynamic covalent bonds of Schiff
base in the cross-linked polyurethane
implemented self-healing and recycling.
• Stress relaxation of the Stress relaxation
of the cross-linked polyurethane was
facilitated largely by the dual dynamic
covalent bonds
• Synergistic effects of the dual dynamic
covalent bonds for the self-healing in
the cross-linked polyurethane are
postulated.

a r t i c l e i n f o a b s t r a c t

Article history: A Schiff base containing dual-dynamic covalent bonds synthesized from the biomaterials, cystine and vanillin,
Received 28 January 2019 showed excellent reversibility under external stimuli by metatheses. The synthesized Schiff base containing
Received in revised form 29 March 2019 imine and disulfide bonds was mixed with 1,4-butanediol (BD) to ensure miscibility with polyurethane (PU)
Accepted 30 March 2019
prepolymers and then employed as a chain extender to introduce self-healing and recyclability to crosslinked
Available online 1 April 2019
PU (CPU). Compared with CPUs containing only one type of dynamic covalent bond such as imine or disulfide
Keywords:
group, the PU crosslinked with the Schiff base (SPU) showed excellent self-healing and recyclability with
Schiff-base lower activation energy for stress relaxation behavior attributable to the synergy of the dual-dynamic metatheses
Self-healing of the imine and disulfide bonds. Furthermore, the developed SPU showed dual-responsive self-healing by heat
Recyclable and UV irradiation. This Schiff base derived from biomaterials is expected to be useful for the design of CPU for
Polyurethane coatings, adhesives, and matrix polymers of composites that require self-healing and recyclability as well as
Dual-dynamic metatheses sustainability.
Dual-responsive © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction adhesives, and matrix polymers of structural composites [1]. In order

to increase the reliability and service life of the structural network poly-
Owing to their excellent mechanical, thermal, and chemical resis- mers by repairing damages, microcapsules containing self-healing
tance, crosslinked network polymers have been used for coatings, agents were embedded in the polymer composites [2,3]. The microcap-
sules have the ability to heal the damages by releasing the self-healing
⁎ Corresponding author.
agent on rupture due to the cracks. However, this extrinsic self-
E-mail address: daisoolee@jbnu.ac.kr (D.-S. Lee). healing method is not suitable for the repetitive self-healing and
1
Contributed equally to this work. recycling of network polymers. Thus, studies on developing intrinsically

