Letter

Cite This: ACS Macro Lett. 2017, 6, 1129-1133 pubs.acs.org/macroletters

One-Pot Preparation of Autonomously Self-Healable Elastomeric

Hydrogel from Boric Acid and Random Copolymer Bearing Hydroxyl
Groups
Yiming Chen,† Wangqiu Qian,† Ran Chen,† Hongji Zhang,*,† Xiaojie Li,† Dongjian Shi,† Weifu Dong,†
Mingqing Chen,*,† and Yue Zhao*,‡
†
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan
University, Wuxi 214122, China
‡
Département de Chimie, Université de Sherbrooke, Sherbrooke, Québec J1K 2R1, Canada
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*
S Supporting Information

ABSTRACT: Self-healable hydrogels based on the dynam-

ically reversible boronate ester or borate ester bonds are
usually prepared by reacting boronic acid or boric acid with
diol compounds or polymer-like poly(vinyl alcohol) bearing a
hydroxyl group in each monomer unit. Herein, we report a
finding that not only facilitates the preparation but also
extends the range of self-healable hydrogels of this kind. By
simply copolymerizing commercially available N,N-dimethyla-
crylamide and 2-hydroxyethyl acrylate (8:2 weight ratio) in the
presence of boric acid in a one-pot fashion, the resulting
random copolymer can gel in aqueous solution at pH = 9,
giving rise to a solid hydrogel (tensile strength >0.5 MPa at
water content of 30%) that, on the one hand, can autonomously self-heal (near 100% fracture stress recovery within 48 h in air at
room temperature) and, on the other hand, shows the characteristics of elastomer (little stress relaxation under loading and small
residual deformation after unloading upon repeated 300% elongation cycles). The results reveal that it can be sufficient to have a
random copolymer with comonomer units bearing hydroxyl groups for reacting with boric acid to generate dynamically reversible
borate ester bonds. This finding thus points out a general, facile, and cost-effective method to obtain and explore new borate ester
bond-based self-healable hydrogels.

ydrogels have found applications in many fields due to

H their hydrophilic nature, porous structure, and similarity
with soft tissues of humans.1−3 However, some hydrogels are
readily damaged during the process of service. To prolong their
lifetime, researchers have been making much effort to prepare
self-healable hydrogels via different strategies, including the use
of dynamic covalent bonds and supramolecular interactions.4−8
Compared to physically cross-linked hydrogels based on
supramolecular interactions, chemically cross-linked systems
using dynamic covalent bonds can be better for retaining both
the structure reversibility and shape stability. Of the many
dynamic bonds, boronate ester bonds formed between boronic
acids and 1,2- or 1,3 diols have been increasingly used to design
smart polymer materials.9,10 Particularly interesting are hydro-
gels that can autonomously self-heal owing to the dynamic
covalent bonding.11−23 Although efficient in imparting the self-
healing functionality, the mechanical strength of boronate ester-
based hydrogels is often week (tensile strength <0.12 MPa),
making them inadequate for load-bearing applications.19,24
Recently, as an interesting development on the topic, He et al.
reported one-pot preparation of poly(ethylene glycol) (PEG)-
based hydrogel using thiol−ene click chemistry with Borax
(sodium tetraborate) as both catalyst and dynamic cross-linker
through complexation between Borax and a 1,2-diol com-
pound.25 In all reported studies thus far, to our knowledge, self-
healable hydrogels were prepared by reacting either substituted
boronic acids or boric acid with 1,2- or 1,3-diols or a polymer
like poly(vinyl alcohol) (PVA) containing a hydroxyl group in
each monomer unit.11−23 This is believed to be a general
requirement for boronate or borate ester-based hydrogels. In
the present study, we investigated the use of boric acid and a
random copolymer containing hydroxyl groups only in the
minority comonomer units. As shown below, we found that this
new formulation, which has little constraint and is applicable to
many systems, is effective in forming self-healable hydrogels
with excellent mechanical and elastomeric properties.
It is known that the complexation of boronic acids and diols
generally occurs at pH ∼ 9 or above (equal to or greater than
pKa of boronic acids).22,26 With a similar pKa of about 9, boric
acid in alkaline solution forms the tetrahedral tetrahydroborate
Received: August 15, 2017
Accepted: September 25, 2017
Published: September 28, 2017

