Supramolecular covalent cellulose-based bioplastics with high transparency, hydrophobicity, ionic conductivity, mechanical robustness, and recyclability

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Supramolecular covalent cellulose-based bioplastics with high transparency, hydrophobicity, ionic conductivity, mechanical robustness, and recyclability† Quanfeng Liang,a Mengqing Li,a Yuchen Cao,a Ren’ai Li

*b and Yunfeng Cao

c

Driven by environmental protection and sustainable development, the exploitation of cellulose-based bioplastics (CBPs) with high transparency, hydrophobicity, mechanical toughness, heat sealability, ionic conductivity, and recyclability is highly desirable. However, it is very challenging to concentrate multiple functionalities into one material. Herein, a series of supramolecular covalent CBPs was innovatively synthesized by simple solvent treatment and rapid photopolymerization based on the compatibility of ethylcellulose with a polymerizable hydrophobic deep eutectic solvent. By regulating the ratio of components, the obtained CBPs exhibited good overall performance, including optical transmittance (B92%), water resistance, mechanical toughness, heatsealing performance, and shape-memory function. Moreover, a wet strength of up to B10 MPa could still be Received 11th October 2023, Accepted 17th December 2023 DOI: 10.1039/d3tc03711h

maintained after long underwater immersion for 24 h. The introduction of lithium salts endowed the obtained CBPs with ionic conductivity, enabling it to exhibit excellent pressure and deformation sensing capabilities both in air and underwater. Moreover, the CBPs could be simply and rapidly recycled by solvents, and the performance did not degrade significantly after recycling many times. The CBPs prepared in this study have

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promising applications in the field of green flexible electronics and smart packaging in the future.

Introduction In recent years, the consumption of non-renewable resources by petroleum-based plastics and the difficulty of recycling waste have rapidly driven the development of green and sustainable materials. In this regard, the development of bioplastics that are simple to prepare, green, and recyclable shows fascinating promise and is considered to be an important part of the future circular economy.1–8 Bioplastics are currently produced on a scale of about millions of tons per year but still account for less than 1% of overall synthetic plastic production.9 The current first-generation bioplastics developed from starch, vegetable oils, etc. also face multiple challenges, including the impacts on agriculture, competition with food production, and higher costs.10 Due to their preparation from abundant cellulose stocks, wide availability, biodegradability, and recyclability, cellulose-based bioplastics (CBPs) have attracted extensive a

Nanjing Forestry University, Nanjing, Jiangsu, China Nanjing Forestry University, Jiangsu Co-innovation Center for Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab Pulp & Paper Science and Technology, Nanjing, China. E-mail: [email protected] c College of Light Industry and Food Science, Nanjing Forestry University, Nanjing 210037, China † Electronic supplementary information (ESI) available. See DOI: https://doi.org/ 10.1039/d3tc03711h b

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interest from researchers.11–18 CBPs are usually produced via, for example, direct blending/crossliking,11,12,19,20 chemical modification of cellulose,18,21 low-temperature alkali/urea system solubilization,22,23 or other solvent treatments.16,17,24 Although CBPs exhibit good overall performance, they are usually associated with hydrophilicity, a dark color or opaqueness, performance degradation upon recycling, and overall monofunctionality. Therefore, it is still highly desirable to endow CBPs with versatile properties, such as high transparency, hydrophobicity, mechanical robustness, ionic conductivity, and recyclability, preferably using facile and green methods. Deep eutectic solvents (DESs) have attracted much attention since they were first reported in 2003.25–29 DESs usually consist of hydrogen bond donors and acceptors, and the hydrogen bonding between the components reduces the melting point of the mixture, resulting in a clear and transparent state at room temperature. DESs can be used to regulate the overall physical and chemical properties of materials by changing the type of hydrogen bond donor and acceptor or by varying the molar ratio of the two. In lignocellulosic applications, DESs are often used as a green solvent for nanoprocessing, dissolution, and in situ graft modification.30–36 Lignocellulosic nanofibers or nanocellulose can also be used as physical cross-linking components for direct mixing in a DES to enhance its mechanical properties.37,38 DESs have also been used in the production of