https://doi.org/10.1016/j.matdes.2019.107774
0264-1275/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 S.-H. Lee et al. / Materials and Design 172 (2019) 107774
self-healable and reprocessable network polymers via dynamic cova-
lent chemistry have attracted much attention [4–8] and has led to ad-
vances in self-healable and recyclable network polymeric materials for
rubbers [9–11], plastics [12–15], and hydrogels [16,17].
The development of self-healing, recyclable polyurethane (PU)
has also been widely studied to improve durability and safety in
the large variety of PU applications, such as coatings, adhesives,
foams, and elastomers [18–22]. A variety of methods have been ex-
amined to provide self-healability and recyclability to crosslinked
PUs (CPUs), such as reversible dynamic covalent chemistries, includ-
ing the Diels–Alder (DA) and retro-DA reactions [23–29]; disulfide
metathesis [30–35]; alkoxyamine chemistry [36]; amine–urea ex-
change reactions [37]; transcarbamoylation [38–41]; reversible ace-
tal chemistry [42]; and diselenide exchange reaction [43]. There are
many reports on the developments of CPUs with excellent self-
healing and reprocessing characteristics. For example, Fortman
et al. proposed an isocyanate-free CPU derived from cyclic carbonate
derivatives and amines. The prepared CPU showed superior
reproccesability through transcarbamoylation reactions among the
pendent hydroxyl groups and carbamate groups without catalyst
[44]. Bonab et al. reported self-healable CPU nanocomposite contain-
ing CNT with very fast self-healing behavior under the microwave ir-
radiation [45]. In the CPU/CNT nanocomposite, CNTs induced
internal heating of the CPU by microwave radiation in order to acti-
vate the exchange reaction for the self-healing. Zhang et al. reported
self-healable and reprocessable CPU by employing aromatic pinacol
as a reversible C\\C bond provider for CPU networks [46].
Yang et al. [34] and Rekondo et al. [35] developed a CPU elastomer
with high self-healing efficiency by coupling dynamic covalent
chemistry and supramolecular interactions. The remarkable self-
healing ability of these systems was attributable to the synergistic ef-
fect of two different intrinsic self-healing mechanism: (i) exchange
reaction of aromatic disulfide and (ii) formation of quadruple hydro-
gen bonding by urea moieties of CPU. Similarly, the coexistence of
two or more covalent or non-covalent dynamic chemistries may
aid in introducing self-healing and recyclability to CPU and other
crosslinking systems [47,48]. Thus, a detailed investigation into the
synergistic effects of various dynamic covalent chemistries for the
self-healing and recycling of network polymers would be beneficial.
However, to the best our knowledge, few reports on two or more dy-
namic covalent chemistries of biomaterials applied to CPU to imple-
ment self-healing or recyclability exist. The application of multiple
dynamic covalent chemistries of renewable biomaterials is specu-
lated to provide sustainability as well as rapid self-healing and
efficient recyclability to PU networks. Thus, herein, we have consid-
ered the use of a Schiff base containing two different dynamic cova-
lent bonds as a bio-based chain extender of PU networks.
In this study, a Schiff base [49,50] containing dual-dynamic cova-
lent bonds, disulfide and imine, was synthesized through a simple
condensation reaction of the renewable biomaterials, cystine and
vanillin. Disulfide bonds generally allow self-healing via metathesis
under mild conditions and low temperature [31–35], and imine
bonds also allow self-healing and reprocessing of various polymeric
network systems via rapid metathesis reactions with few side reac-
tions [47,51]. Thus, a combination of these two reversible dynamic
covalent bonds was selected with the aim of preparing bio-based ef-
ficient self-healing and recyclable PU networks. In addition, the pres-
ence of disulfide groups is expected to enable a dual-responsive self-