© 2017 American Chemical Society 1129 DOI: 10.1021/acsmacrolett.7b00611

ACS Macro Lett. 2017, 6, 1129−1133
ACS Macro Letters
anion that can react with either one diol (1:1 complex) or 2
diols (1:2 complex).25 On the basis of this knowledge, in the
present study, we used the industrially available N,N-
dimethylacrylamide (DMA), 2-hydroxyethyl acrylate (HEA),
and boric acid as starting materials, with 2,2-diethoxyacetophe-
none (DEAP) as photoinitiator for the random copolymeriza-
tion under the alkaline condition (pH = 9) at room
temperature (Scheme 1). We hypothesized that in the resulting
Scheme 1. Schematic Illustration of the One-Pot Preparation
of the Autonomously Self-Healable Elastomeric Hydrogel
random copolymer sequences of two or more HEA units
should exit, which effectively act as diols to react with boric acid
to form dynamically reversible cross-links (1:2 complex). This
was indeed confirmed by the formation of elastomeric hydrogel
(Figure S1) that can autonomously self-heal under ambient
conditions without any need for external stimulus. The
synthetic procedure and the formulations for various hydrogels
are detailed in the Supporting Information (Table S1). In what
follows, unless otherwise stated, the specimen of P82030-30
was used as the example. The sample acronym indicates that
the hydrogel was prepared using 8 g of DMA, 2 g of HEA, and
0.30 g of boric acid in the formulation and has a water content
of 30 wt %.
The self-healing property of the hydrogel was first
investigated visually. Cut-and-heal tests were conducted on
the hydrogel as shown in Figure 1. Two samples of P82030-30
Figure 1. Photographs showing the self-healing behavior of hydrogel
(P82030-30): (a) two pieces of original hydrogel with and without
rhodamine B for coloration; (b) the original hydrogels were cut from
the middle; (c) self-healed hydrogel upon bringing the two separate
halves into contact for 48 h in air at room temperature without any
external stimulus; (d) twisting of the self-healed hydrogel; (e) and (f)
stretching of the self-healed hydrogel to about 300% extension. Logo
published with permission from Jiangnan University.
were chosen for the self-healing test, one of which contains a
red pigment for viewing the interface of cut surfaces (Figure
1a). Each hydrogel sample was cut into two pieces using
scissors (Figure 1b), and then two halves from each of the
samples were taken and put together along the fracture surfaces
(Figure 1c). After healing at room temperature for 48 h without
any external stimulus, the two halves completely merged into
1130
Letter
one single piece. Even though the cut line of the interface was
still visible, the hydrogel could bear twisting (Figure 1d),
bending, and stretching to a large extension without a break at
the interface (Figures 1e and 1f, 300% elongation).
To further assess quantitatively the self-healing property of
the hydrogel, typical tensile tests were performed on the
original and self-healed samples with various healing times. A
series of stress−strain curves obtained with P82030-30 are
shown in Figure 2a. As expected, the fracture of the self-healed
Figure 2. Stress−strain curves of the original and self-healed hydrogel
specimen (P82030-30) at various healing times (a) and the effects of
water content (b), boric acid content (c), and separation time (d) on
the fracture stress of the hydrogel after autonomous self-healing. Error
bars denote the standard deviations from at least three tests.
hydrogels took place along the interface junction at a certain
degree of stretching. The fracture stress of the self-healed
hydrogels increases with increasing the healing time, and the
tensile strength is over 0.1 MPa after only 1 h healing. After 48
h, the recovery degree of the healed hydrogel sample achieves
near 100%, meaning almost full recovery of mechanical
properties. Upon close inspection, a slight increase in the
modulus can be found for the healed samples, which can be
explained by the inevitable water loss during the healing
process. In order to confirm that the hydrogel self-healing is
originated from the borate ester bonds between boric acid and
the hydroxyl groups in the random copolymer of DMA with
HEA under alkaline conditions, control tests were carefully
performed using two samples. One sample was prepared using
the same formulation as for P82030-30 but without boric acid
