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Tough, recyclable and degradable plastics with

Cite this: DOI: 10.1039/d4ta02644f
multiple functions based on supramolecular
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covalent adaptive networks†

a
Shi-Yi Chen, Sumaira Noor,b Zhen Li, b
Zi-Han Zhao*c and Cheng-Hui Li *a

The environmental problem of “white pollution” caused by traditional non-degradable plastics is becoming
increasingly serious. Thus, the development of degradable and recyclable plastics attracts lots of attention
from researchers. However, the currently reported plastics have limitations in eliminating pollution in the
sea and achieving the balance between ductility and strength. Herein, a recyclable, degradable and
water-soluble plastic with robust toughness is prepared based on the supramolecular covalent adaptive
network, which is synthesized through crosslinking copolymer and poly(vinyl alcohol) PVA chains with
dynamic boronic ester/hydrogen bonds and doping the lignin component via forming hydrogen bonds
between polymer chains. Such a plastic exhibits excellent mechanical properties, showing a toughness
of up to 148 MJ m−3 due to the combination of supramolecular and covalent adaptive networks.
Significantly, the water dissolution rates and mechanical properties of plastics can be tuned over a wide
Received 17th April 2024
Accepted 9th July 2024
range by adjusting the molar masses and hydrolysis degrees of PVA and changing the water contents. In
addition, the plastic displays superior functions, such as antimicrobial, anti-UV and antioxidant properties,
DOI: 10.1039/d4ta02644f
making it promising for applications in plenty of fields. This work paves a creative path for designing
rsc.li/materials-a recyclable and degradable plastics with high performance to reduce “white pollution”.

chemistry to construct recyclable or degradable materials has

1. Introduction attracted lots of attention in polymer science recently. However,
Plastics are indispensable in our daily lives, industry, and dynamic polymeric networks oen lead to the decrease of
agriculture due to their low production costs, light weight, and mechanical properties of plastics, hindering their practical
exibility, resulting in an increasing demand for plastics.1,2 applications. Therefore, it is urgently required to exploit new
However, more than 100 million tons of plastic waste is dis- types of plastics that are both mechanically robust and highly
carded into the environment every year,3–5 causing a serious ductile, efficiently recyclable, and green-degradable in the
concern – “white pollution”.6–8 To address plastic pollution, natural environment.
some degradable plastics have been developed, while the The supramolecular system is a typical type of system that
majority are costly to produce,9,10 poor in ductility,11–13 and hard contains dynamic non-covalent interactions. The dynamic
to degrade completely under natural conditions.14 These plas- bonding and dissociation of weak non-covalent interactions
tics usually degrade under composting conditions and are allow energy dissipation in materials to improve their ductility
unrecyclable due to their permanent cross-linking networks.15,16 and also provide recyclability. Poly(vinyl alcohol) (PVA) con-
Moreover, biodegradable plastics tend to break down into taining abundant hydroxyl groups has been widely used in
microplastics17 and are non-degradable in the sea, which is degradable supramolecular systems because it could be fully
another threat to marine animals.18,19 Because of the reversible degraded into CO2 and H2O by microorganisms through the
fracture-reformation of dynamic bonds, utilizing dynamic oxidation of hydroxyl groups and the subsequent hydrolysis of
carbon–carbon diketone bonds. In addition, PVA can be easily
a
co-mingled with natural biomass through hydrogen bonding.20
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical
Engineering, Nanjing National Laboratory of Microstructures, Collaborative Lignin has lots of excellent properties such as antimicrobial,
Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, anti-UV and antioxidant due to the abundance of oxygen-
210023, P. R. China. E-mail: chli@nju.edu.cn containing functional groups (aliphatic hydroxyl, phenolic
b
State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences, hydroxyl, and methoxy).21–25 Combining PVA with lignin is an
Nanjing University, Nanjing, 210023, P. R. China
c
effective strategy to gain biocomposites with outstanding
School of Chemistry and Chemical Engineering, Nanjing University of Science and
properties. However, plastics only based on supramolecular
Technology, Nanjing, 210094, P. R. China. E-mail: ZihanZhao@njust.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
systems generally face problems of low mechanical strength
https://doi.org/10.1039/d4ta02644f and poor creep resistance due to low binding energy and active

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kinetics of dynamic non-covalent interactions.26,27 An effective 99%) and acrylamide (AAm) were purchased from Shanghai
way to solve the problem is introducing dynamic covalent bonds Aladdin Biochemical Technology Co. PVA-27 000 (Mw = 27 000 g
(DCBs) into the supramolecular system. Sun et al.28 dened mol−1, hydrolysis degree of 88%) and dealkaline lignin
such novel polymers as supramolecular covalent adaptive (carboxyl content = 2.4 mmol g−1) were purchased from
networks (supra-CANs). Based on the structure of supra-CANs Shanghai McLean Biochemical Technology Co. Boric acid
containing dynamic hydrogen and imine bonds, they con- (B(OH)3) and sodium hydroxide (NaOH) were purchased from
structed a new type of polymer with high Young's modulus, Nanjing Chemical Reagent Co. 1,1-Diphenyl-2-picrylhydrazyl
large plastic deformation and closed-loop recyclability, sug- (DPPH) and the Calcein-AM/PI live/dead cell double-staining
gesting that the synergetic effect of supramolecular interaction kit were purchased from Beijing Solebo Technology Co.
and dynamic covalent bonds provides a strategy for construct- Carmine was purchased from Tianjin Sions Biochemical Tech-
Published on 10 July 2024. Downloaded by University of Oxford on 8/12/2024 7:12:46 PM.

