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Facile synthesis of hemiacetal ester-based dynamic

covalent polymer networks combining fast
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Cite this: DOI: 10.1039/d1gc02773e

reprocessability and high performance†
Hongzhi Feng,a,b Songqi Ma, *a Xiwei Xu,a,b Qiong Li,a,b Binbo Wang,a,b Na Lu,a,b
Pengyun Li,a,b Sheng Wang,a,b Zhen Yua and Jin Zhua

Received 3rd August 2021,
Accepted 8th October 2021
DOI: 10.1039/d1gc02773e
rsc.li/greenchem
Dynamic covalent polymer networks (DCPNs) can address the recycle or reuse issue of thermosets due
to their network rearrangement from the dynamic bond exchange. However, developing DCPNs combin-
ing fast reprocessability and high performance through a facile and green method is still a huge challenge.
Herein, a facile and green method (in situ polymerization and dynamic cross-linking (ISPDC)) was utilized
to produce hemiacetal ester-based DCPNs which exhibited fast reprocessability and high performance.
No solvent and no purification were required, and the facile synthesis process also showed readily regu-
lated performance for the DCPNs. The obtained DCPNs could be continuously reprocessed by extrusion
as well as compression remolding; meanwhile their solvent resistance, thermo-physical and mechanical
properties are excellent on account of their high cross-link density. The small-molecule model reactions
and theoretical calculation demonstrated that hemiacetal ester exchange follows a dissociative mecha-
nism without or with an extra carboxyl group. This work studied DCPNs which showed great potential to
be efficiently recycled via reprocessing and scaled up. It tallies with sustainable development and contrib-
utes to carbon neutrality.

1. Introduction networks have attracted great attention. In virtue of the cross-

Thermosets are covalently cross-linked three-dimensional
polymer networks.1,2 Due to their superior thermo-physical
and mechanical properties, chemical resistance, and dimen-
sional stability from their network features, thermosets have
been widely used in coatings, adhesives, composites, elec-
tronic packaging, etc., and are irreplaceable in many
applications.2–7 However, their permanently cross-linked net-
works make thermosets arduous to be recycled or reprocessed
after use, and the main disposal methods are landfilling and
incineration,7 which are against the sustainable development
of materials.
In recent decades, covalent adaptable networks (CANs)8,9 or
vitrimers10,11 or dynamic covalent polymer networks
(DCPNs)12,13 which possess dynamic bonds in the cross-linked
a
Key Laboratory of Bio-based Polymeric Materials Technology and Application of
Zhejiang Province, Laboratory of Polymers and Composites, Ningbo Institute of
Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo
315201, P. R. China. E-mail: masongqi@nimte.ac.cn; Tel: +86-574-87619806
b
University of Chinese Academy of Sciences, Beijing 100049, P. R. China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1gc02773e
linked networks, they possess the high performance of thermo-
sets; and on account of the dynamic bonds, they can be repro-
cessed like thermoplastics and have functions such as self-
healing, degradability, recyclability, weldability, shape change-
ability, etc. So far, plenty of dynamic bonds or chemistries such
as ester bond,14 D–A adduct,15,16 disulfide bond,17,18 boronic
esters,19–22 olefin metathesis,23 Schiff base,24–26 vinylogous
urethanes/ureas,27–30 thiol–disulfide exchange,31 transalkyla-
tion,32 silyl ether,33,34 hemiaminals,35 thioacetal,36 hindered
urea bonds,37 carbamates,38 diketoenamine,4 diselenide,39 and
acetal40–43 have been explored to produce DCPNs. However, due
to the slow network rearrangement speed, the overwhelming
majority of reported DCPNs require a long reprocessing time at
elevated temperatures, which not only could damage their net-
works and consequently decrease their properties, but also
could consume a lot of energy. Besides, they are limited to com-
pression remolding (incontinuous reprocessing method) and
not applicable to continuous reprocessing methods such as
extrusion and injection.
Some efforts have been made to accelerate the dynamic
exchange of the DCPNs and a few continuously reprocessable
DCPNs have been achieved.14,28,44–47 The first work was from
Leibler and coworkers,14 and they introduced 5 mol% Zn(Ac)2

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(as the catalyst for transesterification) into a soft epoxy-acid
network and acquired injection remolding ability. Winne and
Du Prez and coworkers28 also introduced catalyst pTsOH
(6 mol%) and pendent amino groups and designed a favorable
macromolecular architecture for vinylogous urethane vitrimers
to gain extrusion capacity. The double neighboring group par-
ticipation method was also disclosed to accelerate the dynamic
exchange and network rearrangement of phthalate monoester-
based DCPNs, and extrudable DCPNs were obtained.44
Commercial thermoplastics such as PE and PET together with
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dynamic cross-linking techniques were also utilized to
produce continuously reprocessable DCPNs.11,46,47 Although
significant advances have been achieved, developing continu-
ously reprocessable DCPNs combining fast reprocessability
and high performance via a facile and green method is still a
huge challenge.