(Figure S2), while the other sample was P82030 at acidic pH =
3, at which borate ester bonds are dissociated to free boric acid
(Figure S3). In both cases, the stress−strain tests show only
limited healing after 48 h intimate contact of fracture surfaces
(about 20% recovery of the tensile strength). This observation
suggests that even though the H-bonds present in the two
samples, together with chain entaglements, can allow them to
sustain a large deformation, H-bonds in the copolymer are not
effective enough to impart a high self-healing efficiency. The
control tests thus indicate that the presence of dynamically
reversible borate ester bonds under alkaline condition is
necessary to make the hydrogels autonomously self-healable.
We also investigated the influence of the hydrogel
composition on the mechanical and self-healing properties.
The effect of water content in the hydrogel was first studied.
The tensile test results for hydrogels with various initial water
contents show a significant effect (Figure 2b). It is under-
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ACS Macro Letters
standable that when the content of water is too high the
hydrogel usually exhibits poor mechanical performance and
could not be readily stretched. Therefore, the hydrogels with
water content from 20% to 70% were chosen for investigation.
As seen in Figure 2b, the original fracture stress decreases with
increasing water content, but the recovery degree in terms of
fracture stress of the sample after 48 h healing at ambient
conditions displays a “U-turn” feature. This result implies that a
sufficient amount of water is necessary to promote a sufficient
number of borate ester bonds formed between polymer chains
across the fracture interface. However, when the water content
is further increased to 70%, both the fracture stress and healing
efficiency go down sharply. The possible reason is that at this
high level of water content the polymer chains are well
dispersed and surrounded by water molecules so that the
chance for different polymer chains to reach each other to form
borate ester bonds can be severely diminished. Next, we
assessed the effect of the boric acid content (Figure 2c). With
increasing content of boric acid, the healing efficiency increases
before decreasing. The healing efficiency of the P82015-30 and
P82030-30 hydrogels healed for 48 h are around ∼65% and
∼100%, respectively. In contrast, for the P82045-30 hydrogel,
the efficiency falls to ∼85%, and the hydrogel is slightly
whitened, likely due to undissolved boric acid. As the content of
boric acid relative to the total mass in the prepolymerization
solution further increased to 4 wt % (boric acid/HEA/DMA =
0.60 g/2 g/8 g) or more, boric acid cannot be completely
dissolved even upon heating. On the one hand, lower boric acid
content results in lower borate ester cross-linking density on
the fracture surfaces and thus a decrease in healing efficiency.
On the other hand, when the content of boric acid is too high,
undissolved boric acid also reduces the chance for boron to
bridge the separated polymer chains in the hydrogel and thus
brings down the healing efficiency as well. In addition, the
separation time-dependent healing behavior was also inves-
tigated. P82030-30 hydrogels were cut into two pieces and left
separated for different times before bringing them together.
The fracture stress of self-healed hydrogel decreases drastically
with increasing separation time (Figure 2d). This result is no
surprise and suggests that, after cutting the hydrogel, if the two
new surfaces are kept separated from each other free boron on
the same surface could rearrange to form either interchain or
intrachain borate ester bonds to minimize the surface energy,
thus reducing the concentration of free boron at the surface. At
the same time, the humidity of the fracture surface decreases
with time due to water evaporation. Both lead to a less efficient
self-healing.
The self-healing capability discussed above indicates that the
cracked portions of hydrogels can be rebonded by borate ester
bonds formed between boric acid and the pendent hydroxyl
groups on the HEA sequences in the random copolymer under
alkaline conditions. In order to get some insights into the
interaction or complexation involved in the hydrogel formation