ing recyclable and degradable materials. To relieve the plastic nology Co. Sterile deionized water was purchased from
pollution in seawater, water-degradable or soluble plastics Shanghai Jizhi Biochemical Technology Co. The rest of the
urgently need to be designed and fabricated. In order to develop water was from deionized water in the laboratory. All the
tough, recyclable and water-degradable materials via supra- starting reagents and solvents used in the syntheses were used
CANs, the boronic ester bond is a suitable choice because it is without further purication.
not only a typical DCB29–31 with high binding energy but also
particularly responsive to water molecules and prefers to
2.2. Sample fabrication
hydrolyze to boronic acid and diols.32,33 It plays a crucial role in
maintaining the high mechanical strengths of supra-CANs in 2.2.1. Synthesis of the copolymer P(AA-co-AAm-co-6CI). The
the normal environment and enabling supra-CANs with green monomers AAm (0.484 g, 6.81 mmol), AA (0.164 g, 2.27 mmol),
degradation in water. As a result, combining dynamic boronic 6CI (0.2 g, 2.27 mmol) and AIBN (0.0678 g, 0.41 mmol) were
ester bonds with supramolecular systems is expected to achieve dissolved in 15 mL of N,N-dimethylformamide (DMF). The
a balance among toughness, recyclability and water solubility of reaction was carried out under the protection of nitrogen and
plastics. stirred at 78 °C for 24 h to obtain a light-yellow solution
Herein, a new type of tough, recyclable and degradable (Scheme 1).
plastic with multiple functions based on supra-CANs is devel- 2.2.2. Synthesis of PPVA-BOL, PPVA-BO, and PPVA-L
oped, which is expected to solve the deteriorating environ- 2.2.2.1 PPVA-BOL. PVA-27 000 (10.36 g), B(OH)3 (0.421 g,
mental pollution problems caused by plastics. The sample 6.81 mmol) and dealkaline lignin (0.284 g, 2.5 wt%) were dis-
synthesized through crosslinking copolymer and PVA chains solved in 150 mL of water and mixed with the solution of the
with dynamic boronic ester/hydrogen bonds and doping the previous step. A small amount of NaOH was added and adjusted
lignin component via forming hydrogen bonds between poly- pH to above 7. The reaction was carried out at 60 °C in an oil
mer chains was dened as “PPVA-BOL”. PPVA-BOL with the bath for 5 h. Subsequently, the obtained solution was poured
double-crosslinking network exhibits an outstanding trade-off into a PTFE mold and dried in an oven at 70 °C for 24 h. Finally,
between mechanical strength and ductility, possessing the composite lm was put into a vacuum oven at 80 °C for 24 h
a tensile strength of up to 25.2 MPa (which is comparable to to thoroughly remove the solvents (Scheme 2).
polyethylene plastic), an elongation at break of up to 778% and The synthesis paths of PPVA-BO without lignin, PPVA-L
a toughness of up to 148 MJ m−3. In addition, PPVA-BOL is without boronic esters and PVA-BOL without copolymer P(AA-
reprocessable due to the dynamic nature of boronic ester and co-AAm-co-6CI) are similar to that of PPVA-BOL.
hydrogen bonds and can be recycled through water. By
controlling the water contents and adjusting the molar masses 2.3. Characterization
and hydrolysis degrees of PVAs, the mechanical properties and
water dissolution rates of PPVA-BOLs are highly tunable. 2.3.1. General characterization. 1H NMR (400 MHz) spectra
Moreover, the addition of functional lignin promises PPVA-BOL were recorded on a Bruker DRX 400 NMR spectrometer in
additional antimicrobial, anti-UV and antioxidant properties,
making it promising for use in a wide range of applications such
as food packaging plastics, dissolvable medical materials and
UV shielding lms.
Scheme 1 The synthesis polymerization reaction of P(AA-co-AAm-
2. Experimental section co-6CI).

2.1. Materials
Acrylic acid (AA) was purchased from Shanghai Titan Tech-
nology Co. But-3-ene-1,2-diol (6CI) was purchased from
Shanghai BiDe Pharmaceutical Technology Co. Azobisisobu-
tyronitrile (AIBN) was purchased from Anhui Zaisheng Tech-
nology Co. PVA-9000 (Mw = 9000 g mol−1, hydrolysis degree of Scheme 2 The synthesis reaction of PPVA-BOL.
80%), PVA-100 000 (Mw = 100 000 g mol−1, hydrolysis degree of

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deuterated dimethyl sulfoxide or deuterated chloroform at 25 ° dimensions were measured (length, width, thickness: 10.00 ×
C. Chemical shis are reported in ppm relative to tetrame- 4.00 × 0.10 mm) and the sample was pulled at ambient
thylsilane as an internal standard (1H). 1H NMR data are re- temperature until break. Values of maximal strength, breaking
ported as follows: chemical shi in ppm, multiplicity (s = strains, and toughness are presented as the means according to
singlet, d = doublet, t = triplet), coupling constants in Hz, and the data from at least three trials.
relative integration in number of protons. Fourier transform 2.3.2.5. Puncture resistance test. The puncture resistance test
infrared spectroscopy (FTIR) spectra were recorded with was performed using an Instron 3365 instrument with
a Bruker Tensor 27 Fourier transform infrared spectrometer. a compression rate of 100 mm min−1. Sample dimensions were
Tensile tests and the puncture resistance test were performed measured (length, width, thickness: 100.00 × 100.00 × 0.11
on an Instron 3365 machine. Dynamic mechanical analyses mm) and the values of maximum puncture force and maximum
Published on 10 July 2024. Downloaded by University of Oxford on 8/12/2024 7:12:46 PM.

(DMA) were conducted on a DMA Q800 apparatus. Thermal puncture displacement were recorded.
gravimetric analysis (TGA) data were obtained on a PerkinElmer 2.3.2.6. Cyclic tensile tests. The cyclic tensile tests were
TA 2100-SDT 2960 ranging from 30 to 600 °C with a heating rate performed using an Instron 3365 instrument with a 500 N load
of 10 °C min−1 under a N2 atmosphere. Differential scanning cell. The samples were loaded, unloaded, and immediately
calorimetry (DSC) experiments were performed using a DSC reloaded 20 times; both loading and unloading were performed
apparatus of Mettler-Toledo under a dry nitrogen atmosphere with a constant extension rate of 50 mm min−1 at room
(80 mL min−1). Temperature and enthalpy calibrations were temperature. In each cycle, the sample was stretched to a strain
performed before the experiments using zinc and indium of 200%. Aer 20 cycles, the samples were allowed to relax at
standards. The temperature range is from 0 to 150 °C, with room temperature for 30 minutes before the next loading cycle.
a heating and cooling speed of 10 °C min−1. The UV-visible 2.3.2.7. Reprocessing tests. The samples were cut completely
transmission spectra of the plastics (0.11 mm thickness) and into fragments and then placed into a rectangular mold under
the absorbance values at 517 nm were measured by using a hot press for 30 min to reform the bulk materials. Aer that,
a Shimadzu UV-2700 UV-vis-NIR spectrophotometer. The scan- the polymers were cooled to room temperature to obtain the
ning electron microscopy (SEM) images were obtained on recycled samples for further measurements.
a Hitachi S-4800 SEM. 2.3.2.8. Swelling test. The polymer samples with a weight of
2.3.2. Details of general measurements 10 mg were immersed in 2 mL of distilled water and other
2.3.2.1. DMA procedure. Rectangular polymer samples solvents at different times at room temperature. The changes of
(length, width, thickness: 6.79 × 6.26 × 0.22 mm) were tested at masses at different times were monitored with swelling ratios
a frequency of 1 Hz and a strain of 0.1%. The temperature sweep (SR) and gel fractions (GF) which were calculated from eqn (2)
experiment was performed in the temperature range of 25–150 ° and (3).32
C at a rate of 3 °C min−1. The frequency sweep experiment was m1
SR ¼  100% (2)
measured in the range of 0.01–10 Hz. m0
2.3.2.2. Stress relaxation procedure. Stress relaxation exper-
iments of polymers were performed on a DMA Q800 apparatus m2
GF ¼  100% (3)
(TA Instrument) with rectangular samples which were the same m0
as those for the DMA tests. Aer equilibrating at each temper- In the equations, m0 represents the original masses of the
ature for 5 min, the experiments were carried out in a strain polymer samples, m1 represents the weights of the samples aer
control mode (5%) at different temperatures, and the stress swelling and m2 represents the masses of the samples aer
decay was monitored. The relaxation modulus was monitored drying. The results were taken as the average of three
over time. The characteristic time (s*) is dened as the time calculations.
required to reach 1/e (37%) of the initial stress. 2.3.2.9. MTT test. The L-O2 (normal human hepatocytes)
2.3.2.3. Creep test. The creep experiments of the PPVA-BOL cells were cultured in Dulbecco's modied Eagle's medium
plastic were performed on a DMA Q800 apparatus (TA Instru- (DMEM) supplemented with 10% fetal bovine serum (FBS; Life
ment) with a rectangular sample which was the same as that for Technology) at 37 °C in a humidied incubator with 5% CO2.
the DMA tests. Aer equilibrating at 60, 80, 100, and 120 °C for The cells were inoculated into 96-well plates at 1 × 104 cells per
5 min, the experiments were carried out in a stress control mode well, with a volume of 200 mL per well. Until the cell monolayer
(0.2 MPa) for 100 min and then the xation stress was removed lls the bottom of the well, wait for the cells to attach to the wall
to restore strain for another 100 min. The changes of strain were and the concentrations of 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and
monitored over time. The creep rates of the PPVA-BOL plastic at 4.5 mg mL−1 of the PPVA-BOL aqueous solutions were added to
different temperatures were calculated using eqn (1).34 DMEM for cell culture, respectively. The cells were grown in the