Recently, Ladmiral and coworkers48 for the first time
reported the catalyst-free dynamic exchange reaction of a car-
boxyl group with hemiacetal ester and utilized it to produce
polystyrene-based vitrimers which could be reprocessed
between 80 and 130 °C. In this work, we further exploited the
dynamic feature of hemiacetal ester and utilized it to achieve
continuously reprocessable DCPNs with high performance. In
addition, a facile, green and efficient synthetic method—in situ
polymerization and dynamic cross-linking (ISPDC)—was devel-
oped to produce hemiacetal ester DCPNs. In this process, all
the raw materials, methacrylic acid, methyl methacrylate and
1,4-cyclohexanedimethanol divinyl ether, were commercially
available, no solvent and no purification were required, and a
high atom conversion rate was achieved, which showed great
economic and ecological advantages. The dynamic exchange
mechanism of hemiacetal ester linkage was investigated
through small-molecule model reactions and theoretical calcu-
lation. The thermo-physical and mechanical properties were
evaluated by examining the glass transition temperature and
tensile properties of the DCPNs. The malleability and the
reprocessability of the DCPNs were studied via stress relaxation
examination, compression remolding (incontinuous), and
extrusion (continuous).
2. Experimental section
2.1. Materials
Methacrylic acid (MAA) ( purity >99.0%), methyl methacrylate
(MMA) ( purity >99.5%), isobutyric acid (IBA) ( purity ≥99%),
Scheme 1 Synthetic route of the hemiacetal ester dynamic covalent polymer networks.
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and propionic acid (PPA) ( purity ≥99%) were purchased from
Macklin Reagent Co., Ltd. 1,4-Cyclohexanedimethanol divinyl
ether (CDVE, a mixture of the cis/trans isomers) was obtained
from Sigma-Aldrich Co., China. Isobutyl vinyl ether (IVE)
( purity ≥99.5%), cyclohexyl vinyl ether (CVE) (a mixture of the
cis/trans isomers, purity ≥99%), benzoyl peroxide (BPO) (AR)
and anhydrous magnesium sulfate (MgSO4) (AR) were pur-
chased from Aladdin Reagent Co., China. Methylbenzene, di-
chloromethane (CH2Cl2), methanol, ethanol and sodium car-
bonate were bought from Sinopharm Chemical Reagent Co.,
Ltd, China. Anhydrous solvents were dried using an activated
molecular sieve before being used. All other chemicals were
used as received unless noted.
2.2. Preparation of hemiacetal ester dynamic covalent
polymer networks
A series of hemiacetal ester dynamic covalent polymer net-
works were prepared, and the total molar amount of MMA and
MAA in each sample was 0.2 mol. The amount of initiator
(BPO) added was 1 mol% of the total molar mass of MAA and
MMA. In a representative procedure for the preparation of
PMMC-10, MMA (18.0216 g, 0.18 mol), MAA (1.7218 g,
0.02 mol), CDVE (1.9629 g, 0.01 mol) and BPO (0.4866 g,
2 mmol) were mixed and poured into a 100 mL round-bot-
tomed flask with a magnetic stirrer. The mixture was stirred in
a water bath at 85 °C for about 10 min until it had a certain vis-
cosity (similar to glycerol); at this point the conversion rate is
about 10%, then the mixture was cooled quickly with ice water
to room temperature. The pre-polymerized material was
injected into a glass plate mould made in-house, which was
polymerized at 60 °C for 2 h, 80 °C for 8 h, and finally treated
at 120 °C for 2 h. The synthetic route is illustrated in
Scheme 1. Other formulations of hemiacetal ester dynamic
covalent polymer networks are summarized in Table 1.