healing mechanism by heating and UV irradiation [15]. To ensure
compatibility with tri-functional PU prepolymers, the synthesized
Schiff base was then mixed with 1,4-butandiol (BD) before being
used as a chain extender of PU prepolymers. The resulting PUs
crosslinked with and without the Schiff base (SPUs and CPUs,
respectively) were then examined for their stress relaxation, self-
healing and recyclability via thermally activated dual metatheses
reactions.
2. Experiment
2.1. Materials
The cystine and vanillin used for the synthesis of the Schiff base, as
well as isophorone diisocyanate (IPDI), 2-hydroxy disulfide (HD), 1,4-
butanediol (BD) and hexyl isocyanate were purchased from Aldrich
Chemical. Chloroform (CH3Cl), 1 M solutions of sodium hydroxide
(NaOH) and hydrochloric acid (HCl) were purchased from Dae-Jung
Chemical. Poly (propylene glycol)-based triol (PPG, OH value: 235 mg
KOH/g) was supplied by Kumho Petrochemical in Korea and vacuum
dried at 60 °C for 1 day prior to use. Poly (propylene glycol) bis(2-
aminopropyl ether) (Jeffamine D-230, PPGA) was obtained from Hunts-
man. The chemical structures of the raw materials used are presented in
Fig. S1 of the Supplementary material.
2.2. Synthesis of Schiff base
A solution of pH 10 was first prepared by adding 1 M NaOH solution
to dionized (DI) water. A Schiff base was then synthesized via the con-
densation of cystine and vanillin by dissolving 10 g (0.041 mol) of cys-
tine and 12.66 g (0.083 mol) of vanillin into this solution and stirring
at room temperature for 12 h. During the reaction, the clear, colorless
solution turned brown, indicating Schiff base formation between alde-
hyde and primary amine groups [52]. To terminate the condensation re-
action and adjust the solution to a pH of 7, 1 M HCl acid was then added.
The solution was then centrifuged for 5 min at 4000 RPM. The superna-
tant was then collected, evaporated at 70 °C to remove the DI water, and
repeatedly washed and purified with CHCl3 to remove any unreacted
cystine and vanillin. Through vacuum drying at 60 °C for 2 days,
18.13 g of brown color Schiff base was obtained, representing a yield
of approximately 80%. The synthesis route and chemical structure of
the resulting Schiff base are presented in Fig. 1.
1
H NMR of Schiff base (600 MHz, CDCl3): δ (ppm) 6.55 (d, 2H, a),
7.22–7.34 (t, 4H, b, d), 3.82 (s, 6H, c), 9.38 (s, 2H, e), 4.98 (s, 2H, f, g).
2.3. Synthesis of imine diol
Imine diol (ID) was prepared via a condensation reaction between
10 g (0.043 mol) of PPGA and 13.23 g (0.087 mol) of vanillin without
solvent at 70 °C under vacuum to remove the water generated during
the Schiff-base formation (Fig. S2). The synthesized imine diol was
then washed and purified with CHCl3 to remove any unreacted reac-
tants; next, it was vacuum dried at 80 °C for 1 day, and finally, the
brownish ID was obtained at a yield of approximately 87%. The synthe-
sized ID was characterized by employing FT-IR and 1H NMR spectra,
shown in Figs. S3 and S4 of the Supplementary material.
2.4. Synthesis of polyurethane (PU) prepolymer
The precursors for PU networks, PU prepolymers, were synthesized
by reacting IDPI and PPG without solvent, as shown in Fig. S5 of the Sup-
plementary material. First, 99.24 g (0.45 mol) of IPDI and 100 g
(0.15 mol) of PPG were placed in reactor with N2 gas purging and
stirred. The reaction temperature was then set to 70 °C. The isocyanate
(NCO) value of the resulting prepolymer was monitored according to
the ASTM D1638-74; the reaction was stopped once the NCO value
reached 9.4%, the theoretical value of the PU prepolymer after the end
capping of PPG with IPDI.
2.5. Preparation of crosslinked PU films
2.5.1. Crosslinked PU with Schiff base
All carboxylic acids and hydroxyl groups of the synthesized Schiff
base were considered reactive sites for the reaction with the N_C_O
of the PU prepolymer (functionality (f) of Schiff base of 4). The 0.18 g
 S.-H. Lee et al. / Materials and Design 172 (2019) 107774 3