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Paper bioplastics. For example, Xia et al.17 prepared a lignocellulosic bioplastic by a simple treatment of poplar wood powder with a DES, which showed high mechanical strength, biodegradability, and recyclability. Fang et al.16 further used a DES to treat dead leaves to prepare bioplastics. The preparation and processing of bioplastics using DESs is undoubtedly green, but it still faces problems with opacity and hydrophilicity of the end product. Herein, a series of novel supramolecular covalent CBPs was synthesized by taking advantage of the good compatibility between ethylcellulose (EC) and a hydrophobic DES (HDES). The prepared CBPs could essentially circumvent the disadvantages of water/moisture sensitivity, opacity/dark color, and monofunctionality, while its physicochemical properties could be comprehensively adjusted by changing the content of poly(HDES) in the network. The prepared CBPs exhibited excellent optical properties, mechanical flexibility/toughness, heat-sealing, and shape-memory functionality. The CBPs also exhibited excellent water resistance, maintaining a mechanical strength of up to B10 MPa after 24 h of underwater immersion. Moreover, the introduction of lithium salt endowed the CBPs with good ionic conductivity, which allowed it to be used in a flexible touchpad and for detecting external pressure/ deformation. In addition, the prepared CBPs have excellent closed-loop recyclability, and its overall performance did not degrade significantly after multiple cycles. The synthesis method proposed in this study will significantly expand the applications of CBPs.

Experimental Materials Ethyl cellulose (EC, CP), bistrifluoromethanesulfonimidate (LiTFSI, 99%), thymol (Thy, AR, 98%), coumarin (Cou, AR, 98%), ethylene glycol phenyl ether acrylate (EGPEA, 90%), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, 97%), and N,N-dimethylformamide (DMF, AR, 99.5%) were purchased from Shanghai Macklin Biochemical Co., Ltd and used as received. Preparation of polymerizable HDES The preparation of HDES was mainly based on the literature.39 Because the prepared HDES had good hydrophobicity and moderate viscosity, the Thy and Cou components were mixed in a 2 : 1 molar ratio. Typically, 6 g of Thy and 2.9 g of Cou were heated and stirred at 80 1C until a homogenous colorless solution was formed. Then, 7.69 g of EGPEA was added to the as-prepared Thy/Cou DES at 80 1C and stirred until a clear and transparent mixture was formed. The prepared polymerizable HDES was then stored in a vacuum desiccator for further use. Preparation of the CBPs First, a 5 wt% EC solution was prepared by dissolving EC in N,N-dimethylformamide (DMF) solvent. Then, HDES, EC solution, LiTFSI, and TPO were mixed homogeneously at a

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Journal of Materials Chemistry C certain mass ratio (details are shown in Table S1, ESI†) and heated at 60 1C for 12 h to ensure that the solvent evaporated thoroughly. Finally, the CBPs were obtained by irradiation with a UV light source (RW-UVA-F200U, Shenzhen Runwing Company, China) for 1 min. The light intensity was 20 mW cm 2 as measured by a UV radiometer (type UV-A, Photoelectric Instrument Factory, Beijing Normal University). Ionic conductivity The ionic conductivity (s) was measured on an electrochemical workstation (CHI600E) by electrochemical impedance spectroscopy (EIS) in the frequency range of 1–105 Hz. The sample was sandwiched between two copper tapes, and the ionic conductivity was calculated by s = L/(R  A), where L is the thickness of the elastomer, R is the bulk resistance, and A is the contact area between the two copper tapes. Sensing performances A CBP film with the dimensions 5 cm  5 cm  0.1 cm was closely attached on to the substrates. Copper tapes at both ends of the film were used to connect the film to the electrical signal test module (Keithley DMM7510 module, resistance mode). 3 M VHB Commercial tapes were used to fix the film. Characterization Differential scanning calorimetry (DSC) was performed using a 214 Polyma NETZSCH tester. The test was performed using two cycles to eliminate potential thermal residues. The test procedure involved heating the CBP sample (B5 mg) in an aluminum pan under nitrogen at 10 1C min 1 from room temperature to 80 1C and holding for 10 min, then cooling down from 80 1C to 80 1C and allowing to equilibrate for 15 mins. Following the procedure, the data were collected during the second heating from 80 1C to 80 1C. Fouriertransform infrared (FTIR) spectra were recorded using a Bruker Vertex 33 spectrometer. Real-time FTIR spectra were recorded using a NICOLET 6700 spectrometer. The amorphous phase of the prepared CBPs was analyzed using X-ray diffraction (Bruker D8 Advance). The water contact angle was measured using a JC2000D system (Zhongchen Digital Equipment Co., Ltd, Shanghai, China). Scanning electron microscopy (SEM) images were obtained using a HITACHI TM3030 Tabletop SEM instrument. Thermogravimetric analysis (TGA) was performed using a NETZSCH tester over a temperature range from 20 to 800 1C with a heating rate of 20 1C min 1 under a nitrogen atmosphere. The transmittance was measured using an Agilent Cary60 UV-Vis spectrophotometer. Tensile testing was performed using a tensile machine (INSTRON 5565, 100-N load cell). The strain rate was set to 10 mm min 1. The samples were cut into pieces with the dimensions of 50 mm  10 mm  0.1 mm. The surface morphologies of the samples on the microsubstrates were measured by tapping-mode atomic force microscopy (AFM; Bruker multimode 8) using tapping MPProtated cantilevers with silicon probes (model: RTESP, part MPP-11100–10). Visual images were taken using a Canon EOS