Table 1 Feed compositions of the hemiacetal ester covalent adaptable
networks
Compositions (mol%)
Sample BPO MMA MAA CDVE
PMMC-5 1 95 5 2.5
PMMC-10 1 90 10 5
PMMC-15 1 85 15 7.5
PMMC-20 1 80 20 10
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2.3. Synthesis of small-molecule model hemiacetal esters
The small-molecule model isobutyric acid–cyclohexyl vinyl
ether hemiacetal ester (IBA–CVE) was synthesized from isobu-
tyric acid and cyclohexyl vinyl ether. Isobutyric acid (4.41 g,
0.05 mol) and cyclohexyl vinyl ether (6.31 g, 0.05 mol) were
mixed without any solvent and stirred at 80 °C for 3 h. Then,
the unreacted isobutyric acid and cyclohexyl vinyl ether were
removed by vacuum distillation. The residue was mixed with
saturated Na2CO3 aqueous solution (50 mL), and extracted
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with dichloromethane (50 mL). The organic phases were com-
bined, washed with deionized water (100 mL × 3), and dried
with anhydrous MgSO4. The solvent was removed on a rotary
evaporator to afford the model hemiacetal ester to obtain the
model hemiacetal ester IBA–CVE. PPA–IVE from propionic acid
and isobutyl vinyl ether, IBA–IVE from isobutyric acid and iso-
butyl vinyl ether, PPA–CVE from propionic acid and cyclohexyl
vinyl ether were synthesized by the same method. The syn-
thetic routes are illustrated in Scheme 2.
Isobutyric acid–cyclohexyl vinyl ether hemiacetal ester (IBA–
CVE): 1H NMR (400 MHz, DMSO-d6) δ 5.95 (q, J = 5.2 Hz, 1H),
3.49 (dp, J = 8.8, 3.9 Hz, 1H), 2.50 ( p, J = 7.0 Hz, 1H), 1.82 ( p, J
= 5.0 Hz, 1H), 1.76–1.67 (m, 1H), 1.70–1.60 (m, 2H), 1.46 (tt, J =
7.8, 2.8 Hz, 1H), 1.34–1.15 (m, 5H), 1.09 (t, J = 6.8 Hz, 5H).
13
C NMR (151 MHz, DMSO-d6) δ 175.73, 93.98, 75.49, 33.49,
32.86, 31.46, 25.11, 23.46, 23.30, 21.16, 18.69, 18.51.
Propionic acid–isobutyl vinyl ether hemiacetal ester (PPA–
IVE): 1H NMR (400 MHz, DMSO-d6) δ 5.83 (q, J = 5.2 Hz, 1H),
3.34 (dd, J = 9.2, 6.5 Hz, 1H), 3.21 (dd, J = 9.3, 6.6 Hz, 1H), 2.32
(qd, J = 7.5, 5.3 Hz, 2H), 1.75 (m, J = 13.3, 6.7 Hz, 1H), 1.30 (d, J
= 5.2 Hz, 3H), 1.03 (t, J = 7.5 Hz, 3H), 0.85 (dd, J = 6.7, 1.0 Hz,
6H).
13
C NMR (151 MHz, DMSO-d6) δ 173.27, 95.59, 74.66, 27.82,
26.96, 20.49, 18.98, 8.83.
Scheme 2 Synthetic routes of small-molecule model hemiacetal
esters.
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Isobutyric acid–isobutyl vinyl ether hemiacetal ester (IBA–
IVE): 1H NMR (400 MHz, DMSO-d6) δ 5.83 (q, J = 5.2 Hz, 1H),
3.27 (m, J = 40.0, 9.3, 6.6 Hz, 2H), 2.58–2.46 (m, 2H), 1.75 (m, J
= 13.3, 6.7 Hz, 1H), 1.31 (d, J = 5.2 Hz, 3H), 1.09 (dd, J = 8.7,
7.0 Hz, 6H), 0.85 (d, J = 6.7 Hz, 6H).
13
C NMR (151 MHz, DMSO-d6) δ 176.16, 96.14, 75.13, 33.90,
28.33, 20.89, 19.46, 19.44, 19.20, 18.98.
Propionic acid–cyclohexyl vinyl ether hemiacetal ester (PPA–
CVE): 1H NMR (400 MHz, DMSO-d6) δ 5.96 (q, J = 5.2 Hz, 1H),
3.52 (tt, J = 8.8, 4.0 Hz, 1H), 2.29 (qd, J = 7.5, 2.7 Hz, 2H), 1.03
(t, J = 7.5 Hz, 3H).
13
C NMR (151 MHz, DMSO-d6) δ 173.65, 94.18, 75.77, 33.25,
31.86, 27.58, 25.58, 23.88, 23.71, 21.61, 9.22.