Fig. 1. Synthesis of Schiff base from cystine and vanillin.

of Schiff base (0.39 mmol) was dissolved in 0.8 g of BD (8.9 mmol) to
ensure miscibility with the PU prepolymer. The Schiff base/BD mixture
was then added to the prepared 8.6 g of PU prepolymer (18.0 mmol)
and stirred. Once homogenous, the mixture was poured into a Teflon
mold and cured at 110 °C for 1 day; a schematic of the resulting SPU is
presented in Fig. 2.
SPU. The mixtures were then cured in a convection oven at 110 °C for
1 day. The prepared PU networks with cross-linkers of BD, HD/BD, or
ID/BD mixtures were named as CPU(B), CPU(D), and CPU(I), respec-
tively. The chemical compositions and a schematic illustration of the
control CPUs are presented in Table 1 and Fig. S6 of the Supplementary
material, respectively.

2.5.2. Control samples of crosslinked PU network films 2.6. Characterization

The three control PU networks were prepared similarly to the
method described in Section 2.5.1. The prepared PU prepolymers were
mixed with either a BD, HD/BD mixture or an ID/BD mixture, as given
in Table 1. The mole ratios of HD/BD and ID/BD for CPUs were adjusted
to maintain the same molar concentration of dynamic covalent bond in
The chemical structures of the prepared samples were characterized
by nuclear magnetic resonance (NMR) (JNM-ECA 600, JEOL, Tokyo,
Japan) and Fourier-transform infrared spectroscopy (FT-IR) (FT/IR
300E, JASCO, Easton, MD, USA). Liquid chromatography mass spectrom-
etry (LC/MS) (AGILENT 1100, Agilent, Santa Clara, CA, USA) was used to
investigate metathesis reactions among the model components. The dy-
namic mechanical property (heating rate: 5 °C/min), stress relaxation
behavior (at 170 °C, 180 °C, and 190 °C with 0.2% strain and 1 Hz fre-
quency), and creep recovery (at 65 °C under 0.1 MPa of stress) were in-
vestigated using a dynamic mechanical analyzer (DMA) (Q800, TA
Instrument, New Castle, DE, USA). The thermal stability was studied
employing a thermogravimetric analyzer (TGA) (Q600, TA) at a heating
rate of 20 °C/min in N2 environment. The energy dispersive spectros-
copy (EDS, JSM-6400, JEOL, Tokyo, Japan) was used to confirm the

Table 1
Investigated sample code and recipes of crosslinked PU.