36000 presence or absence of the PPVA-BOL plastic for 24 h. 10–20 mL
3¼ (1)
6000 of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide
In the equation, 36000 is the strain value of the sample at 6000 s. (MTT) solution (5 mg mL−1) were added to each well and
2.3.2.4. Tensile testing procedure. The bulk static tensile continued to incubate for 5 h. Aspirated the supernatant, added
properties of polymer samples were measured using an Instron 150 mL of dimethyl sulfoxide (DMSO) to each well, and shook
3365 instrument with a pulling rate of 10 mm min−1. Sample the crystals in a shaker at a low speed for 10 min to fully

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dissolve. The wavelength of 490 nm was selected and calibrated observe the changes in the colors of the solutions. 2 mL of
at 630 nm, and the optical density value (OD) of each well was PPVA-BOL aqueous solution with different concentrations (5,
measured on an Innite 200 Pro enzyme immunoassay 10, 15, and 20 mg mL−1) were taken separately and 2 mL of
detector. The measured absorbance values were positively DPPH solution was added and mixed well. The absorbances of
correlated with the number of cells within a certain range. DPPH solutions at 517 nm (xed wavelength) were measured
Therefore, the survival rates of cells can be calculated from eqn aer 3.5 h in the dark. The scavenging rates of the samples for
(4). DPPH radicals were calculated using eqn (5).
 
Ai  Aj
Survival rate = (ODtreatment group/ODcontrol group) × 100% (4) Scavenging rate ð%Þ ¼ 1   100% (5)
Ac

In the equation, Ac is the absorbance value of 2 mL of 95%

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2.3.2.10. Live/dead cell staining tests. The L-O2 cells were ethanol plus 2 mL of DPPH solution, Ai is the absorbance of
cultured in DMEM supplemented with 10% fetal bovine serum 2 mL of different concentrations of the samples to be tested
at 37 °C in a humidied incubator with 5% CO2. Calcein-AM added to 2 mL of DPPH solution and Aj is the absorbance value
and propidium iodide (PI) co-staining were used to assess cell of 2 mL of the corresponding concentration of the samples to be
viability. The concentration of 1.0 mg mL−1 of the PPVA-BOL measured plus 2 mL of anhydrous ethanol.
aqueous solution was added to DMEM for cell culture. The cells
were grown in 6-well plates at a density of 1 × 104 cells per well
in the presence and absence of the PPVA-BOL plastic for 1, 2 and 3. Results and discussion
3 days. Then, the cells were washed twice with cold PBS, 3.1. Materials design and characterization
resuspended in a live/dead double staining kit (Dojindo The synthesis of L-supra-CAN was carried out in two steps. In
Molecular Technologies), and incubated at 37 °C for 20 min. the rst step, the hydrophilic polymer chain P(AA-co-AAm-co-
The above cells were stained with green uorescence of Calcein- 6CI) was obtained by free radical copolymerization (Fig. 1a). The
AM (for live cells) and red uorescence of PI (for dead cells), successful copolymerization reaction of P(AA-co-AAm-co-6CI)
respectively, and observed under an inverted uorescence was evidenced by the basic disappearance of the characteristic
microscope. peaks of the double bonds in 1H nuclear magnetic resonance
2.3.2.11. Antimicrobial tests. The experiment was carried out (Fig. S1, ESI†) and the FTIR spectra (Fig. 1b). The monomer ratio
using the bacterial strain Gram-negative Escherichia coli (E. coli). in the obtained copolymer was calculated to be 10.13–71.69–
Luria Bertani (LB) broth was inoculated with E. coli and stored 18.18% (AA-AAm-6CI) via the integration of the characteristic
overnight at 37 °C with shaking (200 rpm). Aerward, a 5 mL hydrogen atoms of different monomers in the 1H NMR spec-
sample of the bacterial solution (6 × 107 CFU mL−1) was trum (Fig. S1, ESI†). Then, P(AA-co-AAm-co-6CI) and PVA-27
prepared. To this solution, 2.5 mL of the PPVA-BOL plastic 000 g mol−1 were crosslinked through borax by forming ve-
solution was added and incubated for 24 h at 37 °C under membered and six-membered boronic ester rings, respec-
shaking (200 rpm). A ten-fold serial dilution process was fol- tively. A small amount of dealkaline lignin (2.5 wt%) dissolved
lowed, and 100 mL aliquots were then poured from each sample in PVA aqueous solution was added at the same time. As shown
tube onto LB broth agar plates. The same process was repeated in the FTIR spectra of the PPVA-BOL plastic, the characteristic
for the control group without adding the plastic solution, and it peaks for C–H stretching at around 2918 cm−1 and C]O
was incubated at 37 °C for 12 to 16 h. The colony-forming units stretching at 1720 cm−1 were observed (Fig. 1c). The presence of
(CFU) were determined, and then both groups were compared. the strong characteristic single-peak of B–O–C at 1090 cm−1
The values of the log(CFU mL−1) are shown in Table 1. proves the successful occurrence of the esterication dehydra-
2.3.2.12. DPPH test. An amount of DPPH was weighed and tion reaction and the generation of boronic ester linkages. In
prepared as a 0.04 mg mL−1 DPPH solution with anhydrous the FTIR spectrum of PVA-27 000, the broad characteristic peak
ethanol. Rectangular samples of the PPVA-BOL plastic and the at 3320 cm−1 is attributed to the formation of hydrogen
PPVA-BO plastic of the same size (10.0 × 6.0 × 0.2 mm) were bonding between free aliphatic hydroxyl groups and aliphatic
placed into cuvettes containing 4 mL of DPPH solution, hydroxyl groups. The corresponding peak of O–H in the PPVA-
respectively. They were le in the dark for 0, 2, 5, and 10 h to BOL plastic is shied to 3351 cm−1 suggesting that some of the
aliphatic hydroxyl groups have formed hydrogen bonding with
oxygen-containing functional groups of lignin. Therefore, PPVA-
BOL has a dual network structure, which consists of a supra-
Table 1 The values of the log(CFU mL−1) of the experimental group
molecular network linked with high-density hydrogen bonds
and control group
and a covalent network linked with boronic ester bonds
Experimental group Control group (Fig. 1d). To investigate the properties of the dual network,
PPVA-L and PPVA-BO were also synthesized, which only contain
No of colonies 6 350 a supramolecular network without borax and lignin, respec-
Total dilution factor 105 106
tively (Fig. 1e and f, see the Experimental section). The FTIR
Volume plated in mL 0.1 0.1
Log (CFU mL−1) 6.77 9.54 spectra showed no signicant differences between the three
samples, which was because the content of PVA was much