2.4. Gel content test
The samples (including PMMC-5, PMMC-10, PMMC-15 and
PMMC-20) (around 300 mg) were separately put into a Soxhlet
extractor, and extracted with methylbenzene for 48 h, then
dried at 85 °C in a vacuum oven for 24 h. m0 is the initial
mass, and m1 is the final mass after drying; the gel content is
calculated by m1/m0 × 100%.
2.5. Swelling measurement
To prove cross-linking, approximately 50 mg of PMMC-5 was
immersed in sufficient methylbenzene (about 15 mL) at room
temperature for 48 h. Then the sample was taken out and the
solvent on the surface was wiped completely with absorbent
cotton. mi is the initial mass and mf is the final mass after the
swelling experiment. The swelling ratio is calculated by 100%
× (mf − mi)/mi.
2.6. Rheological behavior
The rheological experiments were carried out on a Discovery
HR-3 Rheometer (TA Instrument, America) with a plate dia-
meter of 25 mm shear geometry. The measurements were per-
formed only once, and sometimes repeated a second time if
the results were irregular. An initial compression force of 5 N
was applied and then the measurements were performed at a
fixed gap and a suitable deformation within the linear visco-
elastic region. The samples had a thickness of about 5 mm
and were cut into wafers with a diameter of 25 mm.
Stress relaxation. Stress relaxation tests were carried via the
stress relaxation mode. In order to avoid the deformation of
the samples when heated to the test temperature, the samples
were preloaded with a force of 1 × 10−3 N. When the tempera-
ture rose to the test temperatures (160 °C, 170 °C, 180 °C and
190 °C), the samples were kept for 10 min to reach thermal
equilibrium. During the tests, a constant strain (5%) was
applied to each sample, and the relaxation modulus was
recorded at a constant temperature.
Calculation of activation energies (Eas). Activation energies
(Eas) were determined using the methodology reported in the
literature.10 The measured values of characteristic relaxation
times (τ*s) were plotted versus 1000/T. The plots were fit to the
Arrhenius law in eqn (1)
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τ*ðTÞ ¼ τ*0 eEa=RT ð1Þ
−1 −1
R: universal gas constant; 8.314 J K mol .
Frequency sweep experiments. Frequency sweep experiments
were carried via the frequency sweep mode. The frequency was
varied from 0.1 to 500 rad s−1 and performed in the tempera-
ture range between 140 and 190 °C with a deformation of 1%.
2.7. Reprocess recycling through hot pressing
The reprocess recycling was carried out through a flat vulcani-
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zer (ZG-60T, Dongguan ZhengGong Electromechanical
Equipment Technology Co., Ltd). The samples (including
PMMC-5, PMMC-10, PMMC-15 and, PMMC-20) were cut into
small pieces and placed between two steel sheets covered with
a PI ( polyimide) film. After preheating at 160 °C for 2 min, the
pressure was raised to 10 MPa and maintained for a certain
time (according to samples and experiments). After cooling to
room temperature, reprocessed hemiacetal ester networks were
obtained.
2.8. Reprocess recycling through an extrusion plastometer
Extrusion of the hemiacetal ester dynamic covalent polymer
network was implemented via an extrusion plastometer
(YK-3651A, Dongguan YK Group). According to the standard
test method for melt flow rates of thermoplastics using an
extrusion plastometer (ASTM D-1238), about 5 g of PMMC-5
which was crushed using a shredder was added to the cavity of
the plastometer, after keeping at 200 °C for 2 min, 3.18 kg was
applied to extrude the PMMC-5.
2.9. Reprocess recycling through a twin-screw mini-extruder
Extrusion was performed on a twin-screw mini-extruder
(WLG10/WZS10-D). The extruder was preheated at 200 °C for
10 min and fed with PMMC-5 powder at a rotational speed of
the screws of 15 rpm. The PMMC-5 powder above was dried
thoroughly under vacuum for 6 h at 80 °C.
2.10. Exchange reactions of small-molecule model
hemiacetal esters
In the acid-free system, small-molecule models PPA–IVE
(1.0234 g, 5 mmol) and IBA–CVE (1.2587 g, 5 mmol) were
placed in a 10 mL vial, preheated in an oil bath at different
temperatures for 3 h, and 10 μL of each mixture was taken out
and diluted in 990 μL of CHCl2 for gas chromatography-mass
spectrometry (GC-MS) examination. At 120 °C, 10 μL of the
mixture was taken out at different time durations and diluted
in 990 μL of CHCl2 for GC-MS examination. In the acid system,
small-molecule models PPA–IVE (1.0234 g, 5 mmol), IBA–CVE
(1.2587 g, 5 mmol) and propionic acid (0.0370 g, 0.05 mmol)
were placed in a 10 mL vial, preheated in an oil bath at
different temperature for 3 h, and 10 μL of each mixture was
taken out and diluted in 990 μL of CHCl2 for gas chromato-
graphy-mass spectrometry (GC-MS) examination. At 60 °C,
10 μL of mixture was taken out at different time durations and
diluted in 990 μL of CHCl2 for GC-MS examination.