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Results and discussion

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Preparation and characterization of the CBPs The specific procedure for the preparation of supramolecular covalent CBPs is shown in Fig. 1. In the experiment, EC was first dissolved in DMF to form a 5 wt% solution. The HDES prepolymer was prepared by introducing small amounts of the photoinitiator TPO and LiTFSI (which imparted ionic conductivity, as will be discussed in detail later) into the Thy/Cou/ EGPEA solution. Because of the good compatibility between EC and HDES, a homogeneous network could be formed by a simple co-mixing. After solvent evaporation followed by rapid photopolymerization, the CBPs could be readily prepared. Depending on the amount of liquid HDES added during the preparation process, different samples were obtained, named CBP-x; for example, CBP-12 denoted that HDES made up 12% of the total mass of the system (Table S1, ESI†). The polymerization of the HDES monomer (EGPEA) in the CBP network was monitored by real-time FTIR spectroscopy. As shown in Fig. 2(a), the intensity of the CQC double bond peak at 1635 cm 1 increased rapidly with time, indicating the rapid polymerization. The real-time conversion ratio and rate of the CQC double bond also clearly reflected the rapid and efficient conversion of the monomer in the first 40 s, in which the final conversion ratio and maximum rate of the conversion were 94% and 12 S 1, respectively (Fig. 2(b) and (c)). Due to the homogeneous structure, light scattering was significantly reduced, resulting in a high optical transmittance

Paper of CBPs. The prepared CBPs exhibited an average transmittance of B92% in the visible range (Fig. 2(d) and (e)) and were virtually unaffected by variations in the compositional ratio and thickness (Fig. S1, ESI†). The prepared CBPs possessed mechanical flexibility and could be easily folded into complex shapes (Fig. S2, ESI†). Due to the abundant hydrophobic groups in the networks, the water contact angles of the CBPs were all above 901 (Fig. 2(f) and (g)). The XRD patterns showed that the CBPs had broad diffraction peaks near 2y E 221 indicating an overall amorphous structure. These features also provided the CBPs with good mechanical properties and flexibility. However, a small crystalline peak appeared at CBP-12 with a low poly(HDES) content, which may be related to the precipitation of lithium salts (Fig. 2(h)). The CBPs also possessed excellent thermal stability (Fig. 2(i)). With increasing temperature, the samples showed rapid mass loss in the range of 230–450 1C, which corresponded to the boiling point regions of thymol (B233 1C) and coumarin (B298 1C). In addition, the rate of mass loss accelerated significantly with increasing the poly(HDES) content in the CBP networks. Morphology and mechanical properties of the prepared CBPs The surface morphology of the prepared CBPs was characterized using SEM. As can be seen from Fig. 3(a)–(c), when a small amount of poly(HDES) was introduced into the EC network, due to insufficient contact between the components, some small aggregated particles appeared in CBP-12. This was consistent with the results obtained from the XRD spectra. However, as the poly(HDES) content increased, the CBP surface became wrinkled, which is typical when soft polymers dominate. With further increasing the poly(HDES) content, the CBP-16 surface