and self-healing, 11B NMR spectroscopic measurements were
carried out. As a reference system, a mixture of boric acid with
the homopolymer PHEA was also investigated, in addition to
the random copolymer of P(DMA-HEA). With a hydroxyl
group in every monomer unit like PVA, PHEA should have
segments that bear hydroxyl groups on the same side of the
plane defined by the chain backbone, which makes a succession
of diols to allow the formation of borate ester bonds. As seen in
Figure 3, with PHEA and H3BO3 in D2O at acidic pH = 3, in a
molar ratio n(−OH):n(H3BO3) = 4:1, the resonance signals of
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Letter
Figure 3. 11B NMR spectra for the homopolymer PHEA and the
random copolymer P82030 with H3BO3, respectively, at pH = 3 or pH
= 9 (in D2O, polymer concentration: 35 mg/mL).
boron appear in the 17.0−19.3 ppm region, indicating that
boron exists in the free, uncomplexed boric acid form.27,28 By
contrast, upon addition of NaOH to tune the pH to 9, the
spectral change indicates complexation. At pH = 9, a new peak
at around 5.6 ppm appears and replaces the 17.0−19.3 ppm
peak, and the new peak corresponds to the 4:l complex
between four hydroxyl groups and one tetrahedral boron,29−31
i.e., the 1:2 complex from reaction between one tetrahydrobo-
rate anion and two diols on PHEA chains (Scheme 1). Quite
surprisingly, the spectra show no evidence for other types of
complexes in the PHEA/H3BO3 solution at pH = 9.
Considering that the complexation occurs in a stepwise
manner, each monoborate has a high probability of
encountering another hydroxyl group within the high
concentrated “random-coil” volume of the chain. Then, most
complexes will further react with hydroxyl groups to form
intrachain or interchain cross-links if different chains are close
enough.29 Indeed, PHEA/H3BO3 forms hydrogel at pH = 9
(Figure S4), supporting the above analysis and the formation of
borate ester bonds as interchain cross-links. Figure 3 further
shows that the mixture of boric acid in the random copolymer
P82030-30 displays the same 11B NMR signals under the acidic
(pH = 3) and alkaline (pH = 9) conditions, which confirms
that the same complexes are responsible for the formation of
the self-healable hydrogel of the random copolymer. It is worth
mentioning that the 11B NMR spectra of boric acid alone and in
the monomer mixture for P82030 before polymerization show
the absence of complexation between boric acid and HEA
monomers at pH = 9 (Figure S5), implying the necessity of
having hydroxyl groups in interconnected monomer units
within chain segments. Overall, the 11B NMR spectra and
control experiments clearly prove that boric acid can complex
with the random copolymer of P(DMA-HEA) at pH = 9 to
form a hydrogel with dynamically reversible cross-linking from
borate ester bonds.
Besides the autonomous self-healing capability, the hydrogel
displays excellent elastomer characteristics. Typical tensile
loading−unloading tests were performed to investigate the
hydrogel’s fatigue resistance and self-recovery capabilities. As
can be seen in Figure 4a, the hysteresis area of P82030-30 was
as low as 0.065 MJ/m3 even after being stretched 3-fold. The
residual deformation after each cycle remained at around 18%,
and the curves of several cycles completely overlapped. This
result indicates that the hydrogel exhibits rubber behavior.
Generally, a hysteresis loop is related to the friction dissipation
caused by the chain segmental motion. The high density of
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ACS Macro Lett. 2017, 6, 1129−1133
ACS Macro Letters
Figure 4. (a) Cyclic stress−strain curves of hydrogel P82030-30 with
maximum stretch of 300%. (b) Stress−relaxation curves for hydrogels
with different water content subjected to stretch of 100%.
borate ester bonds can limit the polymer chain slippage, giving
rise to the very small hysteresis loop. To further investigate the
viscoelastic behavior of the hydrogel, stress−relaxation experi-
ments were carried out as well. Figure 4b presents the stress−
relaxation curves for hydrogels with different water contents. It
is seen that with less water, the initial stress is greater and the
stress relaxation at short times is more prominent. However, for
all samples, the stress then tends to reach a constant value over
time, which indicates a stable network structure in the random