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2.11. Theoretical calculation
The Gaussian 16 program was employed for DFT calculations.
Geometry optimization was performed at the B3LYP-D3BJ/6-
31G(d,p) level,49–52 and frequency calculation was followed to
ensure minimum or transition state was located, and to obtain
Gibbs free energy, the SMD implicit solvation model53 was
used to take account of the solvation effect; although the reac-
tion was performed without extra solvent, the solvation effect
originating from the substrates is non-negligible, and ethyl
acetate was employed as the implicit solvation, in order to rep-
resent the polar effect of the substrate mixture.
2.12. Characterization
Nuclear magnetic resonance (NMR) spectroscopy was recorded
on a Bruker AVANCE II spectrometer at 400 MHz (1H NMR) and
Bruker AVANCE III spectrometer at 151 MHz (13C NMR), respect-
ively, using DMSO-d6 as the solvent. Fourier-transform infrared
(FTIR) spectroscopy was recorded with a Micro-FTIR Cary660
(Agilent, America) in the solid state and recorded in attenuated
total reflectance (ATR) mode, respectively. Differential scanning
calorimetry (DSC) was examined via a Mettler-Toledo Star 1
apparatus to investigate the glass transition temperatures of the
hemiacetal ester networks. The cured samples (around 6 mg)
were heated to 180 °C from 0 °C at a heating rate of 10 °C
min−1, and held at 180 °C for 3 min, cooled to 25 °C at a
cooling rate of 20 °C min−1, and finally heated to 200 °C at a
heating rate of 10 °C min−1. The second heating curve was used
to determine glass transition temperatures for each sample.
Thermogravimetric analysis (TGA) was performed on a Mettler
Toledo TGA/DSC1 under a nitrogen atmosphere from 50 °C to
800 °C at a heating rate of 10 °C min−1 with around 6 mg of
sample. Dynamic mechanical analysis (DMA) was used to
obtain the storage modulus and tan delta on a Q800 DMA (TA
Instruments, American). The test was performed in a tension
mode at a frequency of 1 Hz. All the samples were cut into rec-
tangles with dimensions of around 25 mm (length) × 5 mm
(width) × 0.5 mm (thickness) to test the dynamic mechanical
properties of the hemiacetal ester networks from −25 to 200 °C
at a ramp rate of 3 °C min−1. GC-MS spectra were obtained
using a 7890B-5977A gas chromatography-mass spectrometer
(GC-MS) (Agilent, America) using dichloromethane as the
solvent. Tensile properties of the samples were studied on an
Instron 5567 Electric Universal Testing Machine (Instron,
America). The samples with dimensions of 40 mm (length) ×
5 mm (width) × 0.5 mm (thickness) were measured with a
gauge length of 20 mm at a cross-head speed of 2 mm min−1.
For accuracy, the tensile properties of each sample were
reported as the average of five repeated measurements.
3. Results and discussion
3.1. Synthesis and chemical characterization of hemiacetal
ester DCPNs
The hemiacetal ester DCPNs, PMMC-X (X is the molar percen-
tage (mol%) of the carboxyl group based on comonomers, X =
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5, 10, 15, 20), were synthesized via a facile method of in situ
polymerization and dynamic cross-linking (free radical
copolymerization and the carboxyl–vinyl ether addition reac-
tion in one pot) (Fig. 1a, Scheme 1 and Table 1). The chemi-
cal structures of the obtained hemiacetal ester DCPNs were
determined by FTIR (Fig. S1†). As shown in the FTIR spec-
trum of one typical hemiacetal ester DCPN PMMC-10
(Fig. 1b), the signals for carbon–carbon double bonds from
the comonomers MMA and MAA and cross-linker CDVE at
around 1700 cm−1 disappeared. In addition, the successful
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synthesis of the small-molecule hemiacetal ester model
compounds (Scheme 2 and Fig. S2–S9†) demonstrated
the formation of hemiacetal ester linkage at the curing
condition. These results are indicative of the free radical
polymerization of MMA and MAA and the cross-linking reac-
tion between the carboxyl group from MAA and vinyl
ether group from CDVE. The gel contents of these DCPNs
were in the range of 93% to 96% (Fig. 1c) which are relatively
high, and the networks kept stable during the swelling
experiments (Fig. 1d) with the swelling ratios about 52%,
which also indicates the successful synthesis of the DCPNs.