Fig. 1 Preparation of supramolecular covalent cellulose-based bioplastics (CBPs). EC/DMF solution (5 wt%), LiTFSI, HDES, and a small amount of photoinitiator TPO were mixed according to a certain ratio. After evaporating off the DMF solvent, the CBP was prepared by a rapid photopolymerization.

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Fig. 2 (a) Real-time FTIR spectrum of the EGPEA monomer. (b) CQC double bond conversion ratio and (c) polymerization rate of the EGPEA monomer. (d) Optical photograph of CBP, which exhibited a high optical transmittance. (e) Optical transmittance spectrum of CBP in the visible range, where the average transmittance was B92%. (f) Photograph of the water contact angle of CBP-14. (g) Contact angles of different CBPs, all of which were greater than 901. (h) and (i) XRD and TGA spectra of CBP.

showed more dense soft polymer chains, which was consistent with the results observed from the AFM phase diagram (Fig. S3, ESI†). The mechanical properties of the CBPs were tested using a universal tensile machine (Fig. 3(d)). The CBP-12 network exhibited a high tensile strength (B45 MPa) and small strain (B30%). When the proportion of soft poly(HDES) increased, the mechanical strength of the CBPs decreased but the deformation increased. The effect of the lithium salt content on the mechanical properties of the CBPs was also investigated. The mechanical strength of the CBPs significantly decreased with increasing lithium salt content (Fig. S4, ESI†). This was due to the interference of large-sized TFSI anions on the polymer chain stacking. To investigate the water resistance of the CBPs, CBP-14 was selected as a demonstration sample and its mechanical properties were measured by immersing it underwater for different times. As illustrated in Fig. 3(e), the mechanical strength of the

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CBPs showed a decreasing trend under continuous interaction with water molecules. It was worth noting that the CBPs maintained a relatively high mechanical strength (B15 MPa) even after 12 h underwater. Further increasing the immersion time, the mechanical strength of CBP-14 remained B10 MPa after up to 24 h (Fig. 3(f)). CBP-14 exhibited good heat-sealing properties. Folding CBP-14 and subsequent edge heating was used to prepare a transparent, hydrophobic, and robust bag that could easily withstand a load of B3 Kg without any breakage, deformation, or leakage (Fig. 3(g)). The CBPs also demonstrated a shapememory function. After twisting them into spiral shapes at room temperature and freezing at 23 1C for half an hour, they remained in the twisted spiral state (Fig. 3(h) and Fig. S5, ESI†). By comparison, it was found that pure EC almost maintained its initial shape after fixing the shape at 23 1C and then replacing it at room temperature for 1 min. However, with the introduction of poly(HDES), the CBPs showed a trend of shape

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Fig. 3 (a)–(c) Surface morphology of different CBPs. (d) Stress–Strain curves of different CBPs. (e) Stress–Strain curves of different CBPs after 6 h of underwater immersion. (f) Stress–Strain curves of CBP-14 after underwater immersion for different times. (g) CBP could be processed into a transparent hydrophobic and robust bag that could withstand B3 Kg by a heat-sealing process. (h) CBP exhibited shape-memory function. (i) DSC curve of CBP-14.

recovery. With the increase in poly(HDES) content, CBP-14 and CBP-16 with lower Tg rapidly recovered to the initial shape within 1 min (Fig. 3(i)). This was due to the fact that when the overall temperature of the CBPs was elevated above Tg, the hydrogen bonding within the CBPs weakened and the energy stored in the soft poly(HDES) was released, resulting in a fast recovery of the initial shape. For pure EC, the rigid chain segments made it difficult to recover the original shape because of the lack of soft poly(HDES). Electrical properties and sensing applications of the CBPs Considering its high ionic conductivity, electrochemical stability, and compatibility with the CBP network, LiTFSI was introduced as a conductive component to enhance its ionic conductivity. Li+ could be associated/dissociated with the poly(HDES)/EC component through Li+–O interaction. As shown in Fig. 4(a), a small bulb could be easily lit by connecting the CBPs in series into a circuit, indicating good conductivity. The electrical properties of the CBPs were evaluated using the