Sample code Composition (by molar ratio)

PU pre-polymera BD HD ID Schiff base

CPU(B) 1 1.50 – – –
CPU(D) 1 1.32 0.18 – –
CPU(I) 1 1.41 – 0.09 –
SPU 1 1.38 – – 0.06
a
PU prepolymer was synthesized from reaction between 3 mol of IPDI and 1 mol of
Fig. 2. Schematic of synthesized polyurethane crosslinked with Schiff base (SPU). PPG.
4 S.-H. Lee et al. / Materials and Design 172 (2019) 107774
Fig. 3. FT-IR spectra of the Schiff base synthesized from the condensation reaction between cystine and vanillin (a), and 1H NMR spectra of the synthesized Schiff base (b).
presence of sulfur atoms in the disulfide linkages of CPU(D) and SPU.
The tensile properties of dumbbell-shaped specimens were measured
using a universal testing machine (UTM) (LR5K Plus, LLOYD, West Sus-
sex, UK). The measurements were performed at 25 °C with a cross-head
speed of 30 mm/min. The dumbbell-shaped sample specimens were
prepared according to ISO527-2/5A.
3. Results and discussion
3.1. Synthesis and characterization on Schiff base
The synthesized Schiff base was characterized using FT-IR spectra
and 1H NMR, and the results are shown in Fig. 3. As shown in Fig. 3a,
the peak at 1674 cm−1 corresponding to the aldehyde group (\\CHO)
of vanillin was replaced by the peak at 1647 cm−1 in the Schiff base, cor-
responding to an imine linkage (C_N) formed by the condensation re-
action between cystine and vanillin [53,54]. Additionally, the chemical
shifts (δ) found in the 1H NMR spectra of the Schiff base at 9.36 ppm,
designated “e” in Fig. 3b, can be attributed to the \\CH of the C_N
groups that resulted from the condensation reaction. Furthermore, the
integrated area and theoretical number of protons in the 1H NMR spec-
tra matched, as was expected from the chemical structures of the Schiff
base.
The dual-dynamic exchange reaction by imine and disulfide metath-
eses in Schiff base was investigated using the model reaction, as shown
in Fig. 4. The Schiff base and isocyanate-capped Schiff base (Schiff base-I,
see Supplementary material) were mixed together at 80 °C in EtOH/
Fig. 4. Schematic illustration of the representative metathesis reaction between model compounds, Schiff base, and Schiff base-I, at 80 °C for 3 h (a); LC-MS results of model reaction
between Schiff base and Schiff base-I (b).
DMF solution (9:1 by weight ratio) for 3 h and were analyzed using
LC-MS. As shown in the LC-MS result, new peaks corresponding to the
metathesis products between Schiff base and Schiff base-I emerged at
an m/z of 632.8 (P1), 750.1 (P2), 809.4 (P3), 716.9 (P4), and 572.8
(P5) (chemical structures of metathesis products are presented in
Fig. S8), and the reaction reached equilibrium within 1 h. In particular,
P1 and P4 are representative exchange products that could have
emerged via a direct imine and disulfide exchange reaction between
Schiff base and Schiff base-I. The appearance of these new peaks in LC-
MS strongly evidences the dual-exchange reaction of Schiff base via
both imine and disulfide metatheses.
3.2. Characterization of crosslinked PU networks
The PU networks synthesized via the crosslinking of PU prepolymer
with four types of chain extenders were characterized through FT-IR
spectra, and the results are shown in Fig. 5. In the crosslinked networks,
the peak at 2270 cm−1 corresponding to the N_C_O peak of PU
prepolymer was not detected and the intensity of the C_O peak at
1700 cm−1 was enhanced owing to the formation of urethane linkages
after crosslinking. Additionally, peaks at 3500–3400 cm−1 correspond-
ing to the \\OH and \\COOH groups of chain extenders were not ob-
served and broad single peaks at 3300 cm−1 corresponding to -NH of
urethane unit were observed, indicating that all chain extenders partic-
ipated in urethane formation. In the case of CPU(I) and SPU, a broad
C_O peak at 1647 cm−1 was caused by the presence of imine linkages
introduced by the chain extenders, ID/BD or Schiff base/BD mixtures. As
 S.-H. Lee et al. / Materials and Design 172 (2019) 107774
Fig. 5. FT-IR spectra of CPUs and SPU synthesized from PU prepolymer with BD, HD/BD, ID/
BD or Schiff base/BD mixtures.
the presence of disulfide linkages in CPU(D) and SPU were difficult to
identify via FT-IR spectroscopy or Raman scattering in this study; the
presence of sulfur atoms of disulfide linkages was instead confirmed