Fig. 1 Preparation and properties of the hemiacetal ester DCPNs (PMMCs). (a) Schematic diagram of the preparation of the PMMCs. (b) FTIR spectra
of MMA, MAA, CVDE and PMMC-10. (c) Gel content of PMMA and PMMCs in toluene. (d) Digital pictures of the PMMC-10 before and after swelling
in toluene at room temperature for 48 h. (e) Storage modulus and tan δ as a function of temperature for the PMMCs by DMA. (f ) Representative
stress–strain curves of the PMMCs. (g) TGA curves of the PMMCs.
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3.2. Thermo-physical and mechanical properties of the
hemiacetal ester DCPNs
The PMMCs possessed favorable thermo-physical and mechan-
ical properties, which greatly increased its application poten-
tial. Owing to the flexible hemiacetal ester linkage, the glass
transition temperature (Tg) of the hemiacetal ester DCPNs
decreased with increasing cross-linker CDVE content (corres-
ponding to the content of hemiacetal ester linkage) from
126 °C for PMMC-5 to 113 °C for PMMC-20 (Fig. 1e). For the
cross-linked polymers, the Tg has a close tie with cross-link
density and the rigidity of their chain segment.54,55 The cross-
link density (ve) of the hemiacetal ester DCPNs were calculated
from the DMA date via eqn (2):
E′ ¼ 3ve RT ð2Þ
where E′ is the storage modulus of the PU networks at Tg +
30 °C, R is the gas constant (8.314 J mol−1 K−1), and T is the
kelvin temperature of Tg + 30 °C. As shown in Table S1,† the
hemiacetal ester DCPNs have a lower cross-link density, which
might be due to the dissociation of the hemiacetal ester bond
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at those temperatures. They showed superior mechanical pro-
perties especially Young’s moduli (1773–1967 MPa) and tensile
strength (53–57 MPa) which are similar to or even higher than
those of the commercial thermoplastic polymethyl methacry-
late (PMMA, Young’s modulus: 1760 MPa and tensile strength:
39 MPa (ref. 11)). Similarly, their Young’s moduli reduced with
increasing cross-linker CDVE content, while there is not too
much of a difference for their elongation at break and tensile
strength (Fig. 1f and Table S2†). From the thermogravimetric
analysis (TGA), all the PMMCs presented initial degradation
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3.3. Malleability and reprocessability of the hemiacetal ester
DCPNs
The stress relaxation times (τ*s) of DCPNs can demonstrate
their reprocessability. The PMMCs relaxed rapidly at high
temperatures (Fig. S10–S13†), and full relaxation required a
short time. At 190 °C, they could relax to 1/e of the initial
stress in a few seconds and relaxed almost to 0 within two
minutes (Fig. 2a); generally, the τ* increased with the increase
of the cross-linker CDVE content. Take PMMC-5 as an

temperature Td5% (5% weight loss) above 217 °C (Fig. 1g and
Table S1†). The PMMCs showed a two-stage decomposition
trend. We suspect that the weight loss in the first stage was
caused by the dissociation of the hemiacetal ester bond, and
the weight loss in the second stage corresponded to the
decomposition of the main material. Finally, PMMCs were
completely decomposed.
example, the relaxation rate increased with the relaxation
temperature (Fig. 2b). The stress relaxation for the PMMCs
occurred by virtue of the dynamic hemiacetal ester exchange;
therefore, the Ea from the stress relaxation would be the
characteristic of the hemiacetal ester exchange process in the
PMMCs (Fig. 2c). As expected, the Eas of the hemiacetal ester
DCPNs were lower than those of the acetal DCPNs,40–43 which

Fig. 2 Malleability and reprocessing of the PMMCs. (a) Stress relaxation of the PMMCs at 190 °C. (b) Stress relaxation of the PMMC-5 at different
temperatures. (c) Arrhenius analysis of the characteristic relaxation time τ* versus T for the PMMCs and their activation energies. (d) Appearance of
the PMMC-5 before and after compression remolding at 160 °C under 10 MPa pressure for different times. (e) Extrusion of the PMMC-5 on a plas-
tometer at 200 °C. (f ) Extrusion of the PMMC-5 on a twin-screw mini-extruder at 200 °C at a rotation speed of 15 rpm. (g) FTIR spectra and (h)
representative tensile stress–strain curves of the original and reprocessed PMMC-5. (i) Frequency sweep measurements at different temperatures of
the PMMC-10.