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electrochemical impedance spectrum, and the corresponding ionic conductivities were also calculated (Fig. 4(b) and (c)). The results showed that the electrical conductivity of the CBPs significantly improved with increasing the lithium salt content. Given the good transparency, mechanical toughness, hydrophobicity, and ionic conductivity, the CBPs are suitable for comprehensive sensor applications. As shown in Fig. 4(d), CBP14 could be used for a touchpad upon which a corresponding electrical signal could be obtained when writing the letter ‘‘O’’. Similar electrical signals were available when writing repeatedly, indicating that the CBP touchpad had excellent letter recognition capability. When continuous pressure or bending deformation (Movie S1, ESI†) was applied, repeatable electrical signals could be captured, demonstrating the good external pressure and deformation sensing ability (Fig. 4(e) and (f)). Surprisingly, a stable electrical signal could still be obtained by directly exposing the CBPs to an underwater environment and writing underwater (Fig. 4(g)). However, the resistance signal variation was relatively small because the water molecules facilitated

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Fig. 4 (a) CBP strip connected in series into a circuit could make a small light bulb glow, indicating good ionic conductivity. (b) Electrochemical impedance spectra of different CBPs. (c) Ionic conductivities of different CBPs. (d)–(f) Responses of the electrical signals generated by writing, pressing, and bending. (g)–(i) Changes in electrical signals generated when CBPs were written on, lifted up and down (from underwater to air), and bent underwater.

ionic transport to a certain extent. The effect of water molecules on the electrical signal was also verified by the sudden increase in the resistance signal when the CBP sensor was lifted from underwater in to the air (Fig. 4(h) and Movie S2, ESI†). When bending at different angles underwater, possibly influenced by water resistance, the change in the electrical signal was clearly distinguished from the signal peak in the air (Fig. 4(i)). In addition, recycling and reuse play a very important role in the future development of green electronics. It is encouraging to note that the CBPs exhibited good recyclability. As shown in Fig. S6 and S7 (ESI†), the CBPs could be quickly recycled by various solvents (e.g., DMF, dichloromethane, acetone, and ethyl acetate) at room temperature, and there was no significant degradation in the mechanical and electrical properties after multiple recycling (Fig. S8 and S9, ESI†). It is worth pointing out that compared with the CBPs reported so far, poly(HDES) regulated CBPs have comprehensive properties, such as excellent hydrophobicity, transparency, flexibility, stretchability, shape-memory function, heat sealability, underwater sensing capability, and recyclability (Fig. S10, ESI†).

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Conclusions In conclusion, a series of CBPs with excellent overall performance was developed by introducing poly(HDES) into the EC network. Due to the good compatibility among the components, the CBPs could be endowed with good optical transmittance, mechanical flexibility, and water resistance properties by modulating the component ratios. The CBPs still possessed a mechanical strength of B10 MPa even after underwater immersion for 24 h. By incorporating the conductive component LITFSI, the CBPs also had good ionic conductivity and could be used as a stable sensor in air and underwater, e.g., to recognize letters, pressures, deformations, and changes in the surrounding environment. The CBPs could be easily recovered by solvents at room temperature, and the properties of the recycled CBPs did not undergo significant changes. Overall, the prepared CBPs circumvented the problems of high hydrophilicity, poor transparency, monofunctionality, and recycling difficulties resulting from traditional preparation methods and thus provide a feasible solution for the future development of green flexible electronic materials.

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Conflicts of interest There are no conflicts to declare.

Acknowledgements

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This research was financially supported by China Postdoctoral Science Foundation (2022M711229), Opening Funding of National & Local Joint Engineering Research Centre for Mineral Salt Deep Utilization (contract No: SF202203) and the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (22KJB430029).

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