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Fig. 1 (a) The synthesis polymerization reaction of P(AA-co-AAm-co-6CI). (b) FTIR spectra of 6CI, AA, AAm and P(AA-co-AAm-co-6CI). (c) FTIR
spectra of P(AA-co-AAm-co-6CI), PVA-27000 and PPVA-BOL. Schematic illustrations of the internal network structure of (d) PPVA-BOL, (e)
PPVA-L and (f) PPVA-BO.

higher than the other components in these plastics, which all The storage modulus of PPVA-BOL and PVA-BOL was inves-
showed typical PVA absorption characteristics (Fig. S2, ESI†). tigated by DMA and the values of Er can be obtained from it (Fig.
To distinguish our material from the general PVA–borax S4, ESI†). The crosslinking degrees of PPVA-BOL and PVA-BOL
complex, we have synthesized the copolymer P(AA-co-AAm-co- were calculated to be 3086.24 and 451.99 mol m−3, respec-
6CI) to realize the crosslinking points for different types of tively. The value for PPVA-BOL was 6.8 times as high as that for
polymer chain segments linked to form a structure similar to PVA-BOL. This result was consistent with the results of
the double network. A control sample just without adding the mechanical characterization, where it has been proved that the
copolymer P(AA-co-AAm-co-6CI) was synthesized to compare introduction of the copolymer P(AA-co-AAm-co-6CI) was bene-
with PPVA-BOL, which is named “PVA-BOL” with the same cial to the enhancement of plastic performance.
contents of PVA and boronic acid as the PPVA-BOL network. Because of the high density of H bonds and the water-
Because the introduction of the copolymer P(AA-co-AAm-co-6CI) sensitive boronic ester bonds, a rectangular piece of the PPVA-
can increase the crosslink density of the system, PPVA-BOL BOL plastic (56.82 × 47.17 × 0.11 mm) can be completely dis-
exhibited a higher elongation and stress at break than PVA-BOL solved in hot water at 85 °C within 80 s (Movie S1, ESI†).
(Fig. S3, ESI†). Besides, the degrees of cross-linking (ve) of the Moreover, the PPVA-BO and PPVA-BOL plastics display high
two samples were quantitatively evaluated by calculating the transparency, despite PPVA-BOL being brown due to the addi-
storage modulus (Er) of the lm in the rubbery plateau region tion of lignin (Fig. S5, ESI†). The smooth and delicate
(Tg + 40 °C), by using the following equation:35 morphology of PPVA-BOL was observed at different microscopic
Er scales through SEM, whereas the lignin particles had good
ve ¼ compatibility with the matrix and were uniformly distributed in
3RT
the substrate (Fig. S6, ESI†).
where R refers to the universal constant and T is the absolute
temperature.

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3.2. Mechanical properties and mechanisms investigated the mechanical properties of PPVA-BO and PPVA-L
with the same water content (Fig. 2c and d). PPVA-BO showed
To evaluate the effect of crosslinking density on the mechanical
a sharp decrease in elongation at break compared with PPVA-
properties, four samples with different crosslinking densities of
BOL, although it had a higher stress at break, which is because
the covalent networks were prepared by controlling the ratio of
the introduction of lignin increased the formation sites of
6CI/B(OH)3. The water contents of the four samples were all
hydrogen bonds, and the energy could be effectively dissipated
controlled at 10% to eliminate the effect of water on the eval-
by the dissociation of hydrogen bonds during stretching.
uation of mechanical properties. As the ratio of 6CI/B(OH)3
increases, the elongation at the break of the samples decreases Meanwhile, the ductility of the system has been greatly
and the tensile strength gradually increases (Fig. 2a). This is improved. Compared with PPVA-BOL, PPVA-L without boronic
ester bond crosslinking showed a sharp decrease in fracture
attributed to the fact that the introduction of boronic ester
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stress from 25.2 to 15 MPa and a decrease in elongation at break

bonds increases the degree of cross-linking between polymer
from 778 to 573%. The decrease in overall mechanical proper-
chains, thus enhancing the overall rigidity and strength of the
ties is attributed to the fact that dynamic covalent boronic ester
network. Fig. 2b shows the mechanical properties of the four
bonds can not only enhance the rigidity of the polymer system
samples with different crosslinking ratios in terms of tensile
but also cooperate with hydrogen bonds to break during
strength, tensile strain and toughness more visually. Among
them, the sample with a 6CI/B(OH)3 molar ratio of 1 : 3 has stretching to dissipate external energy. Overall, the PPVA-BOL
plastic has the highest toughness compared with PPVA-BO and
a toughness of up to 148 MJ m−3, which demonstrates good
PPVA-L.
exibility and can withstand multiple folding and bending
To further study the energy dissipation of plastics, repeated
without deformation (Movie S2, ESI†). Therefore, the sample
cyclic tensile tests were performed under 50 mm min−1 at
with a ratio of 1 : 3 is a suitable polymer for all subsequent tests.
a strain of 200% (Fig. 2e). The large hysteresis circle in the rst
To further illustrate the effect of the crosslinking networks on
cycle indicated signicant energy dissipation due to the fracture
the mechanical performances of the plastics, we also