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means that hemiacetal ester linkage required lower energy to
activate the exchange reaction than acetal linkage. As a result
of the rapid relaxation at elevated temperatures, the hemiacetal
ester DCPNs possessed excellent and diverse reprocessability.
For the sake of determining the compression remolding
efficiency of the hemiacetal ester DCPNs, the samples were hot
pressed at 10 MPa and 160 °C for different times (Fig. 2d and
Fig. S14†). The pieces of the PMMCs could be recovered into
complete films within 10 min, while the cross-link density was
slightly decreased which could be reflected by the decreased
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screw mini-extruder, the processing conditions of the hemiace-
tal ester DCPNs were first explored with an extrusion plas-
tometer. PMMC-5 as a typical example had an outflow mass of
5.28 g within 10 min under a pressure of 3.8 kg at 200 °C, and
after hot pressing, the extruder became a colorless and trans-
parent film again (Fig. 2e and Fig. S16†). Then, the continuous
reprocessing of the hemiacetal ester DCPNs was carried out
with a twin-screw mini-extruder at 200 °C (Fig. 2f ). During
extrusion, viscous flow was observed for the PMMC-5 at
200 °C. No further flow was observed when the applied heat

modulus after compression remolding (Fig. S15†). In addition
to hot-press recovery, the hemiacetal ester DCPNs show tre-
mendous potential in continuous-extrusion reprocessing. The
melt flow index is used to characterize the viscous flow charac-
teristics of the polymer in the molten state. To guide the pro-
cessing conditions of the hemiacetal ester DCPNs in a twin-
and pressure were removed, which enabled a good retention of
the obtained shape. As can be seen from the FTIR spectra
(Fig. 2g) and tensile properties (Fig. 2h, Fig. S17–S20 and
Table S3†) of the original and reprocessed samples, the chemi-
cal structure was maintained well and there is slight reduction
in tensile strength and elongation after the reprocessing re-

Fig. 3 Hemiacetal ester exchange reactions. (a and d) Metathesis reactions between the model hemiacetal ester 1 and 2 (a) without PPA (acid) and
(d) with PPA. (b and e) Normalized gas chromatograms of the model hemiacetal ester 1 and 2 mixture before and after metathesis (b) without PPA
and (e) with PPA at different temperatures. (c and f ) Metathesis kinetics of the model hemiacetal ester 1 and 2 (c) without PPA at 120 °C and (f ) with
PPA at 60 °C. (g) Gas chromatograms of 1, 2, 3 and 4. (h) Dissociation of the model hemiacetal ester 1 at 120 °C for 3 h, monitored by 1H NMR. (i)
Fraction of 1 as a function of time during the exchange experiment at different temperatures. ( j) Plot of −ln ([1]/[1]0) versus t for 1, kexp at each temp-
erature was determined by its slope value. (k) Arrhenius analysis of the rate constant kexp versus T for the exchange reaction of 1 and 2.

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Paper
cycling. In the frequency sweep measurements (Fig. 2i), there
is a significant decrease in storage modulus with increasing
temperature for PMMC-10, and the storage modulus of
PMMC-10 also decreased during the time sweep measurement
at elevated temperatures (for example, at 120 °C) (Fig. S21†).
These demonstrate the dissociative exchange mechanism of
the hemiacetal ester linkage. This rapid dissociation and
rebinding of the hemiacetal ester structure contributed to the
rapid continuous reprocessing of the networks.
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3.4. Dynamic exchange mechanism of the hemiacetal ester
DCPNs via small-molecule model reactions and theoretical
calculation
To demonstrate the dynamic exchange mechanism of the
hemiacetal ester DCPNs, we utilized small-molecule model
compounds IBA–CVE (1) and PPA–IVE (2) to explore the
exchange reaction, and we also utilized IBA–IVE (3) and PPA–
CVE (4) to confirm that they are indeed the products formed in
Fig. 4 Theoretical calculation of the hemiacetal ester exchange reaction. (a) Dynamic exchange mechanism of the hemiacetal ester. (b) DFT-calcu-
lated energy surface for the exchange reaction between IBA–CVE and PPA–IVE.
