doi:10.11777/j.issn1000-3304.2019.19093

引用本文: 袁涛, 孙俊奇. 具有优异自恢复性能的高强度聚电解质复合物水凝胶[J]. 高分子学报. doi: 10.11777/j.issn1000-3304.2019.19093 shu

Citation: Tao Yuan and Jun-qi Sun. Polyelectrolyte Complexes-based Hydrogels with High Mechanical Strength and Excellent Self-recovery[J]. Acta Polymerica Sinica. doi: 10.11777/j.issn1000-3304.2019.19093 shu

具有优异自恢复性能的高强度聚电解质复合物水凝胶

袁涛 ,
孙俊奇 ^{,
,}

超分子结构与材料国家重点实验室吉林大学化学学院　长春 130012

通讯作者: 孙俊奇, E-mail: sun_junqi@jlu.edu.cn

摘要: 具有高力学强度和优异自恢复性能的水凝胶在组织工程、可拉伸电子器件及可穿戴设备等领域具有潜在的应用价值. 本工作通过将4-甲酰苯-1,3-二磺酸修饰的聚乙烯醇(SPVA)与线型聚乙烯亚胺(LPEI)在水溶液中复合，并经过塑形、干燥和水浸泡过程，制备了具有优异自恢复性能的高强度聚电解质复合物水凝胶. 凝胶中强的静电作用和弱的氢键作用的协同作用使该水凝胶具有高的断裂强度和韧性，其断裂强度和韧性可达 ~ 10.0 MPa和 ~ 14.21 MJ/m³. 该水凝胶被拉伸到200%后，室温下不需要任何外界刺激，在1 h内就可完全恢复其初始形状和力学性能.

关键词:

English

Polyelectrolyte Complexes-based Hydrogels with High Mechanical Strength and Excellent Self-recovery

Tao Yuan ,
Jun-qi Sun

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012

Corresponding author: Junqi Sun, E-mail: sun_junqi@jlu.edu.cn

Received Date: 2019-05-05
Accepted Date: 2019-07-13
Available Online: 2019-12-01

Abstract: Polymeric hydrogels with high mechanical strength and excellent self-recovery are useful in tissue engineering, stretchable electronics and wearable devices. In this work, polyelectrolyte complexes-based hydrogels with high mechanical strength and excellent self-recovery are fabricated by complexation of poly(vinyl alcohol) modified with benzaldehyde-2,4-disulfonic acid disodium salt (BADS) (denoted as SPVA) with linear poly(ethylenimine) (LPEI) in aqueous solution followed by molding, drying and rehydration. The mechanical properties of the LPEI_a/x%-SPVA_b hydrogels, where x% represents the molar ratio of BADS to the monomer molar ratio of PVA, and a and b represent the feed mass ratio of LPEI to SPVA, can be well-tailored by varying the parameters such as the grafting ratio of BADS on SPVA and mass ratio of LPEI to SPVA. Stress-strain measurements indicate that the LPEI₁/18%-SPVA₁ hydrogels have the highest mechanical strength, with a tensile strength of ~ 10.0 MPa and a toughness of ~ 14.21 MJ/m³. A piece of the LPEI₁/18%-SPVA₁ hydrogel strip with a width of 2 mm and thickness of 2 mm can sequentially withstand various deformations such as bending, knotting, and twisting, and can lift a 1 kg weight without any damage. Besides the electrostatic interactions between sulfonate groups of SPVA and protonated amine groups of LPEI, Fourier transform infrared spectroscopy confirms the existence of hydrogen-bonding interactions between hydroxyl and sulfonate groups on SPVA. The synergy of strong electrostatic interactions and weak hydrogen-bonding interactions endows the hydrogels with high mechanical strength and toughness. Moreover, the hydrogels can completely recover from a strain of 200% to their original shape and mechanical properties within 1 h rest at room temperature without any external assistance. The excellent self-recovery of the LPEI₁/18%-SPVA₁ hydrogels originates from the high elastic retraction of polymer chains arising from electrostatic interactions and the reversibility of sacrificial hydrogen-bonding interactions. The high mechanical strength and excellent self-recovery will make the hydrogels have potential applications in aspects such as load-bearing materials, actuators and stretchable electronics.