Fig. 2 (a) Typical stress–strain curves, (b) tensile strength, strain and toughness of the PPVA-BOLs with various cross-linking densities. (c) Typical
stress–strain curves, (d) tensile strength, strain and toughness of PPVA-BOL, PPVA-L and PPVA-BO. (e) Typical cyclic stress–strain tests of PPVA-
BOL. (f) Typical stress–strain curves of the PPVA-BOLs with different water contents. (g) Dynamic oscillatory temperature sweeps of PPVA-BOL
ranging from 25 to 150 °C at 1 Hz. (h) Frequency sweep of PPVA-BOL ranging from 0.01 to 10 Hz at 25 °C. (i) Parameters of the plastic synthesized
in this work and recently reported plastic alternatives.13,36–42

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of the dynamic crosslinks. The hysteresis circle area decreased amount of water contained in the sample (Fig. S8, ESI†). DSC
signicantly in the subsequent loading–unloading cycle, which curves showed the glass transition temperatures (Tg) of the
is because the sacricial bonds that broke during the rst three samples with different crosslinking networks. Due to the
loading did not have enough time to recover to their original absence of a covalently crosslinked network formed by the
states. In the successive tests, the hysteresis loop decreased boronic ester bonds, PPVA-BOL possesses the highest Tg point
slightly with increasing cycles, indicating a balanced state of the (85.67 °C), followed by PPVA-BO (75.99 °C), whereas the PPVA-L
fracture and reorganization of the sacricial bonds. Before the sample had the lowest Tg point (62.81 °C) (Fig. 3a). The high
20th cyclic tensile test, PPVA-BOL was relaxed at room temper- thermal decomposition temperature and the Tg point indicate
ature for 30 min, and a hysteresis loop similar to that of the rst that the PPVA-BOLs can maintain thermal stability even in high-
cyclic tensile test was obtained. The energy dissipation of the temperature environments.
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sample recovered to 90.72% of the original, representing that Polymer creep will lower the safety and reliability of
the dissociated dynamic bonds reformed and the mechanical composite applications, restricting their development and
properties of the sample were recovered. Additionally, the usage in lots of elds.46 Thus, the investigation of the creep
puncture test was performed on the PPVA-BOL lm at resistance of the PPVA-BOL plastic via DMA is indispensable.
a compression rate of 100 mm min−1 to study the ability to The creep experiments were performed by applying a stress of
avoid being damaged by sharp objects (Fig. S7, ESI†). The 0.2 MPa at different temperatures (Fig. 3b). The strains of the
sample showed a maximum puncture force of 26.55 N, sample were tiny below the Tg point (60 °C and 80 °C). Even at
a maximum puncture displacement of 11.88 mm and a punc- a temperature that is higher than the Tg point (100 °C), the
ture energy of up to 123.89 mJ, higher than those of other re- sample only exhibited a small deformation of 1.75% and was
ported materials43–45 and demonstrating the puncture able to recover partial strain aer stress removal. The creep rate
resistance of PPVA-BOL. As a matter of fact, water molecules (_3) indicates the rate at which permanent deformation occurs in
play a crucial role in the strengthening and toughening mech- the polymer network and it is used to evaluate the creep resis-
anism, which can form plenty of hydrogen bonds between water tance.47 The creep rates of the PPVA-BOL plastic were calculated,
molecules and polymer chains. As shown in the tensile stress– and the values are 1.5 × 10−5 to 2.9 × 10−4 (Table S1, ESI†),
strain curves of the samples with different water contents, the which are comparable to the previously reported creep rate of
sample with only 2% water content had an ultra-high tensile creep-resistant CAN.48 The good creep resistance of the PPVA-
strength of up to 65.6 MPa, while its tensile strain was only BOLs allows them to be used as plastic bags that can main-
167%, which presented an overall hard and brittle state (Fig. 2f). tain their original shape for a long period with heavy loads
With the increase in water content, the fracture stress of PPVA- without deformation.
BOL gradually decreased from 65.6 to 20 MPa, and the elonga- The PPVA-BOL plastics also show good stability in organic
tion at break increased from 167 to 945%. The results prove that solvents. The samples of PPVA-BOLs with the same size and
the mechanical properties of the PPVA-BOL plastic can be tuned shape were immersed in dichloromethane (DCM), DMF, DMSO,
in a wide range by controlling the water content and the overall toluene (Tol), acetonitrile (MeCN), tetrahydrofuran (THF),
mechanical properties of all PPVA-BOLs are tough regardless of ethanol (EtOH) and deionized water at 20 °C, respectively.
the water content. Complete dissolution of the sample in water was observed only
The rheological properties of the PPVA-BOL plastic were aer one hour (Fig. S9, ESI†). However, other samples
investigated through DMA. The storage and loss moduli of immersed in different organic reagents showed no signicant
PPVA-BOL decreased with increasing temperature over a wide change in appearance aer 96 h (Fig. 3c). The SR and GF of the
temperature range (Fig. 2g). However, the storage modulus PPVA-BOLs aer one month of immersion in these organic
remained greater than the loss modulus even at the tempera- reagents are shown in Fig. 3d and e, where a relatively
ture up to 150 °C and over the detected frequency range (0.01–10 pronounced swelling of the sample can be observed only in
Hz), suggesting that the polymer is naturally resilient and DMSO. The excellent solvent resistance of the PPVA-BOLs to
ductile due to the abundance of covalent boronated cross- organic solvents is attributed to the covalent and supramolec-
linking sites as well as a high cross-linking dual network ular composition of the dense double crosslinking network.
structure (Fig. 2h). As a result, PPVA-BOL with a water content of 3.3.2. Adjustable water stability. Since the PPVA-BOL
10% displays fairly good mechanical properties. It exhibits plastic is sensitive to moisture, it is also important to evaluate
higher elongation at break and toughness compared to some its stability in daily life use. A piece of PPVA-BOL rectangular
previously reported plastic alternatives (Fig. 2i).13,36–42 sample strip (67.35 × 43.00 × 0.32 mm) was placed in
a constant humidity chamber with a humidity of 60% to
simulate the gradual water absorption process of the plastic
3.3. Environmental stability of the PPVA-BOLs exposed to a normal humidity environment. The water
3.3.1. Thermal, creep and solvent stability. The thermal absorptions at different times were obtained by weighing the
stability of materials is important for practical applications. The material (Table S2, ESI†). The water absorption rate of the
thermodynamic properties of the PPVA-BOLs have been inves- material gradually slowed down and stabilized as time
tigated through TGA and DSC. The thermal initial decomposi- increased. Signicantly, the material could maintain its original
tion temperature of the PPVA-BOL sample was around 250 °C, shape and basic mechanical properties aer being exposed to
whereas the weight loss at 100 °C was attributed to a small 60% humidity for up to two months. The fracture stress was