via EDS analysis, as shown in Figs. S9 and S10 of the Supplementary
material.
The crosslinked structures of the PU networks were then character-
ized through solubility test and gel content measurement. All synthe-
sized crosslinked networks showed excellent chemical resistance
without significant weight losses and high levels of gel contents
(above 97%) due to their crosslinked structures, as shown in Fig. S11
and Table S1. Furthermore, all prepared PU networks showed excellent
thermal stability up to 280 °C owing to the formation of crosslinked
structures with few unreacted reactants, as shown in Fig. S12 of the
Supplementary material. The glass transition temperature (Tg) of PU
thermosets were investigated from tan δ using the DMA; results are
summarized in Fig. 6 and Table 2. The crosslinked polymer networks
containing dynamic covalent bonds showed slightly lower Tg than CPU
(B). This is attributable to the incorporation of dynamic covalent
bonds, which induced slightly lowered gel contents, as summarized in
Table S1. However, there were no significant differences in the gel con-
tents or Tgs of SPU, CPU(D), or CPU(I) because the moles of dynamic co-
valent bonds in each PU network were adjusted to have similar values
(See Table 1). As shown in Fig. 6, the storage moduli (E′) of CPU(B) in
the rubbery plateau remained steady and the height of the tan δ peak
was significantly lowered above Tg (maximum tan δ peak) due to the
Fig. 6. Dynamic mechanical properties of PU networks in DMA measurements: (a) storage modulus (E′) versus temperature; (b) tan δ versus temperature.
5
Table 2
Summary of results of TGA and DMA analysis.
Samples Td (°C)a Tg (°C)b E′ (MPa)c E′ (MPa)d
CPU(B) 302 ± 5 57 ± 0.4 1707 ± 14 0.85 ± 0.08
CPU(D) 297 ± 2 52.7 ± 0.2 1238 ± 28 1.06 ± 0.11
CPU(I) 303 ± 1 51.2 ± 0.2 1208 ± 34 0.62 ± 0.06
SPU 288 ± 2 51.9 ± 0.3 2324 ± 25 0.37 ± 0.12
a
The temperature at 5 wt% loss in TGA.
b
Tgs determined from maximum peak of tan δ from DMA.
c
Storage modulus at glassy state, at −50 °C (bTg).
d
Storage modulus at rubbery plateau region, at 100 °C (NTg) from DMA.
restricted chain mobility resulting from a crosslinked network without
dynamic covalent bonds. Meanwhile, despite the dynamic covalent
bonds in CPU(D), CPU(I) and SPU, the E′ in the rubbery plateau region
(NTg) was dramatically decreased only in SPU. Furthermore, the SPU
samples showed a greater tan δ peak than CPU(B) together with a
shoulder above Tg that was not observed in the other samples. The sig-
nificant drop of E′ and enhanced tan δ peaks in the rubbery plateau re-
gion can be attributed to the metathesis reactions among the dynamic
covalent bonds resulting in tentatively lowered crosslinking density
and enhanced chain mobility. The rearrangements of PU chains via me-
tathesis reactions may have been accompanied by bond cleavage and
reforming, thus lowering the E′ values [30]. The significant decrease of
E′ and increase of tan δ in the rubbery plateau region of the SPU when
compared with CPU(D) and CPU(I) may be attributable to its dual-
dynamic covalent chemistries in the Schiff base.
3.3. Stress relaxation
The characteristics of the thermally activated, reversible, dynamic
covalent chemistry of the PU networks as disclosed by stress relaxation
behaviors were characterized by DMA. The normalized stress relaxa-
tions (G(t)/G(0)) of SPU measured at 170 °C, 180 °C, and 190 °C are
shown in Fig. 7. Stress relaxation data of CPU(B) as control are shown
in Fig. 7(a), and those of CPU(I) and CPU(D) are shown in Fig. S13 of
the Supplementary material. The relaxation time (τ⁎) required of
each sample type to relax to 1/e of the initial modulus is summarized
in Table 3. The τ⁎ of SPU at 170 °C, 180 °C, and 190 °C were determined
as 7, 4, and 3 min, respectively. The CPU(B) samples showed almost no
stress relaxation under the given conditions, due to the absence of dy-
namic covalent bonds. Although CPU(I) and CPU(D) contained either
imine or disulfide bonds, respectively, much longer times were required
for them to relax to 1/e of the initial modulus. The much faster relaxa-
tion behavior of SPU is attributable to the contribution of the dual-
metathesis reaction of imine and disulfide in the Schiff base. To evaluate
the difference in the relaxation behavior of the prepared samples, the
6 S.-H. Lee et al. / Materials and Design 172 (2019) 107774