copolymer hydrogel.
Moreover, the hydrogel also exhibits water-induced shape
memory effect that combines with the autonomous self-healing.
An example is shown in Figure 5, where an autonomously self-
Figure 5. Combined self-healing and shape-memory behavior of
P82030-30 hydrogel: photos of (a) a self-healed hydrogel in its original
shape, (b) the temporary shape obtained by stretching the sample in
(a) to ∼100% strain before drying at 60 °C for 2 h and removing the
external stress upon cooling to room temperature, and (c) fully
recovered permanent shape with the sample in (b) absorbing the same
amount of water lost during drying period; and (d) change in the
stress required to hold a hydrogel sample with a temporary shape of
200% strain upon absorbing the same amount of water.
healed hydrogel specimen of P82030-30 was first obtained by
bringing two pieces (one colored with rhodamine B) into
intimate contact for 48 h at room temperature (photo a). The
original shape can readily be deformed into temporary shape by
bending, folding, twisting, and even stretching the healed
original hydrogel. In this test, a temporary shape was prepared
by stretching the healed hydrogel to around 100% strain,
followed by drying at 60 °C for 2 h with the strain kept
constant and then removing the external stress upon cooling to
room temperature (photo b). The fixation of the temporary
shape comes from the loss of a water molecule during the
drying treatment, which raises the glass transition temperature
Tg above room temperature. By allowing the hydrogel in the
temporary shape to absorb the same amount of water lost
during the drying treatment, the permanent shape can be fully
recovered (photo c). In order to sense the stored strain energy
during the temporary shape fixation process, the stress needed
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Letter
to keep the hydrogel under constant strain upon water
absorption for shape recovery was monitored (Figure 5d).
The increase in stress indicates that the water molecules are
able to trigger the release of the stored strain energy.
In summary, we have demonstrated a one-pot method for
the preparation of autonomously self-healable elastomeric
hydrogels based on borate ester bonds in a random copolymer
of P(DMA-HEA) using all commercially available materials.
The finding that dynamically reversible complexation can
effectively take place between boric acid and hydroxyl groups in
comonomer units within a random copolymer under alkaline
conditions is very significant because it deviates from the
general belief that boronic acids or boric acid react with 1,2- or
1,3-diols or polymer like PVA with a hydroxyl group in each
monomer unit (succession of diols) to form boronate or borate
ester bonds. By copolymerizing two or more monomers, one of
which with a hydroxyl pendent group (like HEA), the resulting
random copolymer normally has sequences of two or more
hydroxyl-bearing comonomer units, which may be enough for
cross-linking of the copolymer through complexation of the
hydroxyl groups with boric acid. This means that the reported
method for preparing self-healable hydrogels can be extended
to many monomers, widening the design, formulation, and
exploitation for applications of new hydrogel systems.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsmacro-
lett.7b00611.
Sample preparation and more characterization results are
included (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: hongjizhang@jiangnan.edu.cn.
*E-mail: mqchen@jiangnan.edu.cn.
*E-mail: yue.zhao@usherbrooke.ca.
ORCID
Weifu Dong: 0000-0002-7432-8362
Yue Zhao: 0000-0001-5544-5697
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is financially supported by the National Natural
Science Foundation of China (21504031), the Natural Science
Foundation of Jiangsu Province (BK20150135), China
Postdoctoral Science Foundation (2015M570404), the Key
Laboratory of Food Colloids and Biotechnology, Ministry of
Education, Jiangnan University (JDSJ2014-06), the Ministry of
Education (MOE), and State Administration of Foreign Experts
Affairs (SAFEA) for the 111 Project (B13025). Y. Zhao
acknowledges financial support from the Natural Sciences and
Engineering Research Council of Canada (NSERC) and le
Fonds de recherche du Québec: Nature et technologies
(FRQNT).
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