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Fig. 3 (a) DSC curves of PPVA-BO, PPVA-L and PPVA-BOL. (b) Creep curves of PPVA-BOL at a fixed stress of 0.2 MPa for 100 min at different
temperatures, followed by 100 min of recovery with the stress withdrawn. (c) Photographs of the PPVA-BOLs immersed in various solvents at 0 h
and 96 h. (d) Swelling ratios and (e) gel fractions of PPVA-BOL samples after being immersed in various organic solvents for a month. (f) Typical
stress–strain curves of the PPVA-BOL plastics containing PVAs with different molar masses and hydrolysis degrees.

30% lower than that of its initial state but still as relatively high evaluate the water solubility, rectangular samples (6.67 × 4.68
as 17 MPa, and the ductility increased by 10.5% (Fig. S10, ESI†), × 0.11 mm) of all three PPVA-BOLs with a mass of 7.1 mg were
which demonstrate that the PPVA-BOL plastic is reliable in long- added into 2 mL of water at 20 °C. The PPVA-BOL sample
term storage and usage when exposed to the normal containing PVA-27 000 dissolved rst, followed by the PPVA-
environment. BOL sample containing PVA-9000, and both of which were
As PVA is the main matrix in PPVA-BOLs, the water solubility dissolved within 30 min (Table S3, ESI†). However, the PPVA-
of PVA occupies an important position in inuencing the water BOL sample containing PVA-100 000 was nearly insoluble in
solubility conditions and rates of PPVA-BOL plastics. Generally, water. These results are consistent with previous studies.
the hydrolysis degree and chain length play decisive roles in the Therefore, the water solubility of PPVA-BOLs is adjustable in
water solubility of PVA.49 Highly hydrolyzed PVAs (hydrolysis a wide range of insolubility, swelling and rapid dissolution by
degree above 98%) require a higher dissolution temperature selecting PVAs with different molar masses and hydrolysis
and a longer time to break the strong hydrogen bonds formed degrees. Different mechanical properties and water solubilities
within and between macromolecules.50 Conversely, lower of PPVA-BOL plastics can satisfy the specic needs in various
hydrolysis grades of PVAs (hydrolysis degree below 82%) are less applications. For example, plastic bags that are unable to
soluble due to the presence of a large number of hydrophobic dissolve in cold water but only dissolve in hot water upon pro-
acetyl groups on the chains.51 PVA with a higher molar mass has longed immersion can be developed based on the PPVA-BOLs to
stronger intermolecular interactions and poorer water solu- achieve durable application and controllable degradation.
bility. Three PVAs with different molar masses and hydrolysis
degrees were selected as the substrates of different PPVA-BOLs 3.4. Reprocessability and recyclability of the PPVA-BOLs
to investigate their inuences on the mechanical properties and
the aqueous dissolution rates, which are PVA-9500, PVA-27 000 Based on the dynamic exchange of boronic ester bonds at
and PVA-100 000, respectively. As shown in Fig. 3f, the tensile elevated temperatures, the PPVA-BOLs exhibit stress relaxation
strength and elongation at break increased with the molar mass behavior. Fig. 4a shows the normalized relaxation modulus (Gt/
becoming higher due to the longer chains possessing better G0) of PPVA-BOL with time in the temperature range of 140–170
mobility. Simultaneously, there are more hydrogen bond °C. The relaxation time (s*) is determined when the value of Gt/
acceptor and donor groups on the polymer chains, which make G0 reaches 1/e, which decreases with increasing temperature. A
the hydrogen bonding between chains stronger. In particular, well-tted linear relationship between ln(s*) and 1000/T is
the tensile strength of the PPVA-BOL plastic synthesized from found, and the activation energy (Ea) is calculated to be
PVA-100 000 is as high as 61 MPa, representing a value 88.44 kJ mol−1 (Fig. 4b), which suggests that PPVA-BOL has the
comparable to most engineering plastics.52 More notably, the typical glass and glassy Arrhenius ow characteristics.53 The Ea
toughness of the sample reaches as high as 461.82 MJ m−3. To value is much smaller than a typical covalent bond dissociation
energy (Ea(C–C) z 350 kJ mol−1),54 indicating the dynamic

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Fig. 4 (a) Stress-relaxation curves of PPVA-BOL at different temperatures. (b) Arrhenius fitting plots and calculated activation energy of PPVA-
BOL. (c) Variable temperature FTIR spectra of the PPVA-BOL sample. (d) Heat-pressing of PPVA-BOL. Photos of the plastic bag made of the
PPVA-BOL plastic containing (e) dried blueberries, (f) and soybeans. (g) Mechanism diagram of the whole recycling process of PPVA-BOL
through water. (h) Schematic diagram of the PPVA-BOL plastic that can be reshaped into the shape of a heart with the addition of red dye.

nature of the internal network of PPVA-BOL. The viscoelastic increasing temperature, indicating dynamic dissociation and
behavior of the plastic is determined by non-covalent interac- exchange in the network (Fig. 4c). As a consequence, the PPVA-
tions and dynamic covalent bonds. The activation energy of BOL plastic that has been cut into pieces can be reformed into
PPVA-L without boronic ester bonds (137.3 kJ mol−1) is signif- a homogeneous lm by heat pressing at 130 °C, 0.5 MPa for 30
icantly higher than that of PPVA-BOL (Fig. S11, ESI†), which minutes (Fig. 4d). We calculated the water that the PPVA-BOL
illustrates that the boronic ester crosslinking points can lost and then concluded that the water content decreased from
signicantly enhance the dynamics of the polymeric network. 10% to 5.64% through weighing before and aer the heating
The activation energy of PPVA-BO (64.13 kJ mol−1) is lower than process. Besides, PPVA-BOL was vacuum-dried at 100 °C for 24
that of PPVA-BOL (Fig. S12, ESI†), which is mainly because the hours to remove all water to evaluate the inuence of water
reduction of hydrogen-bonding crosslinking points makes the content on reprocessability. Although the sample lost all water,
network structure of PPVA-BO less dense than that of PPVA- it could still be reformed into a homogeneous lm by heat-
BOL. pressing under the same conditions due to the dynamic
Attributed to the dynamics of thermally reversible boronic nature of boronic ester and hydrogen bonds (Fig. S13, ESI†).
ester bonds and abundant hydrogen bonds in the network, the The sample aer 5 times of recycling still maintains
plastics exhibit reprocessability. Variable-temperature FTIR mechanical properties comparable to those of the initial plastic
spectra of the PPVA-BOL plastic at 30–120 °C showed that the (Fig. S14, ESI†). The excellent thermal processing properties of
signal peak of the B–O–C bond at 1090 cm−1 decreased with the PPVA-BOL plastic allow it to be spliced with a heat sealer to