Fig. 7. Stress relaxation behavior of CPU(B) (a) and SPU (b) respectively at 170 °C, 180 °C, and 190 °C.

activation energies (Ea) of the prepared PU networks were determined small; moreover, it reached equilibrium after around 8 h of further reac-
using the Arrhenius equation [37,44]: tion owing to the its sluggish disulfide metathesis reaction. Further-
more, the sluggish metathesis reaction of disulfide bonds may also
τ
¼ τ 0 expðEa =RTÞ ð1Þ restrict the exchange of imine bonds by maintaining the crosslinked
PU network, which results in a much higher Ea as compared with SPU.
where τ0 is the characteristic relaxation time at infinite temperature, Ea In contrast, in the model reaction between Schiff base and Schiff
is the activation energy, R is the universal gas constant (8.314 J/K·mol), base-I (see Fig. 4), the peaks at m/z of 632.8 and 716.9 corresponding
and T is the absolute temperature (K). The Arrhenius plot was then lin- to the representative disulfide exchange products, P1 and P4, emerged
early fit to determine the Eas of SPU and control samples. Table 3 sum- and reached equilibrium within 1 h. Thus, Schiff base and Schiff base-I
marize the corresponding results. The developed SPU exhibited the showed much faster equilibrium time for the disulfide metathesis reac-
fastest relaxation time and the lowest activation energy as 77 ± tion as compared with the model reaction of aliphatic disulfide mole-
1.5 kJ/mol, which can be attributed to the combination of the dual- cules. These results suggest that although aliphatic disulfide and imine
dynamic metathesis reactions of the imine and disulfide groups acti- bonds are introduced in the crosslinked PU system together as chain ex-
vated by external heat. These results indicate that the synthesized Schiff tenders, they do not show the synergistic effect in two different metath-
base is an efficient chain extender, providing fast relaxation behavior eses of dynamic covalent chemistries. However, when imine and
with low Ea for the rearrangement of PU networks via dual-metathesis aliphatic disulfide moieties are closely chemically bonded, as seen in
reactions. the Schiff base, they promote the metatheses of both imine and disulfide
To further investigate the synergistic effect of Schiff base in PU ma- bonds and result in a low Ea for the stress relaxation of the crosslinked
trix, the Ea and relaxation behavior of SPU were also compared with PU system.
crosslinked PUs containing imine or disulfide bonds introduced by HD
and ID, respectively (CPU(I/D)), (Supplementary material, Fig. S14). 3.4. Scratch healing test
As shown in Fig. 8, although the CPU(I/D) is a crosslinked PU chain ex-
tended with ID/HD/BD mixture and the molar ratio of ID:HD:BD was ad- 3.4.1. Scratch healing by external heat
justed to provide equivalent amounts of dynamic covalent bonds with Next, the enhanced stress relaxation behavior of SPU thermosets by
SPU, CPU(I/D) showed similar stress relaxation and Ea (118 ± Schiff base was further studied by performing scratch healing tests. A
1.6 kJ/mol) with CPU(D) (122 ± 2.6 kJ/mol) (See Table 3), which was scratch 500 μm deep was introduced on the surface of the prepared
exclusively occupied by disulfide groups as dynamic covalent bonds, thermosets. The samples were then placed in a convection oven at 65
rather than SPU or CPU(D) (Figs. 8 and S13). °C. This temperature was selected because metatheses among mole-
Because imine bonds and disulfide bonds are chemically inert as re- cules rarely occur owing to restricted chain mobility below Tg [56] and
vealed in model reactions (Supplementary material, Fig. S15), the because of the rapid decrease of E′ above Tg observed in the DMA ther-
higher Ea for the relaxation behavior of CPU(I/D) than that of SPU is at- mograms (see Fig. 6). Optical images taken via microscope during test-
tributable to the relatively sluggish exchange reaction of aliphatic disul- ing are shown for CPU(B), CPU(D), CPU(I) and SPU in Fig. 9(a)–(d),
fide bonds [31,35,55]. As investigated in the model reaction between respectively. The CPU(B) sample showed little to no healing. Although
aliphatic disulfide molecules (Supplementary material, both CPU(D) and CPU(I) were slightly healed after 30 min owing to
Figs. S16–17), although the exchange product emerged after 1 h of stir- the rearrangement of the PU networks based on the metatheses, they
ring and heating at 80 °C, the fraction of the exchange product was very did not completely heal, even after 60 min at 65 °C. This is because the
crosslinked network of PU restricts the rearrangement of PU networks
Table 3 via imine or disulfide exchange reactions, thus causing slow relaxations
Relaxation time (τ⁎) and activation energy (Ea) of crosslinked PU networks. with high Ea. Meanwhile, SPU healed faster and more thoroughly than
Samples τ⁎ (min) Results of Ea (kJ/mol) the control samples; the scratches were fully healed within 60 min.
Arrhenius plot This superior healing property of SPU can be attributed to the low acti-
170 °C 180 °C 190 °C Slope (Ea/R) r2a vation energy caused by the synergistic effects of dual-dynamic cova-
lent bonds in Schiff base.
CPU(B) – – – –
CPU(D) 295 ± 0.5 145 ± 0.8 70 ± 1.2 14.7 ± 0.2 0.99 122 ± 2.6 To confirm self-healing properties by rearrangement of PU net-
CPU(I) 39 ± 0.5 17 ± 0.4 9 ± 0.6 13.9 ± 0.2 0.99 116 ± 1.8 works, creep and recovery experiments were also conducted by
CPU(I/D) 235 ± 0.6 109 ± 0.5 61 ± 0.9 14.1 ± 0.2 0.99 118 ± 1.6 employing DMA with 0.1 MPa of stress at 65 °C, the same temperature
SPU 7 ± 0.2 4 ± 0.3 3 ± 0.1 9.5 ± 0.4 0.99 77 ± 1.5 at which the scratch healing test was performed [57]. Around 3% of
a
r square value in Arrhenius plot. strain was given to all PU thermosets for 30 min and then allowed
 S.-H. Lee et al. / Materials and Design 172 (2019) 107774 7