Key words:

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Figure 1. (a, b) Schematic illustration of the synthesis routes of SPVA (a) and LPEI (b); (c, d) ¹H-NMR spectra of 18%-SPVA (c) and LPEI (d) in D₂O

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Figure 2. Schematic illustration of the preparation process of the polyelectrolyte complexes-based hydrogels

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Figure 3. Digital photographs of the aqueous solutions of LPEI (a) and SPVA (b), and precipitates of LPEI/SPVA complexes before (c) and after (d) decanting the turbid supernatant (Inset in (d) is the LPEI/SPVA precipitates collected from the beaker.)

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Figure 4. (a) Stress-strain curves of the LPEI₁/x%-SPVA1 hydrogels with a fixed LPEI to x%-SPVA mass ratio of 1:1 but varied molar fractions of BADS in SPVA; (b) Stress-strain curves of the LPEI_a/18%-SPVA_b hydrogels with different LPEI to 18%-SPVA mass ratio; (c) Digital photographs of the LPEI₁/18%-SPVA₁ hydrogel (i) and the photographs to demonstrate the high strength and toughness of the LPEI₁/18%-SPVA₁ hydrogels: being bent, knotted, twisted, and holding up a weight of 1 kg (ii − v). The hydrogels in (c) has a width of 2 mm and a thickness of 1.5 mm.

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Figure 5. (a, b) FTIR spectra of BADS, PVA and 18%-SPVA in the ranges of 3750 − 800 and 1600 − 800 cm⁻¹. (c, d) Frequency dependence of the storage modulus G′ and loss modulus G″ (c) and Arrhenius plots for the shift factors (d) of the LPEI₁/18%-SPVA₁ hydrogels. The curves in (c) were processed based on the time-temperature superposition principle by horizontally shifting the individual curves corresponding to different temperatures toward the curve corresponding to the reference temperature of 25 °C. The apparent activation energy value (E_a) shown in (d) is calculated from the slopes of the curve

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Figure 6. Self-recovery and fatigue resistance of the LPEI1/18%-SPVA1 hydrogel: (a) digital photographs of LPEI1/18%-SPVA1 hydrogel before (i) and after (ii) being stretched, and recover to its initial state by relaxing at room temperature for 1 min (iii); (b) the fast recovery capability and (c) the recovery of elastic modulus and hysteresis loop at different resting time; (d) ten successive loading-unloading cycles of as-prepared and (e) recovered samples after resting for 12 h at room temperature (The online version is colorful.)

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Table 1. Summary of the mechanical properties of the LPEI_a/x%-SPVA_b hydrogels^*

Hydrogel abbreviations	Tensile strength (MPa)	Young’s modulus (MPa)	Strain at break (%)	Toughness (MJ/m³)
LPEI₁/10%-SPVA₁	5.1 ± 0.3	1.06 ± 0.18	605.4 ± 82.1	12.52 ± 0.32
LPEI₁/14%-SPVA₁	6.4 ± 0. 4	3.89 ± 0.26	450.3 ± 40.8	14.07 ± 0.52
LPEI₁/18%-SPVA₁	10.0 ± 0. 5	5.12 ± 0.33	385.1 ± 35.2	14.21 ± 0.58
LPEI₁/20%-SPVA₁	6.9 ± 0.4	16.41 ± 1.26	203.0 ± 30.3	6.81 ± 0.47
LPEI₁/18%-SPVA_0.67	2.7 ± 0.3	1.01 ± 0.12	438.9 ± 42.1	4.76 ± 0.32
LPEI₁/18%-SPVA_1.5	8.0 ± 0.5	6.08 ± 0.34	308.3 ± 25.2	10.47 ± 0.38
^*Measured at a stretching speed of 100 mm/min