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make a usable plastic bag. Fig. 4e and f demonstrate that the materials, which have the potential for applications in a variety
prepared plastic bag can hold lots of dried blueberries and of electronic devices.
soybeans. Due to its excellent hydrophilicity, the PPVA-BOL
plastic can be recycled in the most common green solvent, 3.5. Multi-functional properties of the PPVA-BOLs
water. As shown in Fig. 4g, when water molecules diffuse into
the internal network structure of the plastic, the weaker 3.5.1. Biocompatible properties. Lignin is a biomass that is
hydrogen bonds between the polymer chains dissociate rst. extracted from the inside of waste woods, and PVA is a degrad-
The reduction of interchain interactions triggers polymer chain able polymer with good biocompatibility. Consequently, the
slippage, and the boronic ester bonds are broken in the pres- biocompatibility of the PPVA-BOLs was investigated to expand
ence of water molecules. Consequently, the three-dimensional the application of boronic ester-based plastics in multiple
elds. In order to investigate the biological toxicity impact of
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crosslinked network structure of PPVA-BOL changes into

a number of loose hydrophilic polymer chains. The hydrogen the PPVA-BOL plastic on the ecological environment in depth,
bonds formed between water molecules and the polymer chains all samples used in the subsequent biological experiments were
make the material easily dissolved in water. During the subse- dissolved in sterile water to simulate the water degradation
quent drying process, the dynamic boronic ester and hydrogen situation.
bonds between the polymer chains are reorganized and nally Firstly, the cytotoxicity of the PPVA-BOLs was studied by MTT
return to the original crosslinked network structure. The basic assay. L-O2 cells were cultured in 96-well plates, and nine
agreement of the FTIR spectra before and aer water recycling groups of PPVA-BOL aqueous solutions with different concen-
veried that the network structure of PPVA-BOL had not trations (0.5–4.5 mg mL−1) were added in gradient increments,
suffered any damage (Fig. S15, ESI†). Impressively, various respectively. Subsequently, the cell survival rates of different
shapes of plastic objects can be manufactured based on the concentrations showed a tendency to increase and then slightly
water recyclability of PPVA-BOL, for example, a new shape of decrease as the concentration of PPVA-BOL increased (Fig. 5a).
heart made by adding a little cochineal dye to the plastic solu- The cell survival rate was the highest at a concentration of 1.0
tion, and then pouring it into the mold (Fig. 4h). As a strong mg mL−1, which was around 133%. Furthermore, the cell
competitor to petroleum-based plastics, the additional survival rate was above 97% even at a concentration of as high
outstanding reprocessable and adjustable color properties pave as 4.5 mg mL−1. This is probably because lignin can be absor-
the way for the PPVA-BOLs to manufacture delicate and durable bed by cells as a nutrient, which occupies a dominant position
in promoting cell proliferation at low concentrations. To further

Fig. 5 (a) Survival rates of L-O2 cells which were grown in the presence of different concentrations of PPVA-BOL aqueous solutions for 24 h. (b)
Live/dead staining of L-O2 cells after being cultured in the presence of 1.0 mg mL−1 PPVA-BOL aqueous solution for 1, 2 and 3 days. (c) Digital
images of the PPVA-BOL plastic after being buried under soil for 1, 5, 15 and 60 d. (d) Photos of E. coli. on agar plates from diluted bacterial
suspensions of a control group and an experimental group. (e) The values of the log(CFU mL−1) of the control group and the experimental group.
(f) UV-vis transmittance spectra of PPVA-BOL and PPVA-BO. (g) Photos of color changes of DPPH ethanol solutions left in the dark for 0, 2, 5 and
10 h in the presence of the PPVA-BOL plastic and the PPVA-BO plastic.