Fig. 8. Schematic illustration of SPU (a) and CPU(I/D) (b); stress relaxation behavior for SPU (filled symbol) and CPU(I/D) (open symbol) at 170 °C, 180 °C, and 190 °C (c).

30 min of recovery; results are presented in Fig. 9(e). CPU(B) recovered
its initial strain with little residual strain (0.003%). Relatively incomplete
strain recoveries were observed in CPU(D), CPU(I), and SPU with resid-
ual strains of 0.148%, 0.286%, and 0.586% respectively, following the re-
verse order of the Ea of each system. This indicates that extent of
network rearrangement via metatheses is significantly affected by the
Ea [30]. Thus, the scratch healing property at elevated temperatures
can be attributed to the metatheses of the dynamic covalent bonds
activated by heating. Moreover, the SPU samples showing excellent
self-healing efficiency during the scratch healing test had much higher
residual strains due to the faster rearrangement of networks via metath-
eses requiring the lowest Ea. This coincides well with results of the
scratch healing tests and indicates that the presence of dual-dynamic
covalent bonds in Schiff base is more efficient for the rearrangement
of PU networks than systems having only one type of dynamic coeffi-
cient bond or simple mixture of two dynamic covalent bonds.

Fig. 9. Photographs taken during scratch healing tests after 0, 30, and 60 min of heating at 65 °C by an optical microscope of CPU(B) (a), CPU(D) (b), CPU(I) (c), SPU (d), and results of creep
and recovery test of prepared PU networks at 65 °C (e).
8 S.-H. Lee et al. / Materials and Design 172 (2019) 107774
Fig. 10. Optical microscope photographs taken during scratch healing tests after 0, 60, and 120 min of UV irradiation of CPU(B) (a), CPU(D) (b), CPU(I) (c), SPU (d), and schematic
illustration of metatheses in Schiff base according to different external stimuli.
3.4.2. Scratch healing via UV irradiation
As disulfide groups can undergo metathesis by UV irradiation
[15,58], self-healing of SPU via UV irradiation may also be possible. As
such, a scratch test followed by 120 min of UV irradiation (365 nm)
was performed and the results are shown in Fig. 10. Here, CPU(B) and
CPU(I), both prepared without disulfide bonds, did not show any trace
of scratch healing after UV irradiation for 2 h. Disulfide-containing
CPU(D) did show a gradual disappearance of the scratch with increasing
UV-irradiation time; however, SPU completely healed in under 120 min.
These improved healing properties can be attributed to the superior re-
laxation behavior of SPU and lower Ea than CPU(D). The differences in
the mechanism of scratch healing by stimuli, heat and UV, are postu-
lated in Fig. 10(e) schematically.
3.5. Recycling
Conventional crosslinked PU polymers cannot be recycled once the
permanent crosslinked network is formed during the curing process.
However, introducing dynamic chemistry may enable the recycling of
PU thermosets [24–43]. Therefore, three cycles of a recycling test were
performed to examine the recyclability of the developed SPU with
dual-reversible imine and disulfide bonds by cutting the material into
pieces and treating at 170 °C and 10 MPa for 30 min. Results of the
recycling tests performed on the SPU and CPU samples are shown in
Fig. 11. Stress–strain curves of pristine and recycled SPU specimens prepared by hot-
pressing at 170 °C and 10 MPa for 30 min.
Figs. 11 and S18 of the Supplementary material, respectively. The
recycling properties of the control sample, CPU(B), were so poor that
uniform films could not be made from the pristine sample. However,
even after the recycling test was repeated three times on the SPU sam-
ple, there was no significant decrease in strength (σ), Young's modulus
(E), or elongation at break (ε), as shown in Table 4. Furthermore, SPU
achieved an average recycling efficiency of 97%, indicating that a PU
thermoset with a low activation energy is more suitable for the
recycling process. Additionally, no significant difference was found be-
tween the pristine and recycled SPUs in the IR or TGA results, as
shown in Figs. S19 and S20 of the Supplementary material. Thus, the
hot-pressing process used for the recycling of SPU does not degrade
the PU networks and or dynamic covalent bonds, which would have re-
sulted in a significant decrease of mechanical properties.
4. Conclusion
A bio-based Schiff base with dual-reversible covalent bonds was
synthesized and used as a chain extender to prepare crosslinked PU net-
works. Using only a small amount of Schiff base mixed with BD (mole
ratio 0.06: 1.38), the synthesized SPUs showed excellent self-healing
and recyclability (average recycling efficiency: 97%) with a low Ea for re-
laxation behavior (77 ± 1.5 kJ/mol) when compared with CPUs using
only disulfide (CPU(D)) or imine (CPU(I)) bonds. Additionally, the pres-
ence of disulfide linkages in the Schiff base provided the synthesized
SPU with dual-responsive self-healing and recycling properties by
heating and UV irradiation. The incorporation of Schiff base is therefore
concluded to provide excellent self-healing and recyclability to
crosslinked PU networks via the combination of imine and disulfide me-
tathesis. It was found that the synergistic effects of dual-dynamic me-
tatheses lowered the Ea for stress relaxations when imine and
disulfide moieties are chemically linked closely as in the Schiff base.
However, when the simple mixture of imine and disulfide was used as
a chain extender, the synergistic effect was not observed.
Table 4
Tensile properties of pristine and recycled SPU and recycling efficiency of SPU.
Properties Pristine SPU Recycled SPU
1st 2nd 3rd
σ (MPa) 34.6 ± 1.4 33.6 ± 1.5 34.3 ± 1.5 32.8 ± 1.9
ε (%) 9.4 ± 1.8 9.4 ± 1.4 9.4 ± 1.6 9.4 ± 1.4
E (MPa) 525 ± 5.2 508 ± 4.4 514 ± 6.2 501 ± 4.8
Recycling efficiency (%)a – 97 ± 4.3 99 ± 3.4 95 ± 4.1
a
(σRecycled SPU / σPristine SPU) × 100%.
 S.-H. Lee et al. / Materials and Design 172 (2019) 107774
The proposed Schiff base is thus attractive for the preparation of
smart crosslinked PU networks with self-healing and recyclability, and
it is expected to play an important role in expanding the sustainable ap-
plication field of crosslinked network polymers for coating, adhesives,
and structural parts of durability. However, for the structural parts of
high dimensional stability, stress relaxation of these materials should
be considered carefully in the design of the parts for the long term
stability.
CRediT authorship contribution statement
Sang-Hyub Lee: Conceptualization, Investigation, Methodology, Writing
- original draft. Se-Ra Shin: Investigation, Methodology. Dai-Soo Lee:
Conceptualization, Writing - review & editing, Validation.
Acknowledgment
This work was supported by the ATC project of KEIT funded by Min-
istry of Trade, Industry and Energy (Project No: ATC-10048672) in
Korea.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
Appendix A. Supplementary data
Chemical structure of raw materials; Synthesis of ID (FT-IR and 1H
NMR spectra); Preparation of PU prepolymer; Schematic of synthesized
CPUs; Synthesis of Schiff base-I and model reaction with Schiff base;
Characterization of CPUS and SPU (EDS, solubility test and TGA thermo-
grams); Stress relaxation behavior of control samples, CPU(D) and CPU
(I). (DMA); Synthesis of CPU(I/D) (FT-IR spectra, EDS); Preparation of
model compounds and model reactions (FT-IR, LC-MS); Results of the
hot-pressing experiment on CPUs (Digital camera images); Sustainabil-
ity of recycled SPU (FT-IR and TGA thermograms). Supplementary data
to this article can be found online at https://doi.org/10.1016/j.matdes.
2019.107774.
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