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the model exchange reaction. They were synthesized by the
addition reaction of carboxylic acid and vinyl ether, and their
chemical structures were characterized in detail by 1H NMR
and 13C NMR (Fig. S2–S9†). GC-MS was used to monitor the
exchange reactions. The small-molecule model compounds
were well separated on a gas chromatogram (GC) (Fig. 3g) and
readily identified by mass spectrometry (MS) because each
component possesses a distinct molecular weight (Fig. S22†).
The exchange reactions of small-molecule model hemiacetal
ester compounds without carboxylic acid (Fig. 3a) and with
carboxylic acid (Fig. 3d) were both investigated. Fig. 3b shows
the gas chromatograms of model systems without carboxylic
acid before and after reactions, and it can be found that the
exchange reaction could reach equilibrium after 3 h at 120 °C
in an acid-free system, while it took shorter time to reach equi-
librium at 120 °C and could occur at lower temperatures in a
carboxylic acid-containing system (Fig. 3e). A quantitative
kinetic study was carried out by considering the total area frac-
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Green Chemistry
tion of the model hemiacetal ester compounds (1) and (3) as a
function of time. In the case of the acid-free system, the
exchange was slow at first, then became fast (Fig. 3c and
Fig. S23†). By contrast, the exchange was the fastest at the
beginning for the carboxylic acid-containing system (Fig. 3f
and Fig. S24†). This manifests that carboxyl group could accel-
erate the exchange reaction of hemiacetal esters. The kinetics
of the exchange reaction between IBA–CVE and PPA–IVE at
different temperatures were also investigated by monitoring
the fraction of PPA–IVE in the reaction system (Fig. 3i). The
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fitting function showed that the exchange reaction was in
accordance with a pseudo-second-order kinetic reaction
(Fig. 3j). Accordingly, the relationship between the reaction
rate constant k and the temperature obeyed the Arrhenius
equation, and the activation energy of the reaction was calcu-
lated to be about 56 kJ mol−1 (Fig. 3k), and the details are
described in Fig. S25–S27.† To further certify the exchange
mechanism of hemiacetal ester, the model hemiacetal ester
compound (1) was heated at 120 °C for 3 h, and the reaction
was monitored using 1H NMR (Fig. 3h). The appearance of
signals for carboxyl and cyclohexyl vinyl ether is indicative of
the dissociative mechanism, which is in agreement with the
result from the frequency sweep measurements (Fig. 2i).
In addition, we had studied the exchange process in more
depth through theoretical calculations. Fig. 4a clearly shows
that the dissociative exchange pathway involves cleavage of the
hemiacetal ester linkages into intermediate vinyl ether groups
and carboxyl groups, then re-connected via the addition reac-
tion to produce new hemiacetal ester linkages. Fig. 4b and
Table S4† exhibit the Gibbs free energy and transition state
geometry of hemiacetal ester exchange with the assistance of
DFT calculations (B3LYP-D3BJ/6-31G(d,p) level). For the system
with carboxylic acid, its Gibbs free energy is lower than the
acid-free system, which proves that the proton from the car-
boxylic acid could catalyze the dissociation of the hemiacetal
ester and further accelerate the exchange rate.
4. Conclusions
In summary, the dynamic feature of hemiacetal ester was suc-
cessfully exploited to produce DCPNs with fast reprocessability
and high performance. A facile and green method combining
free radical copolymerization and dynamic cross-linking reac-
tion—in situ polymerization and dynamic cross-linking
(ISPDC)—was explored to synthesize the hemiacetal ester
DCPNs. The hemiacetal ester exchange proceeded extremely
fast and followed the dissociative mechanism at elevated temp-
eratures. Moreover, the excess carboxyl group in the hemiacetal
ester DCPNs could significantly accelerate the exchange rate of
hemiacetal esters, corresponding to their ultra-fast stress relax-
ation and extremely short reprocessing time at elevated temp-
eratures. As a result, the hemiacetal ester DCPNs could be
reprocessed by extrusion on a twin-screw extruder (continuous)
as well as subjected to compression remolding (incontinuous).
This work disclosed a facile and green method to produce
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DCPNs combining fast reprocessability and high performance,
which is beneficial for the industrialization of DCPNs.
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
We thank the financial support from the National Natural
Science Foundation of China (no. 52073296 and 51773216),
Research Project of Technology Application for Public Welfare
of Ningbo City (no. 202002N3091), and Youth Innovation
Promotion Association, CAS (no. 2018335).
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