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investigate the biocompatibility of PPVA-BOLs, L-O2 cells were 3.5.3. Antioxidant properties. Aromatic rings containing
cultured for live/dead cell staining experiments. The aqueous methoxy and hydroxy functional groups in the lignin structure
solution of PPVA-BOL at a concentration of 1.0 mg mL−1 was can prevent the propagation of oxidation reactions by
added, and L-O2 cell viability was evaluated aer culturing for 1, providing hydrogen atoms, which provide possible antioxidant
2 and 3 days, respectively. On the rst day, almost no dead cells properties of the PPVA-BOL plastic.55 The antioxidant activities
were observed (Fig. 5b). Moreover, the number of cells increased of the prepared lms were investigated through a DPPH test.
rapidly on the second and third days, indicating that the cells DPPHc is a neutral, stable radical that has been frequently
were able to proliferate and grow vigorously in the presence of used to estimate the activity of antioxidants for more than
the PPVA-BOLs. Through MTT and live-dead cell staining 65 years.56,57 The color changes of PPVA-BOL and PPVA-BO
experiments, the PPVA-BOL plastic was conrmed to be non- immersed in DPPH ethanol solution aer being le in the dark
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toxic. Hence, we further investigated the soil degradability of for 0, 2, 5, and 10 h are shown in Fig. 5g. With increasing time,
PPVA-BOL for its safety to the environment. The PPVA-BOL the color of the DPPH alcoholic solution containing the
plastic was buried in the soil to observe its changes in appear- PPVA-BOL plastic changed from initially violet to light pink,
ance, and it appeared smaller as time went by (Fig. 5c). First, the yellow and light yellow, indicating that the content of DPPH
hydrogen and boronic ester bonds were broken by water radicals in the ethanol solution gradually decreased. In
molecules, and the crossing network of the polymer was comparison, the color of the DPPH alcohol solution containing
damaged. The main polymer chain PVA gradually decomposed the PPVA-BO plastic remained unchanged, indicating that the
with the synergistic effect of microorganisms and water in the lignin component in the plastic plays an antioxidant role. To
soil. Finally, the plastic disappeared completely aer 60 days. further quantitatively evaluate the antioxidant properties of
This means the PPVA-BOL plastic can degrade not only in the PPVA-BOL, we have calculated the radical scavenging rates
sea but also in the soil, which is expected to promote the use of aer 3.5 h.58 As the concentration of the PPVA-BOL plastic
plastic bags made of PPVA-BOLs in daily life. gradually increased from 5 to 20 mg mL−1, the radical scav-
Based on the antimicrobial properties of lignin, the antimi- enging efficiencies were 37.39%, 52.66%, 78.59% and 90.45%,
crobial activity of the PPVA-BOLs was further measured using E. respectively, indicating the excellent antioxidant ability of the
coli. We inoculated Luria Bertani (LB) broth with E. coli and then plastic (Fig. S17, ESI†).
added the PPVA-BOL aqueous solution to it as an experimental
group. In contrast, a control group without adding the plastic
solution was set. As shown in Fig. 5d, the number of E. coli on 4. Conclusion
the agar plate of the experimental group is signicantly less
than that of the control group. The log values of the colony- In summary, we have developed a type of tough, recyclable and
forming units (CFU) were calculated, and the statistics were degradable plastic with multiple functions through a simple
6.77 and 9.54 for the experimental and control groups, respec- route. The combination of a covalent crosslinking network with
tively (Fig. 5e). The antimicrobial test has proved that the PPVA- dynamic boronic ester bonds and a supramolecular network
BOL plastic has an obvious inhibitory effect on E. coli. The with hydrogen bonds endows the PPVA-BOLs with excellent
excellent biocompatibility and antimicrobial activity endow the mechanical properties (tensile strength of up to 25.2 MPa and
PPVA-BOLs with great potential for application in dissolvable toughness of up to 148 MJ m−3), as well as superior process-
medical materials. ability and resistance to organic solvents. The strong hydro-
3.5.2. Anti-UV properties. Since lignin contains UV- philicity of the PPVA-BOLs allows for recycling through water.
absorbing functional groups such as phenolic hydroxyl Additionally, the mechanical properties and water solubility of
groups, the introduction of lignin makes the PPVA-BOL lm UV- the PPVA-BOLs can be tuned by controlling the water content
resistant. As shown by the UV-vis transmission spectrum in and selecting PVAs with different molar masses and hydrolysis
Fig. 5e, the PPVA-BOL plastic with only 2.5 wt% of the dealka- degrees. The introduction of lignin additionally endows the
line lignin can achieve absorption shielding for the full UV PPVA-BOLs with excellent antimicrobial, anti-UV and antioxi-
wavelength range (below 400 nm). However, the PPVA-BO lm dant properties, which makes them promising for applications
without lignin has a transmittance of up to 96% in the visible in food, medical and electronic elds. Besides, the PPVA-BOLs
wavelength range and 80% at 400 nm wavelength. The uo- were conrmed to be eco-friendly in the aquatic environment
rescent area of the banknote can be used to visualize the UV through biological experiments. Signicantly, as a recyclable
shielding ability of the PPVA-BOL lm. Under 365 nm UV light alternative to traditional non-degradable plastics, this work is
irradiation, the bright uorescent security marking could be expected to solve the environmental problem of “white pollu-
observed in the banknote covered by the PPVA-BO lm (Fig. S16, tion” and eliminate the threat of plastics to marine life,
ESI†). However, when the banknote was irracdiated with UV contributing to sustainable development.
light through the PPVA-BOL lm, the uorescent patterns on
the banknote disappeared due to the absorption of UV light by
lignin. Thus, the UV-resistant properties of PPVA-BOL can Data availability
effectively solve the “light aging” problem of plastics, which has
good application prospects in the elds of outdoor packaging The data that support the ndings of this study are available in
and UV shielding materials. the ESI† of this article.

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8 E. Schmaltz, E. C. Melvin, Z. Diana, E. F. Gunady,

Author contributions
D. Rittschof, J. A. Somarelli, J. Virdin and M. M. Dunphy-
Shi-Yi Chen: conceptualization (supporting); writing-original Daly, Environ. Int., 2020, 144, 106067.
dra (lead); writing – review & editing (supporting). Sumaira 9 S. Mhiri, N. Mignard, M. Abid, F. Prochazka, J.-C. Majeste
Noor: conceptualization (supporting); writing-original dra and M. Taha, Eur. Polym. J., 2017, 88, 292–310.
(supporting); writing – review & editing (supporting). Zhen Li: 10 H.-J. Kwon, J. Jang, W.-G. Koh, J.-Y. Lee and K. Hwang,
conceptualization (supporting); writing-original dra (support- Polymers, 2023, 15, 3025.
ing); writing-review & editing (supporting). Zi-Han Zhao: 11 Y. Chen, Q. Zhang, Y. Zhong, P. Wei, X. Yu, J. Huang and
conceptualization (supporting); super-vision (supporting); J. Cai, Adv. Funct. Mater., 2021, 31, 2104368.
writing-original dra (supporting); writing-review & editing 12 Q.-F. Guan, Z.-C. Ling, Z.-M. Han, H.-B. Yang and S.-H. Yu,
Published on 10 July 2024. Downloaded by University of Oxford on 8/12/2024 7:12:46 PM.

(lead). Cheng-Hui Li: conceptualization (lead); super-vision Matter, 2020, 3, 1308–1317.

(lead); writing-original dra (supporting); writing-review & 13 X. Fang, N. Tian, W. Hu, Y. Qing, H. Wang, X. Gao, Y. Qin
editing (supporting). and J. Sun, Adv. Funct. Mater., 2022, 32, 2208623.
14 J. C. Worch and A. P. Dove, ACS Macro Lett., 2020, 9, 1494–
1506.
Conflicts of interest 15 X. M. Ding, L. Chen, D. M. Guo, B. W. Liu, X. Luo, Y. F. Lei,
H. Y. Zhong and Y. Z. Wang, ACS Sustainable Chem. Eng.,
The authors declare no conict of interest. 2021, 9, 3267–3277.
16 A. Sienkiewicz and P. Czub, ACS Sustainable Chem. Eng.,
2018, 6, 6084–6093.
Acknowledgements 17 Y. Wang, K. Ding, L. Ren, A. Peng and S. Zhou, Bull. Environ.
This work was supported by the National Natural Science Contam. Toxicol., 2022, 108, 1006–1012.
Foundation of China (Grant No. 22271139) and the Funda- 18 S. M. Kagel, M. Garcia, M. E. Cummings, V. Gruev and
mental Research Funds for the Central Universities P. C. Brady, Mar. Pollut. Bull., 2021, 168, 112438.
(020514380281). 19 M. Potocka, R. C. Bayer and M. Potocki, Mar. Pollut. Bull.,
2019, 138, 545–548.
20 Annu, A. Ali and S. Ahmed, Heliyon, 2021, 7, 